EP0853255A2 - Matériau photosensible en couleurs développable à la chaleur - Google Patents

Matériau photosensible en couleurs développable à la chaleur Download PDF

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EP0853255A2
EP0853255A2 EP98100400A EP98100400A EP0853255A2 EP 0853255 A2 EP0853255 A2 EP 0853255A2 EP 98100400 A EP98100400 A EP 98100400A EP 98100400 A EP98100400 A EP 98100400A EP 0853255 A2 EP0853255 A2 EP 0853255A2
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group
added
solution
compound
water
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EP0853255B1 (fr
EP0853255A3 (fr
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Makoto Yamada
Hideaki Naruse
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498—Photothermographic systems, e.g. dry silver
    • G03C1/49827—Reducing agents
    • 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
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/40—Development by heat ; Photo-thermographic processes
    • G03C8/4013—Development by heat ; Photo-thermographic processes using photothermographic silver salt systems, e.g. dry silver
    • G03C8/408—Additives or processing agents not provided for in groups G03C8/402 - G03C8/4046

Definitions

  • the present invention relates to a heat developing color photosensitive material, and more particularly, to a heat developing color photosensitive material which can provide an excellent image in an extremely short developing time and which is not easily affected by variations in processing conditions.
  • Formation of an image by heat development of a silver halide photographic photosensitive material is publicly known and described, for example, in "Fundamentals of Photographic Enginerring (ed. By Non-Silver Salt Photography) Corona Publishing Co., Ltd.” , 1982, pp. 242 to 255, U.S. Patent No. 4,500,626 and the like.
  • Heat developing photographic materials using silver halide are conventionally widely used due to their excellent photographic properties such as sensitivity, gradation and the like, as compared with the electrophotographic method, or the diazo photographic method and the like.
  • a coloring development method in which a dye image is formed by the coupling reaction of an oxidized compound of a developing agent with a coupler, is listed as one method thereof.
  • the coupler and developing agent which can be used in this coloring development method, a combination of a p-phenylene diamines reducing agent with phenol or an activated methylene coupler described in U.S. Patent No.
  • this method has flaws such as the coloring of the undeveloped part of a undeveloped silver halide remaining after processing due to print out or the lapse of time, or color turbidity arising due to the existence of a color image and reduced silver on the exposed portions at the same time, and the like.
  • a dye transferring method is proposed in which a diffusive dye is formed by heat development and transferred onto an image receiving layer.
  • an image receiving material in which a dye receiving layer is supported on a substrate other than that carrying photosensitive material is used, and the dye is diffused and transferred either simultaneously with or after diffusive dye formation by color development dye to obtain a dye image having high color purity.
  • a method is proposed in which a diffusive dye is released or formed into an image form by heat development, and transferred onto a diffusive dye fixing element.
  • a negative dye image or a positive dye image can also be obtained by changing the kind of dye donative compound used or the kind of silver halide used. More details are described in U.S. Patent Nos. 4,500,625, 4,483,914, 4,503,137, 4,559,290, Japanese Patent Application Laid-Open (JP-A) Nos. 58-149046, 60-133449, 59-218443, 61-238056, EP No. 220,746 A2, RD 87-6199, EP No. 210660 A2 and the like.
  • JP-B Japanese Patent Application Publication
  • JP-A No. 59-111,148 a combination of a ureido aniline-based reducing agent with an active methylene-based coupler in JP-A No. 59-111,148, and a photosensitive material using a coupler which has a polymer chain in a releasable group and releases a diffusive dye in color development in JP-A No. 58-149047.
  • JP-A No. 9-152705 discloses a photosensitive material containing novel carbamoylhydrazine.
  • an object of the present invention is to provide a heat developing color photosensitive material which can provide an excellent image in an extremely short developing time and is not easily affected by variations in processing conditions.
  • a further object of the present invention is to provide a heat developing color photosensitive material which can obtain an image even under low temperature processing conditions.
  • Another object of the present invention is to provide a heat developing color photosensitive material with excellent storage properties.
  • a heat developing color photosensitive material comprising a substrate carrying thereon a photosensitive silver halide, a binder, a compound represented by the general formula (I) or (D) and a compound which forms or releases a diffusible dye by reaction with an oxidized product of the compound represented by the general formula (I) or (D), in which the material further comprises at least one of the compounds represented by the general formulae (II-a), (II-b), (III-a), (III-b), (IV-a), (IV-b), (IV-c), (IV-d), (IV-e), (IV-f) or (IV-g).
  • Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group, and both Q1 and C represent an atomic group forming an unsaturated ring.
  • R 1 to R 4 each independently represent a hydrogen atom or substituent thereof, A represents a hydroxyl group or substituted amino group, X represents a linkage group with a valency of two or more selected from the group consisting of -CO-, -SO-, -SO 2 -, and -PO ⁇ , Y represents a bivalent linkage group, Z represents a nucleophilic group which can attack the X group when the compound represented by the formula D is oxidized, R 1 and R 2 and, R 3 and R 4 each independently may bond with each other to form a ring.
  • Ball represents an organic ballasting group which allows the compounds represented by these formulae to become non-diffusive.
  • R 1 is non-diffusive, Ball may not be required.
  • Y 1 represents a carbon atom group required for completing a benzene nucleus or naphthalene nucleus.
  • R 1 represents an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an amino group, or a heretocyclic group.
  • R 2 represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group.
  • n represents an integer from 0 to 5, and when n is 2 to 5, R 2 may be the same of different, or a plurality may bond together to form a ring.
  • Ball and R 2 can be bonded to any one of the rings formed in this way.
  • R represents an aryl group.
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group or an aryl group, and these may be the same or different.
  • A represents a bivalent electron attractive group
  • R 21 represents an alkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylamino group, an anilino group or a haterocyclic group.
  • l represents an integer of 1 or 2.
  • R 22 represents an alkyl group, an alkoxy group, a hydroxyl group or a halogen atom
  • m represents an integer from 0 to 4.
  • Q 2 represents a benzene ring or heterocyclic ring which may be condensed with a phenol ring.
  • R 23 represents an alkyl group, an aryl group or a heterocyclic group.
  • R' 24 represents an alkylene group, an arylene group or an aralkylene group, R 24 represents an alkyl group or an aryl group.
  • Y 2 and R 24 can not represent an alkyl group simultaneously.
  • Ra and Rb each independently represent an alkyl group, an aryl group, an amino group, an alkoxy group, or an aryloxy group.
  • n represents an integer from 1 to 5.
  • R 25 represents a hydrogen atom, an alkyl group, an aryl group, a phenylsulfonyl group, or an acyl group.
  • R 26 and R 24 have the same meaning.
  • R 25 and R 26 may close a ring to form a 5- to 7-membered ring.
  • R 27 and R 28 have the same meaning as for R 24 , and may close a ring to form a 5- to 7-membered ring.
  • R 29 represents an alkyl group having 12 to 50 carbon atoms in total. represents a 5 to 7-membered heterocyclic ring.
  • Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfonyl group or a sulfamoyl group.
  • a carbamoyl group is preferred, and a carbamoyl group having a hydrogen atom on a nitrogen atom is particularly preferable.
  • carbamoyl group a carbamoyl group having 1 to 50 carbon atoms is preferable and one having 6 to 40 carbon atoms is more preferable.
  • Specific examples thereof include a carbamoyl group, a methylcarbamoyl group, an ethylcarbamoyl group, an n-propylcarbamoyl group, a sec-butylcarbamoyl group, an n-octylcarbamoyl group, a cyclohexylcarbamoyl group, a tert-butylcarbmoyl group, a dodecylcarbamoyl group, a 3-dodecyloxypropylcarbamoyl group, an octadecylcarbamoyl group, a 3-(2,4-tert-pentylphenoxy)propylcarbamoyl group, a 2-hexyldecy
  • an acyl group having 1 to 50 carbon atoms is preferable, and one having 6 to 40 carbon atoms is more preferable.
  • Specific examples thereof include a formyl group, an acetyl group, a 2-methylpropanoyl group, a cyclohexylcarbonyl group, an n-octanoyl group, a 2-hexyldecanoyl group, a dodecanoyl group, a chloroacetyl group, a trifluoroacetyl group, a benzoyl group, a 4-dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, a 3-(N-hydroxyl-N-methylaminocarbonyl)propanyl group and the like.
  • alkoxycarbonyl group and aryloxycarbonyl group an alkoxycarbonyl group having 2 to 50 carbon atoms and an aryloxycarbonyl group having 6 to 50 carbon atoms are preferable and an alkoxycarbonyl group and aryloxycarbonyl group each having 6 to 40 carbon atoms are more preferable.
  • Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an isobutyloxycarbonyl group, a cyclohexyloxycarbonyl group, a dodecyloxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group, a 4-octyloxyphenoxycarbonyl group, a 2-hydroxymethylphenoxycarbonyl group, a 4-dodecyloxyphenoxycarbonyl group and the like.
  • sulfonyl group a sulfonyl group having 1 to 50 carbon atoms is preferable, and one having 6 to 40 carbon atoms is more preferable.
  • Specific examples thereof include a methylsulfonyl group, a butylsulfonyl group, an octylsulfonyl group, a 2-hexyldecysulfonyl group, a 3-dodecyloxypropylsulfonyl group, a 2-n-octyloxy-5-t-octylphenylsulfonyl group, a 4-dodecyoxyphenylsulfonyl group and the like.
  • sulfamoyl group a sulfamoyl group having 0 to 50 carbon atoms is preferable, and one having 6 to 40 carbon atoms is more preferable.
  • Specific examples thereof include a sulfamoyl group, an ethylsulfamoyl group, a 2-ethylhexylsulfamoyl group, a decylsulfamoyl group, a hexadecylsulfamoyl group, a 3-(2-ethylhexyloxy)propylsulfamoyl group, (2-chloro-5-dodecyloxycarbonylphenyl) sulfamoyl group, 2-tetradecyloxyphenylsulfamoyl group and the like.
  • Both Q 1 and C represent an atom group which forms an unsaturated ring, and as the unsaturated ring formed, a 3 to 8-membered ring is preferable, and 5 to 6-membered ring is more preferable.
  • Examples thereof include a benzene ring, a pyridine ring, a pyradine ring, a pyrimidine ring, a pyridazine ring, a 1,2,4-triazine ring, a 1,3,5-triazine ring, a pyrrole ring, an imidazole ring, a pyrazole ring, a 1,2,3-triazole ring, a 1,2,4-triazole ring, a tetrazole ring, a 1,3,4-thiadiazole ring, a 1,2,4-thiadiazole ring, a 1,2,5-thiadiazole ring, a 1,3,4-oxadiazole ring, a 1,
  • the rings may further have a substituent, and examples of the substituent include a straight or branched, linear or cyclic alkyl group having 1 to 50 carbon atoms (such as trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl and the like), a straight or branched, linear or cyclic alkenyl group having 2 to 50 carbon atoms (such as vinyl, 1-methylvinyl, cyclohexene-1-yl and the like), an alkynyl group having 2 to 50 carbon atoms in total (such as ethynyl, 1-propynyl and the like), an aryl group having 6 to 50 carbon atoms (such as phenyl, naph
  • the number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less and further preferably 30 or less.
