Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/485—Direct positive emulsions
  • G03C1/48538—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure
  • G03C1/48546—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent
  • G03C1/48561—Direct positive emulsions non-prefogged, i.e. fogged after imagewise exposure characterised by the nucleating/fogging agent hydrazine compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/061—Hydrazine compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers

Definitions

• the present invention relates to a photographic light-sensitive material, and more particularly, to a silver halide photographic material having at least one layer containing a compound which is capable of releasing imagewise a fogging agent or a development accelerating agent.
• JP-A-57-150845 JP-A-59-50439 and JP-A-59-170840
• JP-A the term "JP-A” as used herein means an "unexamined published Japanese patent application”
• couplers which release a fogging agent upon a reaction with an oxidation product of a color developing agent are disclosed. It is further disclosed that the imagewise release of the fogging agents provides high contrast and accelerated development.
• a surface chemical sensitization treatment is often conducted, particularly in core shell type silver halide emulsions.
• the surface chemical sensitization is ordinarily required to stop in an appropriate degree for the purpose of preventing increases in the minimum density, decreases in sensi tivity, occurrence of pseudo images in highly exposed areas, and other problems caused by superfluous chemical sensitization.
• the surface chemical sensitizing nuclei formed are weak as compared with those formed in conventional negative type photographic materials and their stability over time is extremely poor.
• a high contrast negative photographic material which is sufficiently high contrast and has a high maximum density with reduced amounts of black spots can be obtained.
• an object of the present invention is to provide a silver halide photographic material which has a high contrast.
• Another object of the present invention is to provide a silver halide photographic material which may be developed quickly and may be processed rapidly.
• Still another object of the present invention is to provide a silver halide photographic material which has a high sensitivity.
• a further object of the present invention is to provide a direct positive color light-sensitive material which provides a direct positive image having a high maximum image density and a high resolving power.
• a still further object of the present invention is to provide a direct positive color light-sensitive material which has excellent preservability, particularly under high temperature and high humidity conditions.
• a still further object of the present invention is to provide a direct positive color light-sensitive material which can form a direct positive image having a sufficiently high color density even when it is processed with a stable developing solution having a low pH.
• a silver halide photographic material comprising a support having thereon at least one light-sensitive silver halide emulsion layer, wherein the silver halide photographic material contains at least one compound represented by the following general formula (I): wherein A, and A 2 each represents a hydrogen atom or one of them represents a hydrogen atom and the other represents a sulfonyl group or wherein Ro represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group or an aryloxy group; and t represents 1 or 2); Time represents a divalent linking group; t represents 0 or 1; FA represents a moiety of a nucleating agent or a development accelerating agent; V represents a carbonyl group, a sulfonyl group, a sulfoxy group, (wherein R represents an alkoxy group or an aryloxy group), an iminomethylene group or a thiocarbonyl group; and R represents an ali
• A1 and A 2 each represents a hydrogen atom, an alkylsulfonyl or arylsulfonyl group having at most 20 carbon atoms (preferably a phenylsulfonyl group or a phenylsulfonyl group substituted such that the sum of the Hammett's substituent constants is at least -0.5). or (wherein R o represents a straight chain, branched chain or cyclic alkyl group or alkenyl group preferably having at most 30 carbon atoms.
• an aryl group preferably a phenyl group or a phenyl group substituted such that the sum of the Hammett's substituent constants is at least -0.5
• an alkoxy group for example, ethoxy
• an aryloxy group preferably a monocyclic aryloxy group
• a 2 groups may be substituted with one or more substituents selected from an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group, a ureido group, a urethane group, an aryloxy group.
• a sulfamoyl group a carbamoyl group, an alkylthio group, an arylthio group, a sulfonyl group, a sulfinyl group, a hydroxyl group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, and a nitro group, and these substituents may be further substituted.
• the sulfonyl group represented by A. or A 2 preferably represents one which is specifically described in U.S. Patent 4,478.928.
• a or A 2 may be connected with Time. R or V which is defined hereinafter to form a ring, if desired.
• A. and A 2 are most preferably hydrogen atoms.
• Time represents a divalent linking group and may have a timing control function, and t represents 0 or 1.
• t 0 or 1.
• FA is directly connected to V.
• Time represents a group which releases FA through one or more reaction stages from Time-FA which has been released from an oxidation product of the oxidation-reduction mother nucleus.
• the divalent linking groups represented by Time include, for example, those capable of releasing a photographically useful group (hereinafter simply referred to as "PUG") upon an intramolecular ring-closing reaction of a p-nitrophenoxy derivative as described, for example, in U. S. Patent 4,248,962 (JP-A-54-145135); those capable of releasing PUG upon an intramolecular ring-closing reaction after the ring cleavage as described, for example, in U.S.
• PUG photographically useful group
• Patents 4,310,612 JP-A-55-53330 and 4.358.525; those capable of releasing PUG accompanied with the formation of an acid anhydride upon an intramolecular ring-closing reaction of a carboxy group of succinic acid mono-ester or analogues thereof as described, for example. in U.S. Patents 4,330.617, 4.446,216 and 4.483,919 and JP-A-59-121328; those capable of releasing PUG accompanied with the formation of quinon-monomethide or analogues thereof upon electron transfer via conjugated double bonds of an aryloxy group or a heterocyclic oxy group as described, for example, in U.S.
• Patent 4,420,554 JP-A-57-136640), JP-A-57-135945, JP-A-57-188035, JP-A-58-98728 and JP-A-58-209737; those capable of releasing PUG upon an intramolecular ring-closing reaction of an oxy group formed by electron transfer to a carbonyl group which is conjugated with a nitrogen atom in a nitrogen-containing hetero ring as described, for example, in JP-A-57-56837; those capable of releasing PUG accompanied with the formation of an aldehyde as described, for example, in U.S.
• Patent 4,146,396 JP-A 52-90932), JP-A-59-93442 and JP-A-59-75475; those capable of releasing PUG accompanied with decarboxylation of a carboxy group as described, for example, in JP-A-51-146828, JP-A-57-179842 and JP-A-59- 104641; those capable of releasing PUG accompanied with the formation of an isocyanate as described, for example, in JP-A-60-7429; and those capable of releasing PUG upon a coupling reaction with an oxidation product of a color developing agent as described, for example, in U.S. Patent 4,438,193.
• Time may be composed of a combination of two or more divalent linking groups (for example. those represented by the general formulae (T-1) to (T-10) described hereinafter).
• Preferable divalent timing groups represented by Time in the general formula (I) include those represented by the following general formulae (T-1) to (T-10) wherein the symbol ( * ) denotes the position at which V is bonded, and the symbol (") denotes the position at which FA is bonded.
• Preferable timing groups also include those represented by combining two or more groups represented by the formulae.
• ( * )-Q 1 represents ( * )-0-, (*)-O-CH 2 -O-, (*)-O-CH 2 -, (*)-O-CH 2 -S-, wherein R t1 represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group;
• X 1 represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, -0-R t2 , -S-R t2 , -CO-R t2 , -SO-R t2 , a cyano group, a halogen atom (e.g., fluorine, chlorine, bromine or iodine) or a nitro group, wherein R t2 and R t3 , which may be the same or different, each has the same meaning as defined for R t1 ; X 2 has the same meaning as defined for R t1 ; q represents an integer of from 1
• ( * )-Q 3 represents ( * )-0-, (*)-O-CH 2 -O- or (*)-O-CH 2 -S-; and R t1 , R t2 , R t3 , X 1 and q each has the same meaning as defined for the general formula (T-1).
• T-4 An example of the group represented by the general formula (T-4) is the timing group as described in U.S. Patent 4,409,323.
• (*)-Q 3 , R t2 , R t3 , X and q each has the same meaning as defined for the general formula (T-4).
• X 3 represents an atomic group which contains at least one atom selected from the group consisting of carbon, nitrogen, oxygen and sulfur and which is necessary to form a 5-membered, 6-membered or 7- membered heterocyclic ring, which may be further condensed with a benzene ring or a 5-membered, 6- membered or 7-membered heterocyclic ring.
• preferable heterocyclic rings include pyrrole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, pyridine, pyridazine, pyrimidine, pyrazine, azepin, oxepin, indole, benzofuran, and quinoline.