  • the total number of carbon atoms of an unsaturated ring formed from Q and C and a substituent thereof is preferably from 1 to 30, and more preferably from 1 to 24, and most preferably from 1 to 18.
  • the total ⁇ value of Hammett substituent constants (in the case of 1,2, 1,4, - - - position relative to C, ⁇ p value is adopted, and in the case of 1,3, 1,5, - - - position relative to C, ⁇ m value is adopted) of all substituents is preferably 0.8 or more, more preferably 1.2 or more and most preferably 1.5 or more.
  • Hammett substituent constants ⁇ p and ⁇ m are described in, for example, N. Inamoto, "Hammett rule - structure and reactivity -" (Maruzen), “New Experimental Chemical Seminar 14 . Synthesis and Reaction of Organic Compounds V" p. 2605 (Japan Chemical Institute edit., Maruzen), T. Nakaya, "Theoretical Organic Chemistry Commentary” p.217 (Tokyo Chemical Coterie), Chemical Review, vol. 91, pp. 165 to 195 (1991) and the like.
  • the compound (1) was synthesized according to the following synthesis route.
  • Exemplary compound (5) was synthesized according to the following synthesis route.
  • Exemplary compound (15) was synthesized according to the following synthesis route.
  • the organic layer was washed with a sodium hydrogencarbonate solution, a hydrochloric acid solution, and a sodium chloride solution before drying over anhydrous magnesium sulfate, and after filtration, the solvent was distilled off.
  • the compound represented by the general formula (D) represents a developing agent classified under aminophenol derivatives and phenylenediamine derivatives.
  • R 1 to R 4 each independently represent a hydrogen atom or substituent thereof, and examples thereof include a halogen atom (such as chloro and bromo groups), an alkyl group (such as methyl, ethyl, isopropyl, n-butyl and t-butyl groups), an aryl group (such as phenyl group, tolyl group and xylyl groups), a carbon amide group (such as acetylamino, propionylamino, butyloylamino and benzoyl amino groups), a sulfonamide group (such as methanesulfonylamino, ethanesulfonylamino, benzenesulfonylamino and toluenesulfonylamino groups), an alkoxy group (such as meth
  • R 1 to R 4 is preferably a hydrogen atom.
  • the total value of Hammett constants ⁇ p of R 1 to R 4 is preferably 0 or more, and when A is a substituted amino group, the total value of Hammett constants ⁇ p of R 1 to R 4 is preferably 0 or less.
  • A represents a hydroxyl group or substituted amino group (such as dimethylamino, diethylamino and ethylhydroxyethylamino groups), and preferably a hydroxyl group.
  • X represents a linkage group having a valency of two or more selected from -CO-, -SO-, -SO 2 - and -PO ⁇ , and among then, -CO-, -SO 2 - and -PO ⁇ are preferable.
  • Z represents a nucleophilic group which can effect a nucleophilic attack on a carbon atom, sulfur atom or phosphorus atom of X to form a dye, after the coupling reaction of a coupler with an oxidized compound produced by the reduction of a silver halide by the present compound.
  • moieties manifesting nucleophilicity asis generally the case in organic chemistry include an atom having a non-covalent electron pair (such as nitrogen, phosphorus, oxygen, sulfur and selenium atoms and the like) and anionic species (such as nitrogen, oxygen, carbon and sulfur anions). Examples of this nucleophilic group are groups having partial structures and decomposed materials thereof as listed in the following specific examples.
  • this nucleophilic group are groups having partial structures and decomposed materials thereof as listed in the following specific examples.
  • Y represents a bivalent linkage group.
  • This linkage group represents a group in which Z is linkage in such a position as to enables an intramolecular nucleophilic attack onto X via Y.
  • the atoms in the transition condition when the nucleophilic group effects a nucleophilic attack onto X are connected so as to form a 5 or 6-membered ring.
  • a linkage group Y include a 1,2- or 1,3-alkylene group, a 1,2-cycloalkylene group, a Z-vinylene group, a 1,2-arylene group, a 1,8-naphthylene group, and the like.
  • n represents an integer of 1 or more.
  • R 1 and R 2 and, R 3 and R 4 may each independently bond with each other to form a ring.
  • the developing agent represented by the general formula (D) As a method for adding the developing agent represented by the general formula (D), it is possible that a coupler, developing agent, and solvent having a high boiling point (such as alkyl phosphate, alkyl phthalate and the like) are first mixed and dissolved in a solvent having a low boiling point (such as, ethyl acetate, methyl ethyl ketone and the like), and the resulting solution dispersed in water using an emulsifying dispersion method known in the art before the addition of the developing agent. Further, the developing agent can also be added by a solid dispersion method described in Japanese Patent Application Laid-Open (JP-A) No. 63-271339.
  • JP-A Japanese Patent Application Laid-Open
  • the compound represented by the general formula (D) is an oil-soluble compound when the compound is added by the emulsifying dispersion method from among the above-described methods.
  • the ballast group herein represents an oil-soluble group containing an oil-soluble partial structure having 8 to 80 and preferably 10 to 40 carbon atoms.
  • a ballast group having 8 or more carbon atoms is contained in any of R 1 to R 4 , X, Y or Z.
  • the ballast group is contained in either Y or Z, with the number of carbon atoms being preferably from 8 to 80, and more preferably from 8 to 20.
  • the developing agent of the present invention can be synthesized by combining organic synthesis reactions in stepwise fashion. Typical compound synthesis examples are described below.
  • a developing agent D-1 was synthesized by the synthesis route shown below (Scheme-1).
  • the temperature was lowered to 5°C or less, and a solution, obtained by dissolving 184 g of o-sulfobenzoic anhydride (1 mol) in 250 ml of N,N-dimethylacetoamide (DMAc), was carefully added so that the temperature in the flask did not exceed 35°C.
  • DMAc N,N-dimethylacetoamide
  • the mixture was further stirred for 1 hour at room temperature to complete the reaction, then, 200 g (1.3 mol) of phosphorus oxychloride was added to this dropwise.
  • An exothermic reaction occurred as a result of the addition, and the temperature increased to about 60°C.
  • the temperature was kept at 60 to 70°C by using a hot water bath, and the reaction was continued for 5 hours while stirring.
  • a developing agent D-7 was synthesized-by a synthesis route as shown below (Scheme-2).
  • the prepared solution was vigorously stirred while being maintained at 0°C or lower, and to this was gradually added a solution prepared by dissolving 27.5 g (0.4 mol) of sodium nitrite into 50 ml of water, to produce a diazonium salt.
  • This reaction was effected with ice added appropriately to maintain the temperature at 0°C or lower.
  • the diazonium salt thus obtained was gradually added to the solution of the compound B which had been continually stirred.
  • This reaction was also effected by appropriately adding ice to maintain the temperature at 0°C or lower. As the addition proceeded, the solution turned red due to the azo dye.
  • color developing agent represented by general formula D may include, but are not limited to, the following developing agents.
  • the color developing agent of the present invention represented by the general formula (I) or (D) is used together with a compound (coupler) which forms a dye by an oxidation coupling reaction.
  • a compound (coupler) which forms a dye by an oxidation coupling reaction.
  • a two equivalent coupler in which the coupling position is substituted, and which is used in general silver salt photography using a p-phenylenediamine developing agent as a developing chemical is preferable. Details of the above-described coupler are described, for example, in T. H. James, The Theory of the Photographic Process, 4th. Ed., Macmillan, 1977, pp. 291-334, pp. 354-361, and in Japanese Patent Application Laid-Open (JP-A) Nos.
  • Examples of the coupler preferably used in the present invention may include compounds having structures described in the following general formulae (1) to (12). These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol, naphthol or pyrrolotriazole respectively, and are well known in the art.
  • the compounds represented by the general formulae (1) to (4) are couplers called active methylene type couplers which are described in U.S. Patent Nos. 3,933,501, 4,022,620, 4,248,961, Japanese Patent Application Publication (JP-B) No. 58-10739, BP Nos. 1,425,020, 1,476,760, U.S. Patent Nos. 3,973, 968, 4,314,023, 4,511,649, EP No. 249,473A and the like.
  • R 34 represents an acyl group, a cyano group, a nitro group, an aryl group, a hetero cyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, or an arylsulfonyl group each of which may have a substituent.
  • R 35 represents an alkyl group, an aryl group or a hetero cyclic group which may have a substituent.
  • R 36 represents an aryl group or a hetero cyclic group which may have a substituent. Examples of the substituents that R 34 , R 35 and R 36 may have include the examples of the substituents on a ring formed from Q 1 and C.
  • R 34 and R 35 may be linked to each other to form a ring and R 34 and R 36 may be linked to each other to form a ring.
  • the compound represented by the general formula (5) is a coupler referred to as a 5-pyrazolone-based coupler.
  • R 37 represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group.
  • R 38 represents a phenyl group or a phenyl group having one or more substituents selected from a halogen atom, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, and an acylamino group.
  • R 37 is preferably an aryl group or acyl group
  • R 38 is preferably a phenyl group having one or more substituents selected from halogen atoms.
  • R 37 may include aryl or acetyl groups such as a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecaneamidephenyl group, a 2-chloro-5-(3-octadecenyl-1-succinimide)phenyl group, a 2-chloro-5-octadecylsulfoneamidephenyl group, a 2-chloro-5-[2-(4-hydroxy-3-t-butylphenoxy)tetradecaneamide)phenyl, and the like, acyl groups such as a 2-(2,4-di-t-pentylphenoxy)butanoyl group, benzoyl group, a 3-(2,4-di-t-amylphenoxyacetoamide)benzoyl group, and the like, and these groups may further have a substituent, which is an organic substituent or hal
  • R 38 preferably may include a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group, a 2-chloropheyl group, and the like.
  • the compound represented by the general formula (6) may be a coupler referred to as a pyrazoloazole-based coupler.
  • R 39 represents a hydrogen atom or a substituent.
  • Q 3 represents a non-metal atom group required for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).
  • imidazo[1,2-b]pyrazoles described in U.S. patent No. 4,500,630, pyrazolo[1,5-b]-1,2,4-triazoles described in U.S. patent No. 4,500,654 and pyrazolo[5,1-c]-1,2,4-triazoles described in U.S. patent No. 3,725,067 are preferable from the point of the spectral absorption properties of the color developing dye.
  • substituents on an azole ring represented by R 39 , Q 3 are described, for example, in U.S. patent No. 4,540,654, 2nd column, lines 41 to 8th column, line 27.
  • Preferable examples thereof may include a pyrazoloazole coupler in which a branched alkyl group directly bonds to the 2, 3 or 6-position of a pyrazolotriazole group described in Japanese Patent Application Laid-Open (JP-A) No. 61-65,245, a pyrazoloazole coupler containing a sulfoneamide group in the molecule described in Japanese Patent Application Laid-Open (JP-A) No. 61-65245, U.S. Patent No.
  • the compounds represented by the general formulae (7) and (8) are couplers referred to as a phenol-based coupler and naphthol-based coupler, respectively.
  • R 40 represents a hydrogen atom or a group selected from -CONR 42 R 43 , -SO 2 NR 42 R 43 , -NHCOR 42 , -NHCONR 42 R 43 and - NHSO 2 NR 42 R 43 .
  • R 42 and R 43 represent a hydrogen atom or a substituent thereof.
  • R 41 represents a substituent
  • l represents an integer selected from 0 to 2
  • m represents an integer selected from 0 to 4.
  • R 41 may be different for each of them.
  • the substituents of R 42 to R 43 have the same definitions as defined in the substituents on a ring formed from Q 1 and C.
  • phenol-based coupler represented by the formula (7) may include 2-alkylamino-5-alkylphenol-based couplers described in U.S. patent Nos. 2,369,929, 2,801,171, 2,772,162, 2,895,826, 3,772,002 and the like, 2,5-dialkylaminophenol-based couplers described in U.S. patent Nos. 2,772,162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, OLS 3,329,729, Japanese Patent Application Laid-Open (JP-A) No. 59-166956 and the like, 2-phenylureido-5-acylaminophenol-based couplers described in U.S. patent Nos. 3,446,622, 4,333,999, 4,451,559, 4,427,767, and the like.
  • naphthol coupler represented by the formula (8) may include 2-carbamoyl-1-naphthol-based couplers described in U.S. patent Nos. 2,474,293, 4,052,212, 4,146,396, 4,282,233, 4,296,200 and the like, as well as 2-carbamoyl-5-amide-1-naphthol-based couplers described in U.S. patent No. 4,690,889, and the like.
  • the compounds represented by the general formulae (9) to (12) are couplers each referred to as pyrrolotriazole.
  • R 52 , R 53 and R 54 represent a hydrogen atom or a substituent thereof.
  • Y 3 is as defined above.
  • the substituents of R 52 , R 53 and R 54 have the same definitions as defined in the above-described substituents on a ring formed from Q 1 and C.
  • Preferable examples of the pyrrolotriazole-based couplers represented by the general formulae (9) to (12) may include couplers in which at least one of R 52 and R 53 is an electron attractive group described in EP Nos. 488,248A1, 491,197A1, 545,300 and U.S. Patent No. 5,384,236.
  • Y 3 is a group which imparts diffusion resistance to a coupler and can be released by a coupling reaction with an oxidized product of a developing agent.
  • Y include a heterocyclic group (a 5 to 7 membered saturated or unsaturated monocyclic or condensed ring having at least one hetero atom such as nitrogen, oxygen, sulfur and the like, examples thereof include succinimide, maleinimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzoimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiozolidine-2,4-dione, imidazolidine-2-one, oxazolidine-2-one, thiazoline-2-one, benzoimidazoline-2-one, benzo
  • Y 3 may be substituted with a substituent, and examples of the substituent for Y 3 include the examples of the substituent on a ring formed from Q 1 and C.
  • the total number of carbon atoms contained in Y 3 is preferably from 6 to 50, more preferably from 8 to 40, and most preferably from 10 to 30.
  • Y 3 is preferably an aryloxy, heterocyclicoxy, acyloxy, aryloxycarbonyloxy, alkoxycarbonyloxy or carbamoyloxy group.
  • couplers having a different structure can be used such as condensed ring phenol-based couplers, imidazole-based couplers, pyrrole-based couplers, 3-hydroxypyridine-based couplers, active methylene, active methine-based couplers, 5,5-condensed ring heterocyclic-based couplers and 5,6-condensed ring heterocyclic-based couplers.
  • couplers described in U.S. patent Nos. 4,327,173, 4,564,586, 4,904,575 and the like can be used.
  • 3-hydroxypyridine-based coupler couplers described in Japanese Patent Application Laid-Open (JP-A) No. 1-315736 and the like can be used.
  • couplers described in U.S. patent Nos. 5,104,783, 5,162,196 and the like can be used.
  • pyrrolopyrazole-based couplers described in U.S. patent No. 5,164,289 pyrroloimidazole-based couplers described in JP-A No. 4-174429, and the like can be used.
  • pyrazolopyrimidine-based couplers described in U.S. patent No. 4,950,585, pyrrolotriazine-based couplers described in JP-A No. 4-204730, couplers described in EP No. 556,700, and the like can be used.
  • the total number of carbon atoms in parts other than Y 3 is preferably from 1 to 30, more preferably from 1 to 24, and most preferably from 1 to 18.
  • the amount added of the coupler used in the present invention depends on the molar absorptivity ( ⁇ ) of the dye produced, and in the case of a coupler in which ⁇ of a dye produced by coupling is from about 5,000 to 500,000, it is suitable that the amount coated is from about 0.001 to 100 mmol/m 2 , preferably from about 0.01 to 10 millimol/m 2 , and more preferably from about 0.05 to 5.0 millimol/m 2 , in order to obtain an image density of 1.0 or more in terms of reflection density.
  • the amount added of the color developing agent of the present invention represented by the general formulae (I) or (D) is from 0. 01 to 100 times, preferably from 1 to 10 times and more preferably from 0.2 to 5 times the amount of the coupler. Further, 2 or more couplers may be used in combination.
  • R 1 represents a substituted or unsubstituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, an amino group, or a heterocyclic group.
  • R 1 include a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, e.
  • a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms e. g., a cyclohexyl group and the like
  • a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms e. g., a benzyl group, a ⁇ -phenetyl group, and the like
  • a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, e.
  • a phenetyl group a naphthyl group, a tolyl group, a xylyl group, and the like; a substituted or unsubstaituted amino group having 0 to 30 carbon atoms, e.
  • an amino group e. g., an amino group, a methylamino group, an isopropylamino group, a cyclohexylamino group, a phenylamino group, a benzylamino group, an N,N-dimethylamino group, an N-methyl-N-ethylamino group, an N,N-diisopropylamino group, an N,N-dicyclohexylamino group, an N,N-diphenylamino group, an N,N-dibenzylamino group; a substituted or unsubstituted heterocyclic ring, e. g., a pyridyl group, a furyl group, a thienyl group, and the like.
  • substituents of the aryl group include a halogen atom (such as chlorine, bromine atoms and the like), an amino group, an alkoxy group, an aryloxy group, a carbonamide group, an alkanoyloxy group, a benzoyloxy group, an ureido group, a carbamate group, a carbamoyl group, a carbonate group, a carboxy group, an alkyl group (such as methyl, ethyl and propyl groups and the like), an acylamino group, a sulfamoyl group, an ester group, an alkylsulfonyl group, an alkylsulfonylamino group, an arylsulfonylamino group, and the like.
  • a halogen atom such as chlorine, bromine atoms and the like
  • an amino group such as chlorine, bromine atoms and the like
  • an amino group such as chlorine, bromine atoms
  • R 2 represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acylamino group, an alkylthio group, or an arylthio group.
  • R 2 include a hydrogen atom; a halogen atom, e. g., bromine, chlorine, and the like; a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, e. g., a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and the like; a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, e.
  • a halogen atom e. g., bromine, chlorine, and the like
  • a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms e. g., a methyl group, an ethyl group, an isopropyl group, a t-butyl group, and the like
  • a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, e.
  • a cyclopentyl group, a cyclohexyl group, and the like a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, e. g., a benzyl group, a ⁇ -phenetyl group, and the like; a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, e. g., a phenyl group, a naphthyl group, and the like which are listed for R 1 ; a substituted or unsubstituted heterocyclic group, e.
  • a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms e. g., a methoxy group, a butoxy group, a methoxyethoxy group, and the like
  • a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms e. g., a phenoxy group, and the like
  • a substituted or unsubstituted acyl group having 1 to 20 carbon atoms, e.
  • an acetyl group, a palmitoyl group, and the like a substituted or unsubstituted alkyloxycarbonyl group having 1 to 20 carbon atoms, e. g., a methoxycarbonyl group and the like; an aryloxycarbonyl group having 1 to 20 carbon atoms, e. g., a phenoxycarbonyl group and the like; a substituted or unsubstituted carbamoyl group having 1 to 20 carbon atoms, e.
  • a substituted or unsubstituted sulfamoyl group having 1 to 20 carbon atoms e. g., a dimethylsulfamoyl group and the like
  • a substituted or unsubstituted alkylsulfonyl group having 1 to 20 carbon atoms e. g., a methylsulfonyl group and the like
  • a substituted or unsubstituted acylamino group having 2 to 20 carbon atoms e. g., an acetylamino group, an N-methylacetylamino group, a palmitoylamino group, and the like; a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, e.
  • a methylthio group ethylthio group, and the like
  • a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms e. g., a phenylthio group, an m-methoxycarbonylphenylthio group, and the like.
  • n represents an integer from 0 to 5, and when n is from 2 to 5, R 2 may be the same or different, or may be linked to form a ring.
  • bicyclo[2,2,1]hept-2-en, cyclohexene condensed to a benzene ring which is completed by Y described later, and the like are listed.
  • Ball represents an organic ballasting group which can convert the compound represented by the formula described above into a non-diffusive compound.
  • R 1 is non-diffusive, Ball is not be required.
  • ballasting group (Ball) are not critical provided that this ballasting group imparts diffusion resistance to this compound.
  • General ballasting groups include a linear or branched alkyl group which is directly or indirectly linked to this compound, and a benzene type or naphthalene type aromatic group which is indirectly or directly linked to a benzene nucleus.
  • An effective ballasting group is a group generally having at least 8 carbon atoms.
  • Examples thereof include a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms, an acylamino group having 8 to 30 carbon atoms, an acyl group having 8 to 30 carbon atoms, an acyloxy group having 8 to 30 carbon atoms, an alkoxy group having 8 to 22 carbon atoms, an alkylthio group having 8 to 30 carbon atoms, an alkoxy group having an alkoxycarbonyl group having 8 to 30 carbon atoms, and the like.
  • R 3 is preferably a hydrogen atom, an alkyl group having 1 to 7 carbon atoms (e. g., a methyl group, an ethyl group, and the like), a cycloalkyl group (e. g., a cyclohexyl group and the like) or an aryl group (e. g., a phenyl group and the like).
  • L represents a bivalent group (e. g., an alkylene group, a phenyl group, a bivalent arylthio group, and the like), and m represents 0 or 1.
  • Y 1 represents an atom group which is required to complete a benzene nucleus or naphthalene nucleus.
  • Ball and R 2 can be linked to any ring completed in such a manner.
  • R represents an aryl group.