• (*)-Q 3 , Xi, q, R t2 and R t3 each has the same meaning as defined for the general formula (T-4).
• T-6 An example of the group represented by the general formula (T-6) is the timing group as described in British Patent 2,096,783.
• X 4 represents an atomic group which contains at least one atom selected from the group consisting of carbon, nitrogen, oxygen and sulfur and which is necessary to form a 5-membered, 6-membered or 7- membered heterocyclic ring, which may be further condensed with a benzene ring or a 5-membered. 6- membered or 7-membered heterocyclic ring.
• Xg represents an atomic group which contains at least one atom selected from the group consisting of carbon, nitrogen, oxygen, and sulfur and which is necessary to form a 5-membered. 6-membered or 7- membered heterocyclic ring, which may be further condensed with a benzene ring or a 5-membered. 6- membered or 7-membered heterocyclic ring.
• preferable heterocyclic rings include pyrrolidine. piperidine and benzotriazole besides those described for the general formula (T-6).
• X 1 , X 2 , q and r each has the same meaning as defined for the general formula (T-1).
• X 10 has the same meaning as X 9 defined for the general formula (T-8);
• (*)-Q 3 has the same meaning as defined for the general formula (T-4); and
• u' represents 0 or 1.
• Examples of preferable heterocyclic rings for X 10 are as follows.
• X 1 and q each has the same meaning as defined for the general formula (T-1); and X 11 represents a hydrogen atom, an aliphatic group, and aromatic group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a sulfamoyl group, a heterocyclic group, or a carbamoyl group.
• X 1 and X 2 each has the same meaning as defined for the general formula (T-1);
• (*)-Q 3 has the same meaning as defined for the general formula (T-4); and
• u has the same meaning as defined for the general formula (T-3) and is preferably 1 or 2.
• the aliphatic group when X 1 , X 2 , R t1 , R t2 , R t3 and R t4 contain a portion of an aliphatic group, the aliphatic group preferably has from 1 to 20 carbon atoms and may be saturated or unsaturated, substituted or unsubstituted, straight chain, branched chain or cyclic.
• the aromatic group has from 6 to 20 carbon atoms, preferably from 6 to 10 carbon atoms, and is more preferably a substituted or unsubstituted phenyl group.
• the heterocyclic group is a 5-membered or 6-membered heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom.
• Examples of preferable heterocyclic groups include a pyridyl group, a furyl group, a thienyl group, a triazolyl group, an imidazolyl group, a pyrazolyl group, a thiadiazolyl group, an oxadiazolyl group and a pyrrolidinyl group.
• FA represents a moiety of a so-called nucleating agent which acts on silver halide grains to form fog nuclei capable of initiating development at the time of development, or a development accelerating agent.
• Suitable examples of FA include a group which acts reductively on silver halide grains to form fog nuclei at the time of development or a group which acts on silver halide grains to form silver sulfide nuclei which are fog nuclei capable of initiating development.
• FA include groups containing a group capable of adsorbing silver halide grains and being represented by the following general formula: AD-(L)m-X wherein AD represents a group capable of adsorbing silver halide grains; L represents a divalent group; m represents 0 or 1; and X represents a reducing group or a group capable of acting on silver halide to form silver sulfide.
• X when X is a group capable of acting on silver halide to form silver sulfide, X may also have the function of AD. In such a case, AD-(L) m - is not always necessary.
• AD may be directly connected to Time, or L or X may be connected to Time so long as it is capable of being released from Time.
• Examples of the group capable of adsorbing silver halide grains represented by AD include nitrogen-containing heterocyclic groups containing dissociable hydrogen atoms (e.g., pyrrole, imidazole, pyrazole, triazole, tetrazole, benzimidazole, benzopyrazole, benzotriazole, uracil, tetraazaindene, imidazotetrazole, pyrazolotriazole, or pentaazaindene), heterocyclic groups containing at least one nitrogen atom and other hetero atoms such as an oxygen atom, a sulfur atom and a selenium atom in its rings (e.g., oxazole, thiazole, thiazoline, thiazolidine, thiadiazole, benzothiazole, benzoxazole, or benzoselenazole), heterocyclic groups containing mercapto groups (e.g., 2-mercaptobenzothiazole, 2-mercap
• the group represented by X includes a group derived from reducing compounds (e.g.. hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phenylenediamine, 1-phenyl-3-pyrazolidinone, enamine, aldehyde, polyamine, acetylene, aminoborane, tetrazolium salts, quaternary salts such as ethylenebispyridinium, or carbazinic acid), compounds capable of forming silver sulfide at the time of development (e.g., thiourea, thioamide, dithiocarbamate, rhodanine, thiohydantoin. thiazolidinethione, and other compounds containing a partial structure
• reducing compounds e.g.. hydrazine, hydrazide, hydrazone, hydroquinone, catechol, p-aminophenol, p-phen
• some groups capable of forming silver sulfide at the time of development are themselves capable of adsorbing silver halide grains and therefore may serve as the above-described adsorptive group. i.e., AD.
• Particularly preferred groups of FA are those represented by the following general formulae (II), (III) or (IV): wherein R 2 . and R 3 , each represents an acyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group or a sulfamoyl group; R 22 and R 32 each represents a hydrogen atom, an acyl group, a sulfonyl group, an alkoxycarbonyl group or an aryloxycarbonyl group; R 23 and R 33 each represents a hydrogen atom, an alkoxy group, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a carbonamido group or a sulfonamido group; m represents an integer of from 0 to 4, and when
• R 2 , and R 3 each represents an acyl group (e.g., formyl, acetyl, propionyl, trifluoroacetyl, or pyruvoyl), a carbamoyl group (e.g., N,N-dimethylcarbamoyl), an alkylsulfonyl group (e.g., methanesulfonyl), an arylsulfonyl group (e.g., benzenesulfonyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl group) or a sulfamoyl group (e.g., methylsulfamoyl), R 22 and R 32 each represents a hydrogen atom, an acyl group (e.g., trifluoroacetyl), a sulfonyl group
• Z represents a non-metallic atomic group necessary for forming a substituted or unsubstituted 5- membered or 6-membered heterocyclic ring
• R41 represents a substituted or unsubstituted aliphatic group
• R 42 represents a hydrogen atom, a substituted or unsubstituted aliphatic group or a substituted or unsubstituted aromatic group, or R 42 may be connected with Z to form a ring; provided that at least one of R 41 , R 42 and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R 41 and R 42 are connected with each other to form a 6-membered dihydropyridinium ring; Y represents a counter ion required for charge balance; and n represents 0 or 1.
• the heterocyclic ring formed by Z includes, for example, quinolinium, benzothiazolium, benzimidazolium, pyridinium, thiazolinium, thiazolium, naphthothiazolium, selenazolium, benzoselenazolium, imidazolium, tetrazolium, indolenium, pyrrolinium, acridinium, phenanthridium, isoquinolinium, oxazolium, naphthoxazolium and benzoxazolium nuclei.
• the group Z may be substituted, and the substituents therefore include, for example, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an alkynyl group, a hydroxyl group, an alkoxy group, an aryloxy group, an amino group, an alkylthio group, an arylthio group, an acyloxy group, an acylamino group, a sulfonyl group, a sulfonyloxy group, a sulfonylamino group, a carboxyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, a ureido group, a urethane group, a carbonic acid ester group, a hydrazine group, a hydrazone group, an imino group, and a halogen atom.
• Z may be substituted with at least one substituent selected from the above-mentioned substituents, and when Z is substituted with two or more substituents, the plural substituents may be same or different.
• the substituents may be further substituted with any other substituents, for example, those described above.
• substituents for Z include a heterocyclic quaternary ammonium group formed by Z via the connecting group L.
• the general formula (IV) forms a bis compound.
• Preferred heterocyclic rings formed by Z include quinolinium, benzothiazolium, benzimidazolium, pyridinium, acridinium, phenanthridium and isoquinolinium nuclei. More preferably, the rings are quinolinium, benzothiazolium and benzimidazolium nuclei, and especially preferably they are quinolinium and benzothiazolium nuclei. Most preferably the ring is a quinolinium nucleus.
• the aliphatic group represented by R 41 or R 42 includes an unsubstituted alkyl group having from 1 to 18 carbon atoms or a substituted alkyl group in which the alkyl moiety has from 1 to 18 carbon atoms.