  • R include an aryl group having 6 to 24 carbon atoms such as a phenyl group, a naphthyl group, a tolyl group, an xylyl group, and the like. These groups may be substituted.
  • substituent include a halogen atom (e.
  • a chlorine atom, a bromine atom, and the like an amino group, an alkoxy group, an aryloxy group, a hydroxyl group, an aryl group, a carboamide group, a sulfonamide group, an alkanoyloxy group, a benzoyloxy group, an ureido group, a carbamate group, a carbamoyloxy group, a carbonate group, a carboxyl group, a sulfo group, and an alkyl group (a methyl group, an ethyl group, a propyl group, and the like).
  • R 11 , R 12 , R 13 , R 14 , R 15 and R 16 each independently represent a hydrogen atom, a halogen atom, an acylamino group, an alkoxy group, an alkylthio group, an alkyl group, or an aryl group, and they may be the same as or different to each other.
  • examples of the halogen atom include a chlorine atom, a bromine atom, and the like.
  • acylamino group examples include an acylamino group having 1 to 10 carbon atoms, e. g., an acetylamino group, a benzamido group, and the like. This acylamino group may be substituted with a substituent such as a hydroxyl group, an amino group, a sulfo group, and the like.
  • alkoxy group examples include an alkoxy group having 1 to 10 carbon atoms such as a methoxy group, an ethoxy group, a dodecyloxy group, and the like. This alkoxy group may be substituted with a substituent such as a hydroxy group, an amino group, a sulfo group, a carboxyl group, and the like.
  • alkylthio group examples include an alkylthio group having 1 to 10 carbon atoms such as a methylthio group, an octylthio group, a hexadecylthio group, and the like.
  • This alkylthio group may be substituted with a substituent such as a hydroxyl group, an amino group, a sulfo group, a carboxyl group, and the like.
  • alkyl group examples include an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, and the like. This alkyl group may be substituted with a substituent such as a hydroxyl group, an amino group, a sulfo group, a carboxyl group, and the like.
  • aryl group examples include an aryl group having 6 to 24 carbon atoms such as a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and the like. This aryl group may be substituted, e.
  • a halogen atom a chlorine atom, a bromine group, and the like
  • an alkyl group a methyl group, an ethyl group, a propyl group, and the like
  • a hydroxyl group a hydroxyl group
  • an alkoxy group a methoxy group, an ethoxy group, and the like
  • a sulfo group a carboxyl group, and the like.
  • the compound represented by the general formula (III-b) is more preferably used.
  • R 11 , R 12 , R 13 and R 14 each independently represent preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group, and more preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a phenyl group or a phenyl group substituted with a hydrophilic group such as a hydroxyl group, an alkoxy group, a sulfo group, a carboxyl group, and the like.
  • A represents an electron attracting group represented by the following formula.
  • the alkyl group represents a phenyl group, a 4-t-butylphenyl group, a 2,4-di-t-amylphenyl group, a naphthyl group and the like;
  • the alkoxy group represents a methoxy group, an ethoxy group, a benzyloxy group, a heterodecyl group, an octadecyl group, and the like;
  • the aryloxy group represents a phenoxy group, a 2-methylphenoxy group, a naphthoxy group,
  • examples of the substituent in the substituted alkyl group, substituted aryl group, substituted alkoxy group, substituted aryloxy group, substituted alkylamino group, substituted anilino group, substituted phenylsulfonyl group, substituted acyl group, substituted alkylene group, substituted arylene group, substituted aralkylene group and substituted heterocyclic group in R 21 to R 29 , Q 1 , Q 2 and Y 2 , R' 24 Ra, Rb, include a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, a carbamoyloxy group, a silyloxy group, a sulfonyloxy group, an acylamino group, an anilino group, an ureido group, an imide group,
  • heterocyclic group in Q 2 in the general formula (IV-a) and in P in the general formula (IV-f) has the same definitions as defined in the above-described heterocyclic group, and may have the above-described substituent.
  • the compounds represented by the general formulae (II-a) to (IV-g) may be used alone or in combinations of two or more. And the compounds can be contained in any of an emulsion layer, an intermediate layer, a protective layer, and the like in the photosensitive material, and preferably they are contained in the same layer as that containing the compound represented by the general formula (I) or the coupler.
  • the amount used of the compound represented by the general formulae (II-a) to (IV-g) is preferably in the range from 0.001 to 1000 times by mol, and more preferably from 0.01 to 100 times by mol based on the compound represented by the general formula (I).
  • the compound represented by the general formulae (I) to (IV-g) can be added by the addition method for a hydrophilic compound described below, or added directly after dissolving in a soluble solvent.
  • the compound represented by the general formulae (II-a) to (IV-g) can also be used as a precursor.
  • the precursor is a compound which does not exhibit a developing action during storage of a photosensitive material, and can not release the compound until influenced by a suitable activator (for example, a base, nucleophilic agent and the like) or heat.
  • a suitable activator for example, a base, nucleophilic agent and the like
  • JP-A Japanese Patent Application Laid-Open
  • the developing agent is a compound represented by the general formula (D)
  • compounds represented by the general formulae (II-a), (II-b), (III-a) or (III-b) are preferred as the auxiliary developing agent to be used together with the developing agent.
  • the heat developing color photosensitive material used in the present invention basically comprises a substrate carrying thereon a photosensitive silver halide emulsion and a binder, and optionally, can contain an organic metal salt oxidizing agent, a dye donating compound (a reducing agent may also act as this compound as described later) and the like.
  • these components are added into the same layer in many cases, they can also be divided and added to separate layers. For example, when a dye donating compound which has been colored is contained in a lower layer of a silver halide emulsion, lowering of sensitivity is prevented.
  • the reducing agent is originally contained in the heat developing photosensitive material, it may also be supplied from outside by means such as diffusion from a dye fixing element as described below.
  • At least three silver halide emulsion layers each having light-sensitivity in a different spectral range are combined for use.
  • Examples thereof include a combination of a blue sensitive layer, a green sensitive layer, and a red sensitive layer; a combination of a green sensitive layer, a red sensitive layer, and an infrared sensitive layer; a combination of a red sensitive layer, an infrared photosensitive layer (1), and an infrared photosensitive layer (2) and the like as described in Japanese Patent Application Laid-Open (JP-A) Nos.
  • Each light-sensitive layer can adopt the various arranging orders known in usual color light-sensitive materials. These light-sensitive layers may each be optionally separated into two or more layers as described in Japanese Patent Application Laid-Open (JP-A) No. 1-252,954.
  • various non-photosensitive layers such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, an anti-halation layer, and the like may be provided between the above-described silver halide emulsion layers and also as the top-most layer and bottom-most layer.
  • auxiliary layers such as a backing layer and the like can be provided on the opposite side to the substrate.
  • layer structures and combinations thereof of the above-described patents can be provided, namely an undercoat layer as described in U.S. Patent No. 5,051,335, an intermediate layer having a solid pigment as described in Japanese Patent Application Laid-Open (JP-A) Nos. 1-167,838, 61-20,943, an intermediate layer having a reducing agent and DIR compound as described in Japanese Patent Application Laid-Open (JP-A) Nos. 1-129,553, 5-34,884, 2-64,634, an intermediate layer having an electron transferring agent as described in U.S. Patent Nos.
  • JP-A Japanese Patent Application Laid-Open
  • JP-A Japanese Patent Application Laid-Open
  • the substrate is preferably designed so that it has anti-electrostatic properties and the surface resistivity is 10 12 ⁇ cm or less.
  • the silver halide emulsion which can be used in the present invention may be any of silver chloride, silver bromide, silver iodo bromide, silver chloro bromide, silver chloroiodide and silver chloroiodo bromide.
  • the silver halide emulsion used in the present invention may be a surface latent image-type emulsion or also an inner latent image-type emulsion.
  • the above-described inner latent image-type emulsion is combined with a nuclear forming agent and a light fogging agent and used as a direct reversal emulsion.
  • a so-called core-shell emulsion in which inner part of a particle has a different phase from that of the surface part of a particle may be possible, and silver halide having a different composition may be connected by an epitaxial connection.
  • the above-described silver halide emulsion may be a mono dispersion or a multi dispersion type, and preferably used is a method in which mono dispersion emulsions are mixed and gradation is controlled as described in Japanese Patent Application Laid-Open (JP-A) Nos. 1-167,743 and 4-223,463.
  • the particle size is from 0.1 to 2 ⁇ m, and from 0.2 to 1.5 ⁇ m is particularly preferable.
  • the crystal habit of the silver halide particle may be any of one comprising regular crystals such as a cube, an octahedron, or a tetradecahedron, one comprising an irregular crystal system such as a spherical system, or a tabular system having a high aspect ratio, or one comprising crystal defects such as twin crystal surfaces, or complex systems thereof.
  • RD Research Disclosure
  • JP-A Japanese
  • a desalting, process be conducted in order to remove excessive salt.
  • employable methods include a noodle water-washing method in which gelatin is subjected to gelation, and a flocculation method which utilizes an inorganic salt comprising a polyvalent anion (e.g., sodium sulfate), an anionic surfactant, an anionic polymer (e.g., polystyrene sulfonic acid sodium salt) or a gelatin derivative (e.g., aliphatic-acylated gelation, aromatic-acylated gelatin, aromatic-carbamoylated gelatin and the like).
  • a flocculation method is preferably used.
  • the light-sensitive silver halide emulsion in the present invention may contain a heavy metal such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium. These compounds may be used alone or in a combination or two or more of them. Although the amount added of such compounds varies depending on the purpose of use, this amount is generally in the range of 10 -9 to 10 -3 mol based on 1 mol of silver halide.
  • the heavy metal may be present uniformly in a silver halide grain or may be present in a localized manner within or on the surface of a silver halide grain. Preferred examples of these emulsions are the emulsions described in Japanese Patent Application Laid-Open (JP-A) Nos. 2-236,542, 1-116,637 and Japanese Patent Application No. 4-126,629 and the like.
  • Such compounds as rhodanate, ammonia, a tetra-substituted thioether compound, an organic thioether derivative described in Japanese Patent Application Publication (JP-B) No. 47-11,386, and a sulfur-containing compound described in Japanese Patent Application Laid-Open (JP-A) No. 53-144,319 may be used as a solvent for silver halide in the grain forming stage for the light-sensitive silver halide emulsion used in the present invention.
  • an employable method may be selected from an acidic method, a neutral method and an ammonia method.
  • any method selected from a single jet method, a double jet method and a combination thereof may be used as a method for reacting a soluble silver salt with a soluble halide.
  • a double jet method is preferable for obtaining a monodisperse emulsion.
  • a reversed mixing method in which grains are formed in the presence of an excess of silver iron can also be employed.
  • a so-called controlled double jet method in which pAg of the liquid phase for the formation of silver halide is kept constant can also be employed as the double jet method.
  • the concentrations, amounts to be added and adding rates of the silver salt and halogen salt may be increased in order to accelerate the growth of the grains (Japanese Patent Application Laid-Open (JP-A) Nos. 55-142,329 and 55-158,124 and U.S. Patent No. 3,650,757 and the like).
  • the stirring of the reaction mixture may be effected by any known method. Further, the temperature and pH of the reaction mixture during the formation of silver halide grains may be selected depending on the desired outcome.
  • the pH is preferably in the range of 2.2 to 8.5, and more preferably 2.5 to 7.5.
  • a light-sensitive silver halide emulsion is normally a chemically sensitized silver halide emulsion.
  • a sensitizing method by means of chalcogen such as sulfur sensitization, selenium sensitization or tellurium sensitization, a sensitizing method by means of a rare metal, such as gold, platinum or palladium, and a sensitizing method by means of reduction, which are known sensitizing methods in the preparation of conventional light-sensitive emulsions, may be used alone or in combination thereof as a chemical sensitizing method of the light-sensitive silver halide emulsion used in the present invention (see, for example, JP-A No. 3-110555 and Japanese Patent Application No. 4-75798 and the like).
  • a chemical sensitization according any of the above-mentioned methods can be effected in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open (JP-A) No. 62-253159).
  • a nitrogen-containing heterocyclic compound Japanese Patent Application Laid-Open (JP-A) No. 62-253159.
  • an anti-fogging agent which is described below, may be added to a silver halide emulsion after the chemical sensitization thereof. More concretely, the methods, which are described in Japanese Patent Application Laid-Open (JP-A) Nos. 5-45833 and 62-40446, can be used.
  • pH is preferably in the range of 5.3 to 10.5, and more preferably 5.5 to 8.5, while pAg is preferably in the range of 6.0 to 10.5, and more preferably 6.8 to 9.0.
  • the coated weight of the light-sensitive silver halide to be used in the present invention is in the range of 1 mg/m 2 to 10 g/m 2 , and preferably 10 mg/m 2 to 10 g/m 2 based on the weight of the silver.
  • the light sensitive silver halide emulsion is spectrally sensitized by means of a methine dye or the like. Further, if necessary, a blue-sensitive emulsion may be spectrally sensitized in order to enhance sensitivity to the light of the blue color region.
  • Examples of employable dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
  • sensitizing dyes are disclosed, for example, in U.S. Patent No. 4,617,257 and Japanese Patent Application Laid-Open (JP-A) Nos. 59-180550, 64-13546, 5-45828 and 5-45834 and the like.
  • sensitizing dyes may be used alone, they may also be used in combinations thereof.
  • a combination of these sensitizing dyes in often used particularly for supersensitization or for adjusting the spectral sensitization wavelength.
  • the light-sensitive silver halide emulsion used in the present invention may contain a compound which is a dye having no spectral sensitization effect itself together with the sensitizing dye, or a compound substantially incapable of absorbing a visible light but which exhibits a supersensitizing effect (e. g., compounds described in U.S. Patent No. 3,615,641 and Japanese Patent Application Laid-Open (JP-A) No. 63-23145).
  • a compound which is a dye having no spectral sensitization effect itself together with the sensitizing dye or a compound substantially incapable of absorbing a visible light but which exhibits a supersensitizing effect (e. g., compounds described in U.S. Patent No. 3,615,641 and Japanese Patent Application Laid-Open (JP-A) No. 63-23145).
  • sensitizing dyes can be added to the emulsion at the stage of chemical aging or thereabouts, or before or after the formation of the nucleus of the silver halide grains in accordance with the descriptions in U.S. Patent Nos. 4,183,756 and 4,225,666.
  • These sensitizing dyes or supersensitizers may be added to the emulsion as a solution in an organic solvent such as methanol, as a dispersion such as gelative or as a solution containing a surfactant.
  • the amount to be added is generally in the range of 10 -8 to 10 -2 mol based on 1 mol of silver halide.
  • Additives used in these processes and known photographic additives, which are used in the heat developing photosensitive material and the pigment fixing material of the present invention, are described in the aforementioned RD No. 17,643, RD No. 18,716 and RD No. 307,105, the relationship in the description is shown below.
  • Chemical sensitizer p. 23 p. 648, RC p. 866 2.
  • Spectral sensitizer/Supersensitizer pp. 23-24 pp. 648, RC ⁇ 649 pp. 866-868 4.
  • Anti-fogging agent/Stabilizer pp.24-25 p. 649, RC pp. 868-870 6.
  • Light absorber/Filter dye Ultraviolet ray absorber pp. 25-26 pp. 649, RC ⁇ 650, LC p.873 7.
  • Hardening agent p. 26 p. 651, LC pp. 874-875 9.
  • Plasticizer/Lubricant p. 27 p. 650, RC p. 876 11.
  • Coating aid Surfactant pp. 26-27 p. 650, RC pp. 875-876 12.
  • Matting agent pp. 878-879 (RC: right column, LC: left
  • the binder for the structural layers of the heat developing photosensitive material and dye fixing material is preferably a hydrophilic material.
  • the binder is preferably a transparent or translucent hydrophilic material, exemplified by a naturally occurring compound, such as a protein including gelatin, a gelatin derivative and the like; and a polysaccharide including a cellulose derivative, starch, gum arabic, dextran, pullulane and the like, and by a synthetic polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, acryl amide polymer and the like.
  • binder is a highly water-absorbent polymer described in U.S. Patent No. 4,960,681 and Japanese Patent Application Laid-Open (JP-A) No. 62-245,260, for example, a homopolymer composed of a vinyl monomer having -COOM or - SO 3 M (M stands for a hydrogen atom or an alkali metal), or a copolymer obtained by a combination of these monomers or obtained by a combination of at least one of these monomers and another monomer(s) such as sodium methacrylate and ammonium methacrylate (e. g., SUMIKAGEL L-5H manufactured by Sumitomo Chemical Co., Ltd.).
  • M stands for a hydrogen atom or an alkali metal
  • binders may be used alone or in combinations of two or more. Particularly, a combination of gelatin and any of the above-mentioned non-gelatin binders is preferable. Depending on the desired outcome, a lime-processed gelatin, acid-processed gelatin, and delimed gelatin which has undergone a deliming process to decrease the content of calcium and the like can be used, preferably in combination.
  • the appropriate amount coated of the binder is preferably from 0.2 to 20 g, preferably from 0.2 to 10 g, and more preferably from 0.5 to 7 g per 1 m 2 .
  • An organic metal salt may be used as an oxidant together with a light-sensitive silver halide in the present invention.
  • an organic silver salt is particularly preferable.
  • Examples of the organic compounds which can be used for the preparation of the above-mentioned organic silver salts serving as an oxidant may include benzotriazoles, fatty acids and other compounds described in U.S. Patent No. 4,500,626, columns 52-53.
  • the silver acetylide, which is described in U.S. Patent No. 4,775,613, is also useful.
  • These organic silver salts may also be used in a combination of two or more of them.
  • the above-mentioned organic silver salt can be used in an amount in the range of 0.01 to 10 mol, and preferably 0.01 to 1 mol, based on 1 mol of the light-sensitive silver halide.
  • the total coated weight of the light-sensitive silver halide and the organic silver salt is in the range of 0.05 to 10 g/m 2 , and preferably 0.1 to 4 g/m 2 , based on the weight of silver.
  • reducing agents in addition to the compound represented by the above-described general formulae, known reducing agents can be used together. Further, a dye donating compound having reducing properties as described later is also included (in this case, other reducing agents can also be used together). Further, a reducing agent precursor, which does not have reducing properties itself but exhibits reducing properties by being influenced by a nucleophilic agent and heat in a developing process can also be used.
  • Examples of the reducing agent used in the present invention include reducing agents and reducing agent precursors described in U.S. Patent Nos. 4,500,626, columns 49 to 50, 4,839,272, 4,330,617, 4,590,152, 5,017,454, 5,139,919, Japanese Patent Application Laid-Open (JP-A) Nos. 60-140,335, pp.
  • the above-described reducing agents can be used in the intermediate layer and protective layer for various purposes such as prevention of color mixing, improvement in color reproducibility, improvement in the white background, prevention of silver transfer to a dye fixing material, and the like.
  • Specific examples of the reducing agent which can be preferably used are described in EP Nos. 524,649, 357,040, Japanese Patent Application Laid-Open (JP-A) Nos. 4-249245, 2-64633, 2-46450 and 63-186240.
  • JP-B Japanese Patent Application Laid-Open
  • JP-A Japanese Patent Application Laid-Open
  • the total amount added of the reducing agent is from 0.01 to 20 mol, and particularly preferably from 0.1 to 10 mol based on 1 mol of silver.
  • Hydrophobic additives such as a dye donating compound, a diffusion resistant reducing agent and the like can be introduced into layers of the heat developing photosensitive material according to known methods such as that is described in U.S. Patent No. 2,322,027 and the like.
  • an organic solvent having a high boiling point described in U.S. Patent Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4,599,296, Japanese Patent Application Publication (JP-B) No. 3-62,256 and the like can be optionally used together with an organic solvent having a low boiling point of 50 to 160°C.
  • the dye donating compound, diffusion resistant reducing agent, and organic solvent having a high boiling point can be used in combinations of two or more.
  • the amount of the organic solvent having a high boiling point is 10 g or less, preferably 5 g or less, and more preferably 1 to 0.1 g per 1 g of the dye donating compound used. Alternatively, it is preferably 1 cc or less, more preferably 0.5 cc or less and most preferably 0.3 cc or less per 1 g of binder.
  • JP-B Japanese Patent Application Publication
  • JP-A Japanese Patent Application Laid-Open
  • JP-A Japanese Patent Application Laid-Open
  • JP-A Japanese Patent Application Laid-Open
  • JP-A Japanese Patent Application Laid-Open
  • a fine particle thereof can be dispersed and included in a binder in addition to the above-described methods.
  • hydrophobic compound When the hydrophobic compound is dispersed in a hydrophilic colloid, various surfactants can be used.
  • surfactants described in Japanese Patent Application Laid-Open (JP-A) No. 59-157636, pp. (37) to (38) and the above-described Research Disclosure.
  • a compound which can realize stabilization of an image at the same time as activating development can be used.
  • Specific compounds which are preferably used are described in U.S. Patent No. 4,500,626, pp. 51 to 52.
  • various compounds can be added to the structural layers of the heat developing photosensitive material of the present invention for the purpose of fixing or de-coloring of unnecessary dyes and coloring materials and improvement in the white background of the resulting image.
  • various pigments and dyes can be used for the purpose of improving color discrimination, making the material even more highly sensitive and the like.
  • a dye fixing material is used together with the heat developing photosensitive material to form an image by diffusion transfer of a dye.
  • the dye fixing material may be coated on a substrate other than that coated with the photosensitive material, or may be coated on the same substrate on which the photosensitive material is coated.