• substituents for the alkyl group those described for Z above are included.
• the aromatic group represented by R 42 includes those having from 6 to 20 carbon atoms, which may be, for example, a phenyl group or a naphthyl group.
• the aromatic group may optionally be substituted, and as substituents for the aromatic group, those described for Z above are included.
• At least one of R 41 , R 42 and Z contains an alkynyl group, an acyl group, a hydrazine group or a hydrazone group, or R 41 and R 42 form a 6-membered ring to complete a dihydropyridinium nucleus. These may also be substituted, and as substituents for the groups, those described for Z above are included.
• the hydrazine group is particularly preferably substituted with an acyl group or a sulfonyl group.
• the hydrazone group is particularly preferably substituted with an aliphatic group or an aromatic group.
• the acyl group is preferably a formyl group or an aliphatic or aromatic ketone residue.
• the alkynyl group preferably has from 2 to 18 carbon atoms, and includes. for example, an ethynyl group, propargyl group, a 2-butynyl group. a 1-methylpropargyl group, a 1.1-dimethylpropargyl group, a 3-butynyl group, and a 4-pentynyl group.
• the alkynyl group may be substituted, and as the substituents for this group, those described for Z above are included. For example, there may be described a 3- phenylpropargyl group, a 3-methoxycar- bonylpropargyl group and a 4-methoxy-2-butynyl group.
• At least one substituent on the group or ring represented by R 41 , R 42 or Z is preferably an alkynyl group or an acyl group, and it is also preferred that R 41 and R 42 are connected with each other to form a dihydropyridinium nuclei. Most preferably, at least one alkynyl group is substituted on the group or ring represented by R 41 , R 42 or Z.
• R 41 is a propargyl group.
• the counter ion Y for charge balance may be any anion to neutralize the positive charge caused by the quaternary ammonium salt in the heterocyclic ring, and it may be a bromide ion.
• n is 1.
• the heterocyclic quaternary ammonium salt in the general formula contains an anion substituent such as a sulfoalkyl substituent, the salt may be in the form of a betain.
• Y is a cationic pair ion, which may be. for example. an alkali metal ion (e.g., a sodium ion, or a potassium ion), or an ammonium ion (e.g., a triethylammonium ion).
• alkali metal ion e.g., a sodium ion, or a potassium ion
• ammonium ion e.g., a triethylammonium ion
• V represents a carbonyl group a sulfonyl group, a sulfoxy group.
• R. represents an alkoxy group or an aryloxy group
• an iminomethylene group or a thiocarbonyl group and preferably represents a carbonyl group.
• the aliphatic group represented by R in the general formula (I) includes a straight chain. branched chain or cyclic alkyl group. alkenyl group or alkynyl group, each containing preferably from to 30 carbon atoms, more preferably from 1 to 20 carbon atoms.
• the branched chain alkyl group may contain one or more hetero atoms therein to form a saturated hetero ring.
• the aliphatic group examples include a methyl group, a tert-butyl group. an n-octyl group. a tert-octyl group, a cyclohexyl group, a hexenyl group, a pyrrolidyl group, a tetrahydrofuryl group and an n-dodecyl group.
• the aromatic group represented by R includes a monocyclic or dicyclic aryl group. for example, a phenyl group or a naphthyl group.
• the heterocyclic group represented by R includes a 3-membered to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and which may be a monocyclic ring or may form a condensed ring together with an aromatic ring or a heterocyclic ring.
• a 5-membered or 6-membered aromatic heterocyclic group is preferred.
• heterocyclic group examples include a pyridyl group, an imidazolyl group, a quinolinyl group, a benzimidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group, a benzothiazolyl group and a thiazolyl group.
• the group represented by R may be substituted with one or more substituents.
• substituents include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amino group, an acylamino group, a sulfonylamino group. a ureido group, a urethane group, an aryloxy group, a sulfamoyl group, a carbamoyl group, an alkylthio group.
• a ballast group which is conventionally employed in immobile photographic additives such as couplers, or a group which is capable of accelerating the adsorption of the compound represented by the general formula (I) onto silver halide may be incorporated into R or (TimehFA of the general formula (I).
• the ballast group is an organic group which provides a molecular weight sufficient to substantially prevent the compound represented by the general formula (I) from diffusing into other layers or processing solutions and includes, for example, alkyl, aryl, heterocyclic, ether, thioether, amido, ureido, methane, and sulfonamido groups or a combination of two or more thereof.
• the ballast group is preferably contains a substituted benzene ring, and more preferably contains a benzene ring substituted with a branched alkyl group.
• the adsorption accelerating group for silver halides includes specifically a cyclic thioamido group, for example, 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydantoin, rhodanine, thiocarbituric acid, tetrazoline-5-thione, 1,2,4-triazoline-3-thione, oxazoline-2-thione, benzimidazoline-2-thione, benzoxazoline-2-thione, benzothiazoline-2-thione, thiotriazine and 1,3-imidazoline-2-thione, a chain thioamido group, an aliphatic mercapto group, an aromatic mercapto group, a heterocyclic mercapto group (when the atom adjacent to the carbon atom bonded to the -SH group is a nitrogen atom, the mercapto group is the same as a cyclic thioamide group which is in a tautomeric
• the adsorption accelerating groups may be further substituted with one or more appropriate substituents.
• the substituents can be selected from those described for R above.
• the FA compounds can be synthesized by the methods as described. for example, in the patents cited in Research Disclosure No. 22534 (January, 1983), pages 50 to 54, U.S. Patent 4,471,044. JP-A-57-150845. JP-A-59-157638 and JP-A-59-170840 or by methods which are similar to these methods.
• Compound (1) can be synthesized along the route shown below.
• the compound represented by the general formula (I) according to the present invention can be incorporated into a silver halide emulsion layer or other hydrophilic colloid layer to achieve the desired purpose.
• the amount of the compound to be added may be varied depending on the kind of photosensitive material, but is from 10- 9 to 10' mol, preferably from 10- 7 to 10- 2 mol, per mol of silver halide.
• any known method for example, the method as described in U.S. Patent 2.322.027, can be employed.
• the compound is first dissolved in a solvent, such as an alkyl phthalate (e.g., dibutyl phthalate, dioctyl phthalate), a phosphate (e.g., diphenyl phosphate. triphenyl phosphate.
• a solvent such as an alkyl phthalate (e.g., dibutyl phthalate, dioctyl phthalate), a phosphate (e.g., diphenyl phosphate. triphenyl phosphate.
• tricresyl phosphate dioctylbutyl phosphate
• a citrate e.g., tributyl acetylcitrate
• a benzoate e.g., octyl benzoate
• an alkylamide e.g., diethyllaurylamide
• a fatty acid ester e.g., dibutoxyethyl succinate. diethyl azelate
• trimesate e.g., tributyl trimesate
• an organic solvent having a boiling point of from about 30 C to about 150 ⁇ C such as a lower alkyl acetate (e.g., ethyl acetate.
• JP-B-51-39853 the term "JP-B” as used herein means an "examined Japanese patent publication”
• JP-A-51-59943 may also be employed.
• any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used.
• the silver halide grains in the photographic emulsion may be regular grains having a regular crystalline form such as a cubic, octahedral or tetradecahedral crystalline form, or irregular grains having an irregular crystalline form such as a spherical crystalline form or having a crystal defect such as a twin plane. or may also be grains having a composite form of these crystalline forms. In addition, a mixture of grains with various crystalline forms may be used.
• the grains may be fine grains having a grain size of about 0.1 u.m or less or may be large grains having a grain size, as a diameter of the projected area. of up to about 10 u.m.
• the emulsion may be either a monodispersed emulsion having a narrow grain size distribution or a polydispersed emulsion having a broad grain size distribution.
• the silver halide photographic emulsion for use in the present invention can be prepared by any conventional method, for example, in accordance with the methods as described, for example, in Research Disclosure, Vol. 176, No. 17643 (December, 1978), pages 22 to 23, "I. Emulsion Preparation and Type" and ibid., Vol. 187, No. 18716 (November, 1979). page 648.