  • the relation between the photosensitive material and the dye fixing material, the relation between the photosensitive material and the substrate, and the relation between the photosensitive material and the white reflective layer are described in U.S. Patent No. 4,500,626, column 57, and can also be applied to the present invention.
  • the dye fixing material preferably used in the present invention has at least one layer containing a mordanting agent and a binder.
  • a mordanting agent an agent known in the photography field can be used, and specific examples thereof include mordanting agents described in U.S. Patent No. 4,500,626, column 58 to 59, Japanese Patent Application Laid-Open (JP-A) Nos. 61-88,256, pp. (32) to (41) and 1-161,236, pp. (4) to (7), mordanting agents described in U.S. Patent No. 4,774,162, 4,619,883, 4,594,308 and the like. Further, dye receptive polymer compounds described in U.S. Patent No. 4,463,079 may also be used.
  • the binder used in the dye fixing material of the present invention is preferably the above-described hydrophilic binder. Further, carageenans described in EP No. 443,529 can be preferably used, and latexes having a glass transition temperature of 40°C or less described in Japanese Patent Application Publication (JP-B) No. 3-74,820 can preferably be used.
  • Auxiliary layers such as protective layers, peeling layers, undercoat layers, intermediate layers, backing layers, curl prevention layers and the like can be provided in the dye fixing material where necessary. It is particularly useful to provide a protective layer.
  • a plasticizer and lubricant or an organic solvent having a high boiling point as a peeling improving agent between the photosensitive layer and the dye fixing material. Concrete examples thereof are described in the above-described Research Disclosure, JP-A No. 62-245,253 and the like.
  • various silicone oils can be used.
  • Effective examples thereof include various modified silicone oils described in "Modified Silicone Oil” technical data P6-18B published by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (X-22-3710) and the like.
  • silicone oil described in Japanese Patent Application Laid-Open (JP-A) Nos. 62-215953 and 63-46449 is also effective.
  • a brightening agent may also be used in the heat developing photosensitive material and dye fixing material. It is preferable that the brightening agent is originally contained inside the dye fixing material, or it is supplied from outside through the heat developing photosensitive material, transfer solvent, or the like. Examples thereof may include compounds described in K. Veenkataraman, "The Chemistry of Synthetic Dyes” , vol. V, chapter 8, JP-A No. 61-143752 and the like. More specific examples thereof include stylbene-based compounds, cumarine-based compounds, biphenyl-based compounds, benzooxazolyl-based compounds, naphthalimide-based compounds, pyrazoline-based compounds, carbostylyl-based compounds and the like.
  • the brightening agent can be used in combination with a fading inhibitor and an ultraviolet ray absorber.
  • Examples of the hardening agent used in the structural layers of the heat developing photosensitive material and dye fixing material may include those described in the above-described Research Disclosures, U.S. Patent Nos. 4,678,739, column 41 and 4,791,042, and in Japanese Patent Application Laid-Open (JP-A) Nos. 59-116655, 62-245261, 61-18942, 4-218044 and the like.
  • examples of these hardeners may include an aldehyde (e.g., formaldehyde), an aziridine, an epoxy, a vinylsulfone (e.g., N,N'-ethylene-bis(vinylsulfonylacetamide)ethane), a N-methylol compound (e.g., dimethylolurea) and a polymeric compound (e.g., a compound described in Japanese Patent Application Laid-Open (JP-A) No. 62-234,157).
  • aldehyde e.g., formaldehyde
  • an aziridine an epoxy
  • a vinylsulfone e.g., N,N'-ethylene-bis(vinylsulfonylacetamide)ethane
  • a N-methylol compound e.g., dimethylolurea
  • a polymeric compound e.g., a compound described in Japanese Patent Application Laid-Open (JP-A) No. 6
  • the amount of the hardener added may be in the range of 0.001 g to 1 g, and preferably 0.005 to 0.5 g, based on 1 g of coated gelatin.
  • the layer to which the hardener is added may be any of the structural layers of a light-sensitive material and dye fixing material, and also may be separated into two or more layers before addition of the hardener.
  • the structural layers of the heat developing photosensitive material and dye fixing material may contain various anti-fogging agents or photographic stabilizers or precursors thereof. Specific examples thereof include azole and azaindenes described in RD 17643 (1978), pp. 24 to 25, carboxylic acids and phosphoric acids containing nitrogen described in Japanese Patent Application Laid-Open (JP-A) No. 59-168,442, mercapto compounds and metal salts thereof described in Japanese Patent Application Laid-Open (JP-A) No. 59-111636, acetylene compounds described in Japanese Patent Application Laid-Open (JP-A) No. 62-87957, and the like.
  • a precursor when a precursor is used, it is preferably contained in the photosensitive silver halide emulsion layer as described above, and can also used in the dye fixing material.
  • the amount of the compound added may be preferably in the range of 5 ⁇ 10 -6 to 1 ⁇ 10 -1 mol, and more preferably 1 ⁇ 10 -5 to 1 ⁇ 10 -2 mol, based on 1 mol of silver. In the case of a precursor, the amount more preferably used is as described above.
  • various surfactants may be added to the structural layers of the heat developing photosensitive material and dye fixing material.
  • specific examples of the surfactants include those described in the above-described Research Disclosure, Japanese Patent Application Laid-Open (JP-A) Nos. 62-173,463, 62-183,457 and the like.
  • an organic fluorine-containing compound may be added to the structural layers of the heat developing photosensitive material and dye fixing material.
  • organic fluorine-containing compounds include a fluorine-containing surfactant, a hydrophobic fluorine-containing compound, such as an oily fluorine-containing compound, e.g., fluorocarbon oil, and a solid fluorine-containing resin, e.g., tetrafluoroethylene, described in Japanese Patent Application Publication (JP-B) No. 57-9053, column 8-17, Japanese Patent Application Laid-Open (JP-A) Nos. 61-20944 and 62-135826 and the like.
  • JP-B Japanese Patent Application Publication
  • JP-A Japanese Patent Application Laid-Open
  • a matting agent can be used in the heat developing photosensitive material and dye fixing material.
  • the matting agent may include compounds described in Japanese Patent Application Laid-Open (JP-A) Nos. 63-274944 and 63-274952 such as a benzoguanamine resin bead, polycarbonate resin bead, ABS resin bead-and the like, in addition to compounds described in Japanese Patent Application Laid-Open (JP-A) No. 61-88256, p. 29 such as silicon dioxide, polyolefin, polymethacrylate and the like. Further, compounds described in the above-described Research Disclosure can be used.
  • matting agents can be added, if necessary, not only to the top layer (protective layer) but also to a lower layer.
  • the structural layers of the heat developing photosensitive material and dye fixing material may contain a heat solvent, a de-foaming agent, an antimicrobial agent, colloidal silica and the like. Specific examples of these additives are described in Japanese Patent Application Laid-Open (JP-A) No. 61-88256, pp. 26 to 32, Japanese Patent Application Laid-Open (JP-A) No. 3-11338, Japanese Patent Application Publication (JP-B) No. 2-51496 and the like.
  • an image formation accelerator can be used in the heat developing photosensitive material and/or dye fixing material.
  • the image formation accelerator has such functions as promoting a redox reaction of a silver salt oxidizing agent with a reducing agent, promoting reactions such as the formation or decomposition of a dye from the dye donating material or the releasing of a diffusive dye, and promoting the transfer of a dye from the layer of the heat developing photosensitive material to the dye fixing layer, and the like, and is classified from the view point of physicochemical functions into a base or base precursor, nucleophilic compound, high boiling point organic solvent (oil), heat solvent, surfactant, compound having mutual action with silver or silver ion, and the like. Since these compounds have generally complex functions, they usually have several of the functions described above in combination. The details thereof are described in U.S. patent No. 4,678,739, pp. 38 to 40.
  • the base precursor examples include a salt of a base and an organic acid which is de-carbonated by heating, a compound which releases amines by intramolecular nucleophilic substitution reaction, Lossen transformation or Beckmann transformation, and the like. Specific examples thereof are described in U.S. Patent Nos. 4,514,493, 4,657,848 and the like.
  • a method in which a base and/or base precursor is contained in the dye fixing material is preferable from the view point of increasing in preservability of the heat developing photosensitive material.
  • a combination of a poor-soluble metal compound with a compound (complex forming compound) which can effect a complex forming reaction with a metal ion constituting this poor-soluble metal compound described in EP No. 210,660 and U.S. Patent No. 4,740,445, a compound which generates a base by electrolysis described in Japanese Patent Application Laid-Open (JP-A) No. 61-232451, and the like can also be used as the base precursor.
  • the former method is particularly effective. It is advantageous that the poor-soluble metal compound and complex forming compound are added separately to the heat developing photosensitive material and dye fixing material as described in the above-described patents.
  • various development stopping agents can be used in the heat developing photosensitive material and/or dye fixing material for the purpose of obtaining a constant image in spite of variations in the processing temperature and processing time during developing.
  • the development stopping agent is a compound which, at the appropriate stage of development, quickly neutralizes or reacts with a base to decrease the concentration of the base in a film for stopping the development, or which effects a mutual reaction with silver or silver salt to suppress the development.
  • Specific examples thereof include an acid precursor which releases an acid by heating, an electrophilic compound which generates by heating a substitution reaction with a coexisting base, or a nitrogen-containing heterocyclic compound, mercapto compound and precursors thereof. Further details thereof are described in Japanese Patent Application Laid-Open (JP-A) No. 62-253159, pp. (31) to (32).
  • the substrate of the heat developing photosensitive material and dye fixing material a material which can endure the processing temperature can be used.
  • substrates for photography such as paper, synthetic polymer (film) and the like described in Japan Photograph Assosiation's "Base for Photographic Technology (ed. by Silver Salt Photography)" Corona Corp., 1979, pp. (223) to (240), can be listed.
  • This laminated layer can optionally contain pigments and dyes such as titanium oxide, ultramarine blue pigment, carbon black and the like.
  • JP-A Japanese Patent Application Laid-Open
  • substrates described in Japanese Patent Application Laid-Open (JP-A) Nos. 62-253159, pp. (29) to (31), 1- 61,236, pp. (14) to (17), 63-316848, 2-22651, 3-56955, U.S. Patent No. 5,001,033 and the like can be used.
  • the back surface of this substrate may be coated with a hydrophilic binder and a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents.
  • a hydrophilic binder and a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents.
  • substrates which are described in Japanese Patent Application Laid-Open (JP-A) No. 63-220246 and the like can be used.
  • the front surface of the substrate is preferably subjected to various surface processes and under coating for the purpose of improving adhesion with the hydrophilic binder.
  • the light source for recording an image on the heat developing photosensitive material there can be used light sources and exposing methods described in U. S. patent No. 4,500,626, column 56, Japanese Patent Application Laid-Open (JP-A) No. 2-53,378 and 2-54,672 such as natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source and the like, as described above.
  • JP-A Japanese Patent Application Laid-Open
  • image exposure can also be conducted using a wavelength converting element which is obtained by combining a non-linear optical material with a coherent light source such as a laser light and the like.
  • the non-linear optical material is a material which can manifest non-linear characteristics between an electric field and the polarization which occurs when a strong light electric field such as from a laser light is imparted, and preferably used are inorganic compounds represented by lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, BaB 2 O 4 and the like, urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM), compounds described in Japanese Patent Application Laid-Open (JP-A) Nos. 61-53462 and 62-210432.
  • Various forms of the wavelength converting element such as a monocrystalline light directing route type, a fiber type, and the like are known, and all of them are
  • the above-described image information can utilize image signals obtained from a video camera, an electronic still camera, and the like, television signals represented by that stipulated by Nippon Television Signal Criteria (NTSC), image signals obtained by dividing an original image into many picture elements such as that obtained from a scanner, and image signals made by a computer represented by CG, CAD.
  • NTSC Nippon Television Signal Criteria
  • the heat developing photosensitive material and/or dye fixing material of the present invention may adopt a form having an electroconductive heat generating layer as a heating means for heat developing and diffusion transferring of a dye.
  • the heat generating element in this case, one from those described in Japanese Patent Application Laid-Open (JP-A) No. 61-145544 and the like can be used.
  • the heating temperature in the heat developing is from about 50 to 250°C, and a temperature from about 60 to 180°C is particularly useful.
  • the diffusion transfer process of a dye may be conducted simultaneously with the heat development or may be conducted after the completion of the heat development process. In the latter case, it is particularly preferable that the heating temperature in the transfer process is 50°C or higher, and about 10°C lower than the temperature during the heat developing process, although the transfer process can be conducted at between room temperature to the temperature in the heat developing process.
  • a solvent may be used to promote the dye movement.
  • a method is also useful in which development and transfer are conducted simultaneously or continuously by heating in the presence of a small amount of solvent (especially, water) as described in U.S. Patent Nos. 4,704,345, 4,740,445, Japanese Paten Application Laid-Open (JP-A) No. 61-238,056 and the like.
  • the heating temperature is preferably 50°C or higher and not more than boiling point of the solvent.
  • the solvent is water, it is preferably from 50 to 100°C.
  • Examples of the solvents used for promoting the development and/or the diffusion transfer of a dye include water, an aqueous basic solution containing an inorganic alkaline metal salt and an organic base (as these bases, those described in the column of the image formation promoter can be used), solvents having a low boiling point, or a mixture of solvents having a low boiling point and water or the above-described aqueous basic solution.
  • the solvent may contain a surfactant, an anti-fogging agent, a compound which forms a complex with a poor-soluble metal salt, an antifungal agent and, an antimicrobial agent.
  • water is preferably used, and any water usually used may be used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in a heat developing apparatus using the heat developing photosensitive material and dye fixing material of the present invention, water may be used without recycling or may be recycled and used repeatedly. In the latter case, water containing components eluted from material shall be used. Apparatuses and water described in Japanese Paten Application Laid-Open (JP-A) Nos. 63-144354, 63-144355, 62-38460, 3-21055 and the like may also be used.
  • JP-A Japanese Paten Application Laid-Open
  • solvents may be added to the heat developing photosensitive material, the dye fixing material or to both of them.
  • the amount used thereof may not be more than the weight of solvent corresponding to the maximum swollen volume of the total coated film.
  • the temperature of water added may be from 30 to 60°C as described in Japanese Paten Application Laid-Open (JP-A) No. 63-85544 and the like. It is particularly useful that the temperature is 45°C or higher for the purpose of preventing proliferation of contaminant bacteria in water.
  • a hydrophilic hot solvent which is solid at ordinary temperature and is dissolved at high temperatures can be contained in the heat developing photosensitive material and/or dye fixing material.
  • the layer which contains the solvent may be any of a photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, or a dye fixing layer, with dye fixing layer and/or adjacent layer thereof being preferable.
  • hydrophilic hot solvent examples include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic rings.
  • Examples of heating methods in the developing and/or transferring processes include contacting with a heated block and plate, contacting with a heat plate, hot pressing, heat rolling, using a heat drum, a halogen lamp heater, infrared and far infrared lamp heaters and the like, passing through a high temperature atmosphere, and the like.
  • methods described in Japanese Paten Application Laid-Open (JP-A) Nos. 62-253159, 61-147244 p. (27) and the like can be adopted.
  • any of various heat developing apparatuses can be used.
  • apparatuses described in Japanese Paten Application Laid-Open (JP-A) Nos. 59-75,247, 59-177,547, 59-181,353, 60-18,951, 62-25,944, Japanese Patent Application Nos. 4-277517, 4-243072, 4-244693 and the like are preferably used.
  • PICTOSTAT 100, 200, PICTOGRAPHY 3000, 2000 manufactured by Fuji Photo Film Co., Ltd., and the like can be used.
  • the method of density expression thereof may be any of a continuous gradation control method, an area gradation control method utilizing parts of discontinuous density, or a gradation control method obtained by combining the first two.
  • DDCP is an effective means for conducting output of a proof efficiently in the field of color proofs.
  • a color printer has a relatively simple structure and is inexpensive, and by using the color printer, as is well known, production of a preparation film for a color printer and production of a press plate (PS plate) and the like are not necessary, therefore, a hard copy obtained by forming an image on a sheet can be easily produced in a short period of time for several times.
  • LD or LED When LD or LED is used as a light source, it is preferable that three spectral sensitivities of yellow, magenta and cyan color forming layers, four spectral sensitivities of yellow, magenta, cyan and black color forming layers, or, for the purpose of obtaining a desirable hue, spectral sensitivities of the respective colors forming layers obtained by mixing two or more dye forming compound, have respective peaks of the spectral sensitivities at separate wavelengths respectively apart by 20 nm or more. Further, as another method, when the spectral sensitivities of two or more different colors differ by 10 times or more, a method in which an image of two or more colors is obtained by one radiation wavelength is also adopted.
  • the respective net point area ratio data aj of a CMYK4 size plate are respectively converted to 48800DPI bit map data b'j by referring to a threshold matrix 24. Then, the area ratio ci of each color is counted by referring simultaneously to the bit map data b'j in a given range. Then, the primary three stimulation value data X, Y, Z of 1600DPI, which show the measured value data of the above-described respective colors previously calculated, are calculated.
  • the secondary three stimulation value data X', Y', Z' of 400 DPI are calculated by anti-areazing filter processing of the primary three stimulation value data X, Y, Z.
  • the calculated data are used as input data for the color printer. (This is described in Japanese Patent Application No. 7-5257 in detail.)
  • a plurality of known color patches having different colors are produced using the output apparatus, and the colors of the above-described color patches are measured, to obtain, for example, a conversion relation (hereinafter referred to as the orderly conversion relation) in which the known color signals CMY of the above-described color patch are converted to stimulus value signals XYZ which do not depend on the output apparatus, then a conversion relation (hereinafter referred to as a reverse conversion relation) by which the stimulus value signals XYZ are converted to color signals CMY is calculated utilizing the orderly conversion relation, and the above-described color conversion processing is conducted using this reverse conversion relation.
  • a conversion relation hereinafter referred to as the orderly conversion relation
  • a conversion relation hereinafter referred to as a reverse conversion relation
  • the size of an image obtained from the heat developing photosensitive material and dye fixing element may be any of A line book size, A1 to A6, KIKU line book size (636mm ⁇ 939mm), B line book size, B1 to B6, four-six size.
  • the size of the heat developing photosensitive material and dye fixing element may be any size in the width range from 100 mm to 2000 mm, corresponding to the above-described sizes.
  • the materials may be supplied in the form of either a roll or sheet, and it is also possible that only one of them is in the form of roll, and the other is in the form of sheet.
  • Image receiving elements R101 having the structures shown in Table 1 and Table 2 were produced.
  • an oil-soluble compound was dissolved in the organic solvent having a high boiling point (1) and emulsified and dispersed before being added to the composition, and a water-soluble compound or latex was directly added to the composition.
  • a method for producing a photosensitive element is described.
  • Photosensitive silver halide emulsion (1) [for red sensitive emulsion layer]
  • a solution (I) having the composition shown in Table 4 was added to an aqueous solution having the composition shown in Table 3 at a constant flow rate with sufficient stirring over a period of 9 minutes, and a solution (II) was added at a constant flow rate 10 seconds before the addition of the solution (I) over a period of 9 minutes and 10 seconds. 36 minutes after the addition, a solution (III) having the composition shown in Table 4 was added at a constant flow rate over a period of 24 minutes, and a solution (IV) was added at a constant flow rate simultaneously with the solution (III) over a period of 25 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 880 g of lime-processed ossein gelatin was added to control pH to 6.0 before the addition of 12. 8 g of ribonucleic acid dissociated compound and 32 mg of trimethylthiourea, and the mixture was chemically sensitized for 71 minutes at 60°C, then, 2.6 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 3.2 g of a dye (a), 5.1 g of KBr and 2.6 g of a stabilizer described below were added one by one, and the resulting mixture was cooled.
  • Photosensitive silver halide emulsion (2) [for green sensitive emulsion layer]
  • Solutions (I) and (II) each having the composition shown in Table 6 were simultaneously added to an aqueous solution having the composition shown in Table 5 at a constant flow rate with sufficient stirring over a period of 9 minutes. 5 minutes after the addition , solutions (III) and (IV) each having the composition shown in Table 6 were simultaneously added at a constant flow rate over a period of 32 minutes. After completion of the addition of the solutions (III) and (IV), 60 ml of a methanol solution of dyes (containing 360 mg of a dye (b1) and 73.4 mg of a dye (b2)) was added at one time.
  • the mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.6 before addition of 1.8 mg of sodium thiosulfate and 180 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and the mixture was chemically sensitized at 60°C , then 90 mg of an anti-fogging agent (1) were added, and the resulting mixture was cooled. In this manner, 635 g of monodispersed cubic silver chloride bromide emulsion having an average particle size of 0.30 ⁇ m was obtained.
  • Photosensitive silver halide emulsion (3) [for blue sensitive emulsion layer]
  • Solutions (I) and (II) each having the composition shown in Table 8 were added to an aqueous solution having a composition as shown in Table 7, in a manner that the solution (II) was added first, and 10 seconds after, the solution (I) was added respectively over a period of 30 minutes with sufficient stirring. 2 minutes after completion of the addition of the (I) solution, a solution (V) was added, and 5 minutes after completion of the addition of the solution (II), a solution (IV) was added over a period of 28 minutes, and 10 seconds after, a solution (III) was added over a period of 27 minutes and 50 seconds.
  • the mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 1230 g of lime-processed ossein gelatin and 2.8 mg of a compound (b) were added to control pH to 6.1 and pAg to 8.4, before addition of 24.9 mg of sodium thiosulfate, and the mixture was chemically sensitized at 60°C, then, 13.1 g of a dye (c) and 118 ml of a compound (c) were added successively, and the resulting mixture was cooled.