• the photographic emulsions for use in the present invention can also be prepared in accordance with the methods as described, for example, in P. Glafkides, Chemie et Physique Photographique (published by Paul Montel, 1967); G.F. Duffin, Photographic Emulsion Chemistry (published by Focal Press, 1966): V.L. Zelikman et al., Making and Coating Photographic Emulsion (published by Focal Press, 1954). More specifically, the silver halide emulsion may be prepared by an acid method, a neutral method, or an ammonia method. Also, as a method of reacting a soluble silver salt and soluble halide(s), a single jet method, a double jet method, or a combination thereof may be used.
• a reverse mixing method capable of forming silver halide grains in the presence of excess silver ions can also be employed.
• a controlled double jet method of keeping a constant pAg in a liquid phase for forming silver halide grains can also be employed. According to the method, a silver halide emulsion containing silver halide grains having a regular crystal form and almost uniform grain sizes can be obtained.
• the silver halide emulsion for use in the present invention can be physically ripened in the presence of a known silver halide solvent (for example, ammonia or potassium thiocyanate, as well as the thioethers and thione compounds as described, for example, in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 and JP-A-54-155828. According. to this method, a silver halide emulsion containing silver halide grains having a regular crystal form and almost uniform grain sizes can also be obtained.
• a known silver halide solvent for example, ammonia or potassium thiocyanate, as well as the thioethers and thione compounds as described, for example, in U.S. Patent 3,271,157, JP-A-51-12360, JP-A-53-82408, JP-A-53-144319, JP-A-
• the above-described silver halide emulsion containing regular crystal grains may be obtained by properly controlling the pAg value and the pH value in the formation of the grains.
• the details are described, for example, in Photographic Science and Engineering, Vol. 6, pages 159 to 165 (1962), Journal of Photographic Science, Vol. 12, pages 242 to 251 (1964), U.S. Patent 3,655,394 and British Patent 1,413,748.
• an emulsion in which the silver halide grains have a mean grain size (diameter) larger than about 0.05 u.m and at least 95% by weight of the grains have a grain size falling within the range of the mean grain size ⁇ 40% is typical.
• an emulsion in which the silver halide grains have a mean grain size of from 0.15 to 2 u.m and at least 95% by weight or by number of the grains have a grain size falling within the range of the mean grain size ⁇ 20% can also be used. The method of preparing such emulsions is described, for example, in U.S.
• Patents 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferably used.
• tabular grains having an aspect ratio of 5 or more may be used in the present invention.
• Tabular grains can easily be prepared by the methods as described, for example, in Gutoff, Photographic Science and Engineering, Vol. 14, pages 248 to 257 (1970); U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439.520 and British Patent 2,112,157.
• Tabular grains are preferably used since the covering power of the emulsion is increased and the spectral sensitizing efficiency by sensitizing dyes is elevated, and the details thereof are described in the aforesaid U.S. Patent 4,434,226.
• a sensitizing dye or an additive can be added to the grains so as to properly control the crystal form of the grains formed.
• the crystal structure of the grains may be uniform, or the inner part and the outer part of the grain may have different halogen compositions.
• the grain may also have a stratified structure.
• These emulsion grains are illustrated, for example, in British Patent 1,027,146, U.S. Patents 3,505,068 and 4,444,877 and JP-A-60-143331.
• Silver halides of different compositions may be combined by epitaxial junction, or the grains may also be combined with any compounds other than silver halides, such as silver thiocyanate or lead oxide, by a junction structure.
• the emulsion grains of this type are illustrated, for example, in U.S. Patents 4,094,684, 4,142,900 and 4,459,353, British Patent 2,038,792, U.S. Patents 4,349,622, 4,395,478, 4,433,501, 4,463,087, 3,656,962 and 3,852,067 and JP-A-59-162540.
• internal latent image type grains formed by surface chemical ripening of silver halide grains to give a light-sensitive nucleus (e.g., Ag 2 S, Agn (wherein n is an integer of 1 or more), Au) in the grain crystal and then growing a silver halide phase around the grains can also be used in the present invention.
• a light-sensitive nucleus e.g., Ag 2 S, Agn (wherein n is an integer of 1 or more), Au
• the silver halide grains may also be formed or physically ripened in the presence of a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof.
• the various kinds of emulsions may be surface latent image type emulsions which form a latent image mainly on the surface of the grain or internal latent image type emulsions which form a latent image mainly in the inside of the grain.
• the emulsion may also be a direct reversal emulsion.
• the direct reversal emulsion may be any of a solarization type, an internal latent image type, a light fogging type or a nucleating agent-containing type, or a combination thereof.
• a non-previously fogged internal latent image type emulsion be used, and this is fogged with a light before or during photographic processing, or a nucleating agent is used to obtain a direct positive photographic light-sensitive material.
• the non-previously fogged internal latent image type silver halide emulsion for use in the present invention is such that the surface of the silver halide grain is not previously fogged and a latent image is formed mainly in the inside of the grain.
• the term "internal latent image" emulsion as used herein is an emulsion defined as follows. A silver halide emulsion in a certain amount is coated on a transparent support and this is exposed to a light for a fixed period of time of from 0.01 to 10 seconds. Then this is developed with the following Developer (A) (internal developer) for 6 minutes at 20° C and the maximum density obtained is measured by a conventional photographic densitometric method.
• Developer internal developer
• a second portion of the same silver halide emulsion is coated in the same amount on another transparent support and then exposed in the same manner. This is then developed with the following Developer (B) (surface developer) for 5 minutes at 18° C and the maximum density obtained is also measured in the same manner.
• Developer (B) surface developer
• the former maximum density is at least five times larger than the latter maximum density, and more preferably, the former is at least ten times larger than the latter.
• Illustrative examples of the internal latent image type emulsion include conversion type silver halide emulsions as described, for example, in British Patent 1,011,062 and U.S. Patents 2.592.250 and 2,456.943, as well as core shell type silver halide emulsions.
• core shell type silver halide emulsions are described, for example, in JP-A-47-32813, JP-A-47-32814, JP-A-52-134721, JP-A-52-156614, JP-A-53-60222, JP-A-53-66218, JP-A-53-66727, JP-A-55-127549, JP-A-57-136641, JP-A-58-70221.
• JP-A-59-208540 JP-A-59-216136, JP-A-60-107641.
• the emulsion may be subjected to noodle washing, flocculation precipitation or ultrafiltration.
• the emulsion for use in the present invention is, in general, physically ripened, chemically ripened or spectrally sensitized.
• the additives usable in the ripening steps are described in the above Research Disclosure, No. 17643 (December, 1978) and ibid.. No. 18716 (November, 1979), and the relevant parts are listed in the following Table.
• Color couplers are compounds which can react with the oxidation product of an aromatic primary amine color developing agent by a coupling reaction to form or release a substantially non-diffusible dye, and the color couplers themselves are preferably substantially non-diffusible compounds.
• Specific examples of useful color couplers include naphthol or phenol compounds, pyrazolone or pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Examples of cyan, magenta and yellow couplers for use in the present invention are described in Research Disclosure No. 17643 (December, 1978), page 25, VII-D, ibid., No. 18717 (November, 1979) and Japanese Patent Application No. 61-32462, as well as in the publications cited therein.
• the yellow couplers for use in the present invention include oxygen atom releasing type or nitrogen atom releasing type 2-equivalent yellow couplers as typical examples.
• a-pivalo ylacetanilide couplers are excellent in fastness, especially light fastness of the dyes formed, while ⁇ -benzoylacetanilide couplers are excellent in color density.
• the 5-pyrazolone magenta couplers which may be preferably used in the present invention include 5-pyrazolone couplers in which the 3-position is substituted with an arylamino group or an acylamino group (especially sulfur atom releasing type 2-equivalent couplers).
• pyrazoloazole couplers and the pyrazolo[5,1-c][1,2,4]triazoles as described in U.S. Patent 3,725,067 are especially preferred among them.
• the imidazo[1,2-b]pyrazoles as described in U.S. Patent 4,500,630 are more preferred from the view point of the small yellow side- absorption and the high light-fastness of the dyes formed, and the pyrazolo[1,5-b][1,2,4]triazoles as described in U.S. Patent 4,540,654 are particularly preferred.
• the cyan couplers which can preferably be used in the present invention include the naphthol and phenol couplers as described, for example, in U.S. Patents 2,474,293 and 4,052,212, and the phenol cyan couplers having an alkyl group of two or more carbon atoms at the meta-position of the phenol nucleus as described in U.S. Patent 3,772,002.