  • the halide particles in the resulted emulsion were potato-like particles, and had an average particle size of 0.53 ⁇ m, with a yield of 30700 g.
  • Gelatin dispersions of yellow coupler (1), magenta coupler (1), cyan coupler (1) and developing agent were prepared respectively according to formulations shown in Table 9. Namely, oil phase components were heated at about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
  • a gelatin dispersion of an anti-fogging agent (4) was prepared according to the formulation shown in Table 10. Namely, oil phase components were heated at about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.
  • a dispersion of a polymer latex (a) was prepared according to the formulation shown in Table 11. Namely, to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 1 was added an anionic surfactant (6) over a period of 10 minutes while stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using a ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth. Dispersion composition Polymer latex (a) aqueous solution (solid content: 13%) 108ml Surfactant (5) 20g Anionic surfactant (6) 600ml Water 1232ml
  • a gelatin dispersion of zinc hydroxide was prepared according to a formulation shown in Table 12. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using glass beads having an average particle size of 0.75 mm by a mill. Further, the glass beads were separated and removed, to give a uniform dispersion. Dispersion composition Zinc hydroxide 15.9g Carboxymethylcellulose 0.7g Sodium polyacrylate 0.07g Lime-processed gelatin 4.2g Water 100ml Preservative (2) 0.4g
  • a gelatin dispersion of a reducing agent (1) was prepared according to the formulation shown in Table 13. Namely, oil phase components were heated at 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion. Further, ethyl acetate was removed from the resulted dispersion using a vacuum organic solvent removing apparatus.
  • a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described.
  • a solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed.
  • methylene chloride was removed by using a vacuum solvent removing apparatus to give a uniform dispersion having an average particle sized of 4.3 ⁇ m.
  • photosensitive materials 102 to 115 shown in Table 16 were produced by adding the compound of the present invention to the 1st, 3rd and 5th layers or the 2nd, 4th and 6th layers, and by changing the coupler and developing agent.
  • image output was conducted using photosensitive elements 101 to 117 and image receiving element R101 in heating conditions of 80°C for 30 seconds or 75°C for 30 seconds using a PICTOSTAT 330 manufactured by Fuji Photo Film Co., Ltd.
  • the resulting image was a clear color image.
  • ⁇ Maximum density and minimum density were measured by a reflection density meter X-lite 304 manufactured by X-lite Corp. ⁇
  • d-value (Minimum density/Maximum density) (when d value is low, discrimination is excellent).
  • Each photosensitive element was left for 5 days under 60°C -60%RH, then image formation was conducted under conditions of 80°C for 30 seconds as described above, and preservability of the photosensitive element was evaluated.
  • the photosensitive element of the present invention provided a clear color image even after preservation.
  • Image receiving elements were produced in the same manner as in Example 1.
  • Photosensitive silver halide emulsion (1) [emulsion for 5th layer (680 nm photosensitive layer)]
  • Solutions (I) and (II) each having the composition shown in Table 19 were simultaneously added to an aqueous solution having the composition shown in Table 18 with sufficient stirring over a period of 13 minutes, and 10 minutes after, solutions (III) and (IV) each having the composition shown in Table 19 were added over a period of 33 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 4.1 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.9, and the mixture was chemically sensitized at 60°C.
  • the compound used in the chemical sensitization is shown in Table 20.
  • the resulted emulsion (630 g) was a monodispersed cubic silver chloride bromide emulsion having a variation coefficient of 10.2% and an average particle size of 0.20 ⁇ m.
  • Drug used in chemical sensitization Amount added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.36g Sodium thiosulfate 6.75mg
  • Anti-fogging agent (1) 0.11g Preservative (1) 0.07g Preservative (2) 3.31g
  • Photosensitive silver halide emulsion (2) [emulsion for 3rd layer (750 nm photosensitive layer)]
  • Solutions (I) and (II) each having the composition shown in Table 22 were simultaneously added to an aqueous solution having a composition shown in Table 21 with sufficient stirring over a period of 18 minutes. 10 minute after the addition , solutions (III) and (IV) each having the composition shown in Table 22 were added over a period of 24 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 22 g of lime-processed ossein gelatin which had been subjected to de-calcium processing (calcium content: 150 PPM or less) was added, and the mixture was dispersed at 40°C, and 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to control pH to 5.9 and pAg to 7.8. Then, the mixture was chemically sensitized at 70°C using the chemicals shown in Table 23.
  • sensitizing dye (2) was added in the form of a methanol solution (the solution having the composition shown in Table 24). Further, after chemical sensitization, the solution was cooled down to 40°C, to this was added 200 g of a gelatin dispersion of a stabilizer (1) described later, and they were sufficiently stirred before being stored. The resulting emulsion was a monodispersion cubic silver chloride iodide having a variation coefficient of 12.6% and an average particle size of 0.25 ⁇ m, and the yield was 938 g. The emulsion for 750 nm photosensitive layer had J-band type spectral sensitivity.
  • Photosensitive silver halide emulsion (3) [emulsion for 1st layer (810 nm photosensitive layer)]
  • Solutions (I) and (II) each having the composition shown in Table 26 were added to an aqueous solution having the composition shown in Table 25 over a period of 18 minutes with sufficient stirring, and 10 minutes later, solutions (III) and (IV) each having the composition shown in Table 26 were added over a period of 24 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 3.8 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 7.4 and pAg to 7.8 before chemical sensitization at 60°C.
  • the compounds used in the chemical sensitization are shown in Table 27.
  • the resulting emulsion was a monodispersion cubic silver chloride bromide emulsion having a variation coefficient of 9.7% and an average particle size of 0.32 ⁇ m, and the yield was 680 g.
  • Gelatin dispersions of a yellow dye-forming coupler (1), a magenta dye-forming coupler (1), a cyan coupler dye-forming (1), and a developing agent were prepared respectively according to the formulations shown in Table 30. Namely, oil phase components were heated to about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed. It was then dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
  • a gelatin dispersion of an anti-fogging agent (4) was prepared according to the formulation shown in Table 31. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.
  • a gelatin dispersion of a reducing agent (1) was prepared according to the formulation shown in Table 32. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion. Further, ethyl acetate was removed from the resulting dispersion using a vacuum organic solvent removing apparatus.
  • a dispersion of a polymer latex (a) was prepared according to a formulation shown in Table 33. Namely, to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 33 was added an anionic surfactant (6) over a period of 10 minutes with stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using an ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth. Dispersion composition Polymer latex (a) aqueous solution (solid content: 13%) 108ml Surfactant (5) 20g Anionic surfactant (6) 600ml Water 1232ml
  • a gelatin dispersion of a reducing agent (1) was prepared according to the formulation shown in Table 34. Namely, oil phase components were dissolved at room temperature, to this solution were added aqueous phase components heated to about 40°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a dispersion. Further, water added and the mixture was stirred to give a uniform dispersion.
  • a gelatin dispersion of zinc hydroxide was prepared according to the formulation shown in Table 35. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using a glass bead having an average particle size of 0.75 mm by a mill. Further, the glass bead was separated and removed, to give a uniform dispersion. Dispersion composition Zinc hydroxide 15.9g Carboxymethylcellulose 0.7g Sodium polyacrylate 0.07g Lime-processed gelatin 4.2g Water 100ml Preservative (2) 0.4g
  • a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described.
  • a solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed.
  • methylene chloride was removed by using a vacuum solvent removing apparatus to give a uniform dispersion having an average particle size of 4.3 ⁇ m.
  • photosensitive elements 202 to 212 were prepared in the same manner as for the photosensitive element 201 except that the developing agents were changed to developing agents of yellow, magenta and cyan and the compounds of the present invention as shown in Table 38.
  • image output was conducted using the photosensitive elements 201 to 212 and image receiving element R101 under heating conditions of 83°C for 35 seconds or 78°C for 35 seconds, by a digital color printer FIJIX PICTOGRAPHY PG-3000 manufactured by Fuji Photo Film Co., Ltd.
  • the resulting image was a clear color image.
  • ⁇ Maximum density and minimum density were measured by using a reflection density meter X-lite 304 manufactured by X-lite Corp. ⁇
  • the photosensitive element of the present invention is not easily affected by differences in the processing conditions, and can provide an image having an excellent discrimination even under low temperature developing conditions.
  • Each photosensitive element was left for 5 days under 45°C -80%RH, then image formation was conducted under conditions of 83°C for 35 seconds as described above.
  • the photosensitive element of the present invention provided a clear color image.
  • the heat developing color photosensitive material of the present invention can provide an excellent image in an extremely short developing time and is not easily affected by variations in processing conditions. Further, the heat developing color photosensitive material is able to provide an image in lower temperature processing conditions and has excellent ptorability.
  • a method for preparing a photosensitive element (heat developing photosensitive material) is described below.
  • Photosensitive silver halide emulsion (1) [for red sensitive emulsion layer]
  • a solution (I) having the composition shown in Table 41 was added to an aqueous solution having the composition shown in Table 40 at a constant flow rate with sufficient stirring over a period of 9 minutes, and a solution (II) was added at a constant flow rate 10 seconds before the addition of the solution (I) over a period of 9 minutes and 10 seconds. 36 minutes after the addition, a solution (III) having the composition shown in Table 41 was added at a constant flow rate over a period of 24 minutes, and a solution (IV) was added at a constant flow rate simultaneously with the solution (III) over a period of 25 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 880 g of lime-processed ossein gelatin was added to control pH to 6.0 before the addition of 12. 8 g of ribonucleic acid dissociated compound and 32 mg of trimethylthiourea, and the mixture was chemically sensitized for 71 minutes at 60°C, then, 2.6 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 3.2 g of a dye (a), 5.1 g of KBr and 2.6 g of a stabilizer (1) described below were added one by one, and the resulting mixture was cooled.
  • Photosensitive silver halide emulsion (2) [for green sensitive emulsion layer]
  • Solutions (I) and (II) each having the composition shown in Table 43 were simultaneously added to an aqueous solution having the composition shown in Table 42 at a constant flow rate with sufficient stirring over a period of 9 minutes. 5 minutes after the addition , solutions (III) and (IV) each having the compositions shown in Table 43 were simultaneously added at a constant flow rate over a period of 32 minutes. After completion of the addition of the solutions (III) and (IV), 60 ml of a methanol solution of dyes (containing 360 mg of a dye (b1) and 73.4 mg of a dye (b2)) was added in one time.
  • the mixture was washed with water and desalted (conducted at a pH of 4.0 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.6 before the addition of 1.8 mg of sodium thiosulfate and 180 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and the mixture was chemically sensitized at 60°C, then 90 mg of an anti-fogging agent (1), and the resulting mixture was cooled. In this manner, 635 g of monodispersed cubic silver chloride bromide emulsion having an average particle size of 0.30 ⁇ m was obtained.
  • Photosensitive silver halide emulsion (3) [for blue