• 2,5-diacylamino-substituted phenol couplers are also preferred from the viewpoint of the fastness of the color images formed.
• Couplers for correcting any unnecessary absorption of the dyes formed in a short wavelength range couplers forming dyes with an appropriate diffusibility, colorless couplers, DIR couplers which release a development inhibitor upon a coupling reaction and polymerized couplers can also be used in the present invention.
• the standard amount of the color coupler for use in the present invention is from 0.001 to 1 mol per mol of the light-sensitive silver halide.
• the amount is from 0.01 to 0.5 mol for a yellow coupler; it is from 0.03 mol to 0.3 mol for a magenta coupler; and it is from 0.002 mol to 0.3 mol for a cyan coupler.
• a color forming enhancing agent can be used in the present invention so as to improve the color forming property of the couplers used. Specific examples of such compounds are those described in JP-A-62-215272.
• the coupler is first dissolved in a high boiling point organic solvent and or a low boiling point organic solvent and then emulsified and dispersed in gelatin or other aqueous hydrophilic colloid solution by high speed stirring with a homogenizer or the like. or by mechanical milling with a colloid mill or the like, or by means of an ultrasound technique, and the resulting dispersion is added to the intended emulsion layer.
• the high boiling point organic solvent is not always necessary but the compounds as described in JP-A-62-215272 are preferably used.
• the couplers according to the present invention can be dispersed in a hydrophilic colloid by the method as described in JP-A-62-215272.
• the photographic material of the present invention preferably contains one or more compounds capable of reacting with formaldehyde gas to fix the same, which are described in detail hereunder.
• the compounds capable of reacting with formaldehyde gas to fix the same are those represented by the following general formulae (SI) or (SII), which have a relative molecular weight of 300 or less per one unit of the active hydrogen in the molecule.
• the relative molecular weight is defined as follows: wherein R and R 2 , which may be the same or different, each represents a hydrogen atom. an alkyl group. a substituted alkyl group, an aryl group. a substituted aryl group, an acyl group. an alkoxycarbonyl group, a carbamoyl group or an amino group, or R.
• R and R 2 may combine with each other to form a ring, provided that at least one of R and R 2 is an acyl group, an alkoxycarbonyl group, a carbamoyl group or an amino group;
• X represents - CH- or - N -;
• R 3 represents a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group or a substituted aryl group, and R 3 may be connected to the phenyl ring to form a bicyclic compound; and n represents an integer of 2 or more.
• the formalin scavenger described above can be incorporated into at least one of the silver halide emulsion layer, a subbing layer, a protective layer, an interlayer, a filter layer, an anti-halation layer and other auxiliary layers which constitute the silver halide color photographic material of the present invention.
• the formalin scavenger may be incorporated into a magenta polymer coupler-containing silver halide emulsion layer the photographic properties of which would be deteriorated by contact with formaldehyde gas, or into a layer which is nearer to the support than the emulsion layer or a layer which is farther from the support than the emulsion layer, and in any case, the object of the present invention can be attained.
• the photographic material of the present invention may contain various color fading prevention agents.
• organic color fading prevention agents usable in the present invention include hindered phenols such as hydroquinones, 6-hydroxychromans. 5-hydrox- ycoumarans, spirochromans, p-alkoxyphenols and bisphenols, gallic acid derivatives, methylenedioxyben- zenes, aminophenols. and hindered amines. as well as ether or ester derivatives formed by silylation or alkylation of the phenolic hydroxyl group in these compounds.
• metal complexes such as (bis- salicylaldoximato)rnickel complexes and (bis-N,N-dialkyldithiocarbamato)/mckel complexes may also be used.
• the compounds having both partial structures of hindered amines and hindered phenol moieties in one molecule as described in U.S. Patent 4,268,593 may advantageously be used.
• the spiroindanes as described in JP-A-56-159644, and the hydroquinonediether or monoether-substituted chromans as described in JP-A-55-9835 may give a good result.
• These compounds may be added to a light-sensitive layer by co-emulsifying them with the corresponding color coupler in an amount of generally from 5 to 100% by weight of the coupler, whereby the intended object can be attained.
• incorporation of an ultraviolet light absorbing agent into both layers adjacent to the cyan color forming layer is effective.
• an ultraviolet light absorbing agent may also be added to a hydrophilic colloid layer such as a protective layer.
• the photographic material of the present invention may contain a dye for anti-irradiation or anti-halation and may also contain an antistatic agent or a slide property-improving agent.
• the present invention may also be applied to a multilayer and multicolor photographic material having at least two layers each having a different spectral sensitivity on a support.
• a multilayer natural color photographic material generally has at least one red-sensitive emulsion layer, at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer on a support. The order of these layers as arranged on the support is not critical.
• Each of the emulsion layers may contain two or more emulsion layer parts each having a different speed; or a light insensitive layer may be between two or more emulsion layers having the same spectral sensitivity.
• the red-sensitive emulsion layer contains a cyan forming coupler
• the green-sensitive emulsion layer contains a magenta forming coupler
• the blue-sensitive emulsion layer contains a yellow-forming coupler
• the photographic material of the present invention have auxiliary layers such as a protective layer, an interlayer, a filter layer, an anti-halation layer and a white reflective layer, if desired, in addition to the silver halide emulsion layers.
• auxiliary layers such as a protective layer, an interlayer, a filter layer, an anti-halation layer and a white reflective layer, if desired, in addition to the silver halide emulsion layers.
• the photographic emulsion layers and other layers are coated on a support which is generally used in conventional photographic materials, for example, a flexible support such as a plastic film, paper or cloth, or a rigid support such as glass, porcelain or metal.
• a flexible support such as a plastic film, paper or cloth, or a rigid support such as glass, porcelain or metal.
• films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate or polycarbonate, and paper coated or laminated with a baryta layer or an a-olefin polymer (e.g., polyethylene, polypropylene or ethylene'butene copolymer).
• the support may be colored with a dye or pigment.
• the support may be blackened for the purpose of light-shielding.
• the surface of the support is generally coated with a subbing layer to improve adhesion of the emulsion layers and other layers. Before or after coating with the subbing layer, the surface of the support may be processed by glow discharge, corona discharge, ultraviolet ray irradiation or flame treatment.
• the photographic material of the present invention has a non-previously fogged internal latent image type emulsion as described above, the material is imagewise exposed, and then the material is fogged by light or a nucleating agent.
• the material is developed with a surface developer containing a p-phenylenediamine color developing agent, and thereafter subjected to bleaching and fixing to form a direct positive color image. Fogging may be an integral part of the development process.
• a "light fogging method” in which a second exposure is applied to the whole surface of the light-sensitive layer of the material
• a “chemical fogging method” in which the material is developed in the presence of a nucleating agent
• the material may also be developed in the presence of both a nucleating agent and light.
• a nucleating agent may previously be incorporated into the photographic material, which may be fogged by exposure.
• Nucleation accelerating agents which can be used in the present invention include tetraazaindenes, triazaindenes and pentaazaindenes having at least one mercapto group which may optionally be substituted with an alkali metal atom or an ammonium group, as well as the compounds as described in JP-A-63-106506.
• nucleation accelerating agents which can be used in the present invention are set forth below, but the present invention is not to be construed as being limited thereto:
• nucleation accelerating agents may be incorporated into either the photographic light-sensitive material or a processing solution, it is preferred that they be incorporated into the photographic light-sensitive material, especially into the internal latent image type silver halide emulsion layer or other hydrophilic colloid layers (e.g., an interlayer or a protective layer) of the material. Particularly preferably, they are incorporated into the silver halide emulsion layer or into the layers adjacent thereto in the photographic material.
• the amount of nucleation accelerating agents to be added is preferably from 10- 6 to 10- 2 mol. more preferably from 10 -5 to 10- 2 mol. per mol of silver halide in the material.
• the amount of the agent is preferably from 10- 8 to 10- 3 mol. more preferably from 10- 7 to 10 -4 mol, per liter of the processing solution.
• Two or more kinds of nucleation accelerating agents can be used in a mixture.
• a dye developer can be used as the coloring agent. It is preferable that a coloring agent which itself is non-diffusible (or immobile) in an alkaline condition (e.g., in a developing solution), but which may release a diffusible dye (or a precursor thereof) as a result of development be used in this process.
• the diffusible dye releasing coloring agents include couplers or redox compounds which are capable of releasing a diffusible dye. These are useful not only for the color diffusion transfer process (wet type) but also for heat-developable photographic materials (dry type) as described, for example, in JP-A-58-58543.
• DRR compounds The diffusible dye releasing redox compounds (hereinafter referred to as "DRR compounds”) can be represented by the following general formula:
• the amount of the dye compound to be coated is generally from about 1 ⁇ 10 -4 to 1 ⁇ 10 -2 mol/m 2 , preferably from 2x 10- 4 to 2x 10- 2 mol/m2..
• the coloring agent can be incorporated into the corresponding silver halide emulsion layer or into the layers adjacent thereto.
• the photographic emulsion may be coated on the same support having an image receiving layer, or alternatively, it may be coated on a different support.
• the silver halide photographic emulsion layer (light-sensitive element) and the image-receiving layer (image-receiving element) may be combined to provide a combined slim unit, or they may be provided independently in the form of the respective separate photographic material units.
• the combined film unit type it may be either a completely integrated type for exposure, development and observation of transfer images formed or a semi-integrated type for exposure and development where the developed sheet is released to observe the image formed. The latter type is preferred for the present invention.
• the present invention can be applied to various kinds of photographic materials.
• black-and-white negative films include black-and-white negative films, black-and-white reversal films, color negative films for general use or for movies, color reversal films for slides or television use, color reversal papers and instant color films.
• present invention may also be applied to color hard copies for preservation of images from full color duplicators or CRT.
• present invention can be applied to black-and-white photographic materials consisting of three color coupler mixtures as described in Research Disclosure, No. 17123 (July, 1978).
• the color developing solution to be used for development of the photographic material of the present invention is preferably an alkaline aqueous solution consisting mainly of an aromatic primary amine color developing agent.
• an aromatic primary amine color developing agent p-phenylenediamine compounds are preferably used although aminophenol compounds are also useful.
• the compounds include 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N- ⁇ -methoxyethylaniline and sulfates, hydrochlorides and p-toluenesulfonates thereof.
• These compounds can be used in the form of a mixture of two or more of them, in accordance with the object thereof.
• the color developing solution generally contains a pH buffer such as carbonates, borates or phosphates of alkali metals, as well as a development inhibitor or an anti-foggant such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
• a pH buffer such as carbonates, borates or phosphates of alkali metals
• an anti-foggant such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds.
• the color developing solution has a pH value of generally from 9 to 12, preferably from 9.5 to 11.5.
• the amount of the replenisher for the developing solution is generally one liter or less per m 2 of the material being processed. and the amount may be reduced to 300 ml or less if the bromide ion concentration in the replenisher is lowered.
• the amount of the replenisher may be reduced by means of inhibiting the accumulation of bromide ions in the developing solution.
• the photographic emulsion layer thus processed is generally bleached.
• Bleaching may be carried out simultaneously with fixing (i.e., a bleach-fixing step), or may be carried out separately therefrom.
• bleaching may be followed by bleach-fixing.
• other various modifications for example. bleach-fixing in two continuous bleach-fixing bathes, fixing prior to bleach-fixing, or bleach fixing followed by bleaching, may also be employed in accordance with the object of the photographic processing.
• Suitable bleaching agents include compounds of polyvalent metals such as iron(III). cobalt(III), chromium(VI) or copper(II), as well as peracids, quinones and nitro compounds.
• Specific examples of bleaching agents include ferricyanides; bichromates; organic complexes with iron(III) or cobalt(III), for example, complexes with an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid or glycoletherdiaminetetraacetic acid, or an organic acid such as citric acid.
• an aminopolycarboxylic acid such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,
• aminopolycarboxylic acid-iron(III) complexes such as ethylenediaminetetraacetic acid/iron(III) complex and persulfates are preferred from the viewpoint of rapid processability and prevention of environmental pollution.
• Aminopolycarboxylic acid fron(III) complexes are especially useful both in bleaching solutions and in bleach-fixing solutions.
• the pH value of the bleaching solution or bleach-fixing solution containing the aminopolycarboxylic acid.iron(III) complex is generally from 5.5 to 8, but the solution may have a lower pH value so as to accelerate processing.
• the bleaching solution, bleach-fixing solution and any prebath thereof may contain a bleach accelerating agent, if desired.
• Suitable fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas and a large number of iodides.
• Use of thiosulfates is general, and ammonium thiosulfate in particular is preferred.
• sulfites, bisulfites or carbonyl-bisulfite adducts are preferred.
• the silver halide color photographic material of the present invention is generally subjected to washing with water andior stabilization after being desilvered.
• the amount of wash water may be determined within a broad range in accordance with the characteristics of the photographic material to be processed (for example, the nature of the couplers and other components), the intended use of the material. as well as the temperature of the wash water, the number of washing tanks (stages), the kind of replenishment system (countercurrent or ordinary current) and various other conditions. Among these conditions. the relation between the number of washing tanks and the amount of wash water may be determined by the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64. pages 248 to 253, (May, 1955).
• the pH value of the wash water is from 4 to 9, preferably from 5 to 8.
• the temperature of the wash water and the washing time may vary within a broad range, in accordance with the characteristics of the photographic material to be processed and the intended use thereof, and in general, the range of from 15° C to 45 C and from 20 seconds to 10 minutes, preferably from 25 C to 40 C and from 30 seconds to 5 minutes, may be selected.
• the photographic material of the present invention may be processed directly by a stabilizing solution. In such a stabilization step, the methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be utilized.
• the stabilizing bath for the stabilization step may contain various kinds of chelating agents and fungicides.
• the overflow solution resulting from the replenishment of the water washing bath and / or stabilizing bath may be re-used in the previous desilvering step or in other steps.
• the silver halide color photographic material of the present invention can contain a color developing agent for the purpose of simplifying and accelerating processing of the material.
• a precursor of the color developing agent is preferably used.
• precursors for example, there may be the indoaniline compounds described in U.S. Patent 3,342,597, the Schiff's base compounds described in U.S. Patent 3,342,599, Research Disclosure, No. 14850 and ibid., No. 15159, the aldol compounds described in Research Disclosure, No. 13924, the metal complexes described in U.S. Patent 3,719,492 and the urethane compounds described in JP-A-53-135628.
• the respective processing solutions for the photographic material of the present invention are used at from 10°C to 50 C.
• a standard temperature is from 33°C to 38 C
• the processing temperature may be increased so as to accelerate the processing step and shorten the processing time, or the processing temperature may be decreased so as to improve the quality of the image formed and to improve the stability of the processing solution.
• the amount of replenisher to be replenished in the respective processing steps it is preferable to use as small an amount as possible.
• the amount of replenisher is preferably from 0.1 to 50 times, more preferably from 3 to 30 times, the amount of the solution carried over from the preceding bath, per unit area of the material.
• the photographic material of the present invention is black-and-white photographic material, it may be developed with various kinds of known developing agents.
• polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol or pyrogallol
• aminophenols such as p-aminophenol, N-methyl-p-aminophenol or 2,4 diaminophenol
• 3-pyrazolidones such as 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidones or 5,5-dimethyi-1-phenyi-3-pyrazoiidone
• ascorbic acids can be used, alone or in combination.
• the developing solution described in JP-A-58-55928 may be used.
• the developing agent may be incorporated into an alkaline processing composition (processing element) or into an appropriate layer in the light-sensitive element.
• the internal latent image type emulsion photographic material of the present invention can be developed with a surface developer to obtain a direct positive image.
• the surface developer is such that the development therewith is induced substantially by the latent image or fog nuclei existing on the surface of the silver halide grains.
• the surface developer preferably does not contain a silver halide solvent, it may contain a silver halide solvent (for example, sulfites) provided that the silver halide solvent does not substantially participate in developing the internal latent image before the completion of the development of the silver halide grains by the surface development.
• the developing solution may contain, as an alkaline agent or as a buffer, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate or sodium metaborate.
• the content of these agents in the developing solution may be selected so that the pH value of the resulting solution falls within the range of from 9 to 13, preferably from 10 to 11.2.
• the developing solution contains a compound which is generally used as an anti-foggant, such as a benzimidazole (e.g., 5-nitrobenzimidazole), a benzotriazole (e.g., benzotriazole or 5-methylbenzotriazole) or the like, so as to further lower the minimum density of the direct positive image to be formed.
• a compound which is generally used as an anti-foggant such as a benzimidazole (e.g., 5-nitrobenzimidazole), a benzotriazole (e.g., benzotriazole or 5-methylbenzotriazole) or the like, so as to further lower the minimum density of the direct positive image to be formed.
• the developing agent can be incorporated into an alkaline development processing solution (processing element) or may also be incorporated into an appropriate layer of the photographic element.
• the developing agents which may be used in the present invention include hydroquinone, an aminophenol such as N-methylaminophenol, 1-phenyl-3-pyrazolidinone, 1-phenyl-4,4-dimethyl 3 pyrazolidinone, 1-phenyl-4-methyl-4-oxymethyl-3-pyrazolidinone, N,N-diethyl-p-phenylenediamine, 3-methyl-N,N-diethyl-p-phenylenediamine and 3-methoxy-N-ethoxy-p-phenylenediamine.
• black-and-white developing agents which are capable of reducing stains in an image-receiving layer (mordant layer) are especially preferred for same reasons as in the case of the above described alkaline development processing solution.
• the photographic material of the present invention is used as a film unit for a diffusion transfer process, it is preferably processed with a viscous developing solution.
• the viscous developing solution is a liquid composition containing components necessary for development of silver halide emulsions (and formation of diffusion transferred dye images), and the main component of the solvent is water. which may often contain other hydrophilic solvents such as methanol or methyl cellosolve.
• the processing composition contains a hydrophilic polymer such as a macromolecular polyvinyl alcohol. hydroxyethyl cellulose or sodium carboxymethyl cellulose. It is preferred that the polymer be added to the composition in such an amount to give a processing composition having a viscosity of 1 poise or more, preferably from about 500 to 1000 poises, at room temperature.
• the above described processing composition is preferably employed in a container capable of being ruptured under pressure, for example, as described in U.S. Patents 2,543.181, 2,643.886. 2.653.732. 2,723,051, 3,056,491, 3,056,492 and 3.152.515.
• the following First to Fourteenth layers were coated on the front side of a paper support (having a thickness of 100 ⁇ m), both surfaces of which were laminated with polyethylene. and the following Fifteenth and Sixteenth layers were coated on the back side of the paper support to prepare a color photographic light sensitive material.
• the polyethylene laminated on the First layer side of the support contained titanium dioxide (4 gm2) as a white pigment and a slight amount (0.003 gm2) of ultramarine as a bluish dye (chromaticity of the surface of the support was 88.0, -0.20 and -0.75 in an L * , a * and b" system).
• each layer is shown below.
• the coating amounts of the components are in g/m 2 . With respect to silver halide, the coating amount is indicated in terms of a silver coating amount.
• the emulsion used in each layer was prepared according to the method for preparation of Emulsion EM1.
• the emulsion used in the Fourteenth layer was a Lippmann emulsion not being chemically sensitized on the surfaces of grains.
• An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added simultane ously to an aqueous gelatin solution at 75°C over a period of 15 minutes while vigorously stirring, to obtain an octahedral silver bromide emulsion having an average grain diameter of 0.40 um.
• 0.3 g of 3,4-dimethyl-1,3-thiazoline-2-thione per mol of silver was added.
• 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) were added to the emulsion per mol of silver in order and the emulsion was heated to 75°C for 80 minutes to be chemically sensitized.
• the thus-prepared silver bromide grains were used as cores and were further grown under the same precipitation conditions as above to obtain a monodispersed octahedral core shell type silver bromide emulsion having an average grain diameter of 0.7 ⁇ m.
• the coefficient of variation of the grain size was about 10°0.
• each light-sensitive layer was added as a nucleating agent.
• ExZK-1 in an amount of 10 -3 °o by weight based on silver halide.
• Cpd-22 in an amount of 10- 2 °o by weight based on silver halide.
• each layer As emulsifying dispersing aids, Alkanol XC (manufactured by Du Pont) and sodium alkylbenzenesulfonate, and as coating aids, succinic acid ester and Megafac F-120 (manufactured by Dai Nippon Ink and Chemical Co, Ltd.) were added. Furthermore, to the layers containing silver halide or colloidal silver, as stabilizers, Cpd-23. 24, and 25 were added.
• the sample thus-prepared was designated Sample 101.
• ExZK-1 7-(3-Ethoxythiocarbonylaminobenzamido)-9-methyl-10-propargyl-1,2,3,4-tetrahydroacridinium trifluoromethanesulfonate
• Samples 102 to 112 were prepared in the same manner as described for Sample 101. except that a compound represented by the general formula (I) according to the present invention or a comparative compound as shown in Table 1 below were added in the amount of 4.5 ⁇ 10 -3 mol per mol of silver to the sixth and seventh layers, respectively.
• a group of samples thus-obtained were stored for 3 days in an atmosphere of 40 C and 80% RH (incubation), then subjected to wedge exposure (1 10 sec, 10 CMS) together with a group of samples which were not stored in incubation. All samples were then continuously processed in accordance with the processing method described below by an automatic developing machine until the total amount of replenisher added equaled three times the tank capacity.
• the replenishment system for the wash water was a countercurrent replenishment system in which a replenisher was added to water washing bath (2) and the overflow solution from water washing bath (2) was introduced into water washing bath (1).
• the amount of the bleach-fixing solution carried over from the bleach-fixing bath to water washing bath (1) was 35 ml/m 2 of photographic material being processed, and the volume of the replenisher added to water washing bath (2) was 9.1 times the amount of bleach-fixing solution carried over.
• compositions of the processing solutions used were as follows:
• City water was passed through a mixed bed type column filled with an H-type strong acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm & Haas Co.) and an OH-type anion exchange resin (Amberlite IR-400 manufactured by Rohm & Haas Co.) to prepare water containing not more than 3 mglliter of calcium ion and magnesium ion.
• H-type strong acidic cation exchange resin Amberlite IR-120B manufactured by Rohm & Haas Co.
• an OH-type anion exchange resin Amberlite IR-400 manufactured by Rohm & Haas Co.
• Samples 104 to 112 which contain a compound represented by the general formula (I) according to the present invention exhibit higher maximum image density (D max ) in comparison with Sample 101 (containing no compound), Sample 102 (containing comparative Compound A) and Sample 103 (containing Comparative Compound B) in the case of no incubation. Further, with Samples 104 to 112, the decrease in maximum image density (D max ) and the increase in minimum image density (D m , n ) due to the incubation are less in comparison with Sample 101 (containing no compound).
• each of Compounds (1), (4), (5), (7), (9), (13) or (14) according to the present invention were added to the third and fourth layers of test materials and color printing paper samples were prepared in the same manner as the preparation of Sample 101. These samples were incubated under the same conditions as above then exposed and developed in the same manner as above, and similar results were obtained.
• each of Compounds (2), (4), (8), (11) or (14) according to the present invention were added to the eleventh and twelfth layers of test materials and color printing paper samples were prepared in the same manner as above. Similar results were obtained.
• Color printing paper samples were prepared in the same manner as in Example 1, except the nucleating agent ExZK-1 was eliminated from each of the light-sensitive layers. The samples were subjected to incubation, exposure to light and processing in the same manner as described in Example 1. During color development, 15 seconds after the initiation of the development, fogging exposure was conducted for a period of 10 seconds (0.5 lux on the surface of the photographic material processed, with color temperature of 5400 K).
• a processing solution (0.8 g) having the following composition was put in a container capable of being ruptured under pressure.
• the above described light-sensitive sheet was designated Sample 301.
• Other samples were prepared in the same manner as the preparation of the Sample 301, except that the comparative Compound B described in Example 1 or a compound according to the present invention was added to Layer (2) in an amount of 1 ⁇ 10 -5 mol per mol of silver as indicated in Table 3 below.
• the thus-prepared samples were incubated in an atmosphere of 40 C and 80% RH for 3 days and then exposed to light.
• the thus-exposed samples were super posed on the above described dye image receiving sheet in face-to-face relation and the above described processing solution was spread therebetween in a thickness of 60 u.m by the use of a pressing means.
• Thus transferred color images were obtained.
• Core/shell type emulsions I, II and III were prepared in accordance with the methods described below.
• Emulsion I is a diagrammatic representation of Emulsion I:
• An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring over a period of about 20 minutes, while the pAg value of the reaction system was controlled to 7.90 at 40 C.
• a cubic monodispersed silver bromide emulsion having an average grain size of 0.08 ⁇ m was obtained.
• sodium thiosulfate and chloroauric acid (tetra-hydrate) each in an amount of 580 mg per mol of silver, and the emulsion was heated at 75 C for 80 minutes to effect chemical sensitization.
• the thus-obtained silver bromide grains, as cores, were further grown under the same precipitation conditions as in the first step to obtain a core/shell type monodispersed cubic silver bromide emulsion having an average grain size of 0.18 ⁇ m.
• sodium thiosulfate and chloroauric acid tetra-hydrate were added to the emulsion each in an amount of 6.2 mg per mol of silver and the emulsion was heated for 60 minutes at 65°C to effect chemical sensitization.
• Emulsion I was obtained.
• Emulsion II is a composition of Emulsion II:
• An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring over a period of about 40 minutes, while the pAg value of the reaction system was controlled to 9.70 at 45 C.
• An octahedral silver bromide emulsion having an average grain size of 0.2 ⁇ m was obtained.
• sodium thiosulfate and chloroauric acid (tetrahydrate) each in an amount of 5 mg per mol of silver, and the emulsion was heated at 75 C for 80 minutes to effect chemical sensitization.
• the thus-obtained silver bromide grains, as cores, were grown for a further 40 minutes under the same precipitation conditions as in the first step to obtain a core/shell type monodispersed octahedral silver bromide emulsion having an average grain size of 0.35 ⁇ m.
• To the emulsion were added sodium thiosulfate and chloroauric acid (tetrahydrate) each in an amount of 4.5 mg per mol of silver, and the emulsion was heated for 60 minutes at 65°C to effect chemical sensitization.
• an internal latent image type silver halide emulsion (Emulsion II) was obtained.
• Emulsion III is a diagrammatic representation of Emulsion III:
• An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous solution of gelatin with vigorous stirring over a period of about 40 minutes, while the pAg value of the reaction system was controlled to 8.60 at 75 C.
• An octahedral monodispersed silver bromide emulsion having an average grain size of 0.4 ⁇ m was obtained.
• sodium thiosulfate and chloroauric acid (tetra-hydrate) each in an amount of 4 mg per mol of Ag, and the emulsion was heated at 75 C for 80 minutes to effect chemical sensitization.
• the thus-obtained silver bromide grains, as cores, were grown for a further 40 minutes under the same precipitation conditions as in the first step to obtain a core/shell type monodispersed octahedral silver bromide emulsion having an average grain size of 0.6 ⁇ m.
• sodium thiosulfate was added to the emulsion in an amount of 0.9 mg per mol of silver, and the emulsion was heated for 60 minutes at 65°C to effect chemical sensitization.
• an internal latent image type silver halide emulsion (Emulsion III) was obtained.
• an anti-halation layer composed of Anti-halation Dyes (A), (B) and (C) (65 mg / m 2 , 80 mg/m 2 and 40 mg / m 2 , respectively) and gelatin (5 g/m 2 ), and a protective layer (upper layer) composed of barium strontium sulfate (average grain size 1.0 um) (0.1 g/m 2 ) and polymethyl methacrylate (average grain size 1.3 ⁇ m) (0.07 g/m 2 ), as matting agents, Coating Aid (D) (30 mg/m 2 ), Antistatic Agent (E) (1 mg/m 2 ), Hardening Agent (F), (100 mg / m 2 ) and gelatin (1 g/m 2 to prepare a two-layered backing layer.
• an anti-halation layer composed of Anti-halation Dyes (A), (B) and (C) (65 mg / m 2 , 80 mg/m 2 and 40 mg / m 2 , respectively) and gelatin (5 g/
• Sensitizing Dye (G) was added to Core/shell Emulsions I, II and III, in an amount of 150 mg, 200 mg and 180 mg, respectively, per mol of silver, and Nucleating Agent (N-II-1) was also added in an amount of 1.0 ⁇ 10 -3 mol per mol of silver. Further, sodium dodecylbenzenesulfonate as a coating aid and a viscosity increasing agent were added so as to balance the surface tension and the viscosity. Thus coating compositions for a first, second, and third layer were prepared.
• Antistatic agent (E) sodium dodecylbenzenesulfonate (coating aid) and a viscosity increasing agent were added to gelatin to prepare a coating composition for a fourth layer (protective layer).
• the thus-prepared coating compositions for the first to fourth layers were coated in order on the above described support on the surface opposite to that coated with the backing layer.
• the amount of silver halide in the first layer was 1 g m 2 (as silver); that in the second layer was 0.8 g/m 2 (as silver); and that in the third layer was 1.5 g m 2 (as silver).
• the amount of gelatin in the first layer was 1.3 g m 2 : that in the second layer was 1.3 g;m 2 ; that in the third layer was 2.4 g/m 2 ; and that in the fourth layer was 1.7 g/m 2 .
• a direct positive photographic material (Sample 401) was prepared.
• the thus-prepared samples were exposed with a 1 kw tungusten lamp (color temperature: 2854° K) for one second through a step wedge and then developed by an automatic developing machine (FMCP-4800 Type Camera Processor manufactured by Fuji Photo Film Co., Ltd.) using Developer (D) which was prepared by mixing the following Replenisher (A) (one liter) and Starter (B) (20 ml), at 36 C for one minute. After development, the samples were stopped, fixed, washed with water and then dried in a conventional manner. The maximum density (D max ) and the minimum density (D min ) of the image formed in each sample were measured. The results obtained are shown in Table 4 below.
• the thus prepared light-sensitive materials were wedgewise exposed using a sensitometer with a 1 kw tungusten lamp (color temperature: 2854° K) for 0.1 second through a step-wedge. Then, the thus exposed samples were developed with an automatic developing machine (Kodak Proster I Processor) using Kodak Proster Plus processing solution (developing solution: pH 10.7) at 38 C for 18 seconds and successively with the developing machine washed with water, fixed, washed with water and dried. The maximum density (D max ) and the minimum density (D min ) of the direct positive image formed in each sample were measured. The results obtained are shown in Table 5 below.
• the compounds according to the present invention are advantageous since they are effective for increasing the D max value without increasing the D min value, as compared with the comparative sample (Sample 502).
• Example 601 The layers having the compositions described below were coated in order on a cellulose triacetate film support having a subbing layer to prepare a multi-layer color photographic material (Sample 601).
• the amounts of the respective components are represented in units of g m 2 , and the amount of the silver halide is indicated as an amount of silver therein.
• the amount of the sensitizing dye is represented in units of mol per mol of the silver halide present in the layer.
• a gelatin hardening agent (H-1) and a surface active agent were added to the respective layers.
• Samples 602 to 613 were prepared in the same manner as the preparation of the Sample 601. except that a compound according to the present invention or Comparative Compound A or B as described in Example 1 was added to the thirteenth layer in an amount of 5 ⁇ 10 -5 mol per mol of silver as shown in Table 6 below.
• the color development processing was effected in accordance with the following steps at 38°C.
• Potassium hexachloroiridium (III) (4 ⁇ 10 -7 mol per mol of silver) was added to an aqueous gelatin solution kept at 50 C.
• An aqueous silver nitrate solution and an aqueous solution containing potassium iodide and potassium bromide were simultaneously added thereto over a period of 60 minutes in the presence of ammonia, while the pAg value of the reaction system was kept at 7.8.
• a cubic monodispersed emulsion having an average grain size of 0.25 ⁇ m and an average silver iodide content of 1 mol% was obtained.
• the thus prepared samples were exposed and developed, and the photographic characteristics of the respective samples were determined.
• the development processing was effected with a developing solution having the composition described below, in an automatic developing machine (FG-660F type manufactured by Fuji Photo Film Co., Ltd.), at 38° C for 30 seconds.
• the relative sensitivity is defined as the reciprocal of the exposure amount giving a density of 1.5 by development at 38° C for 30 seconds, based on the standardized value (100) of Sample 701.
• the compounds according to the present invention are advantageous in view of the increase in D max and y and the prevention of occurrence of black spot as compared with the comparative compound.

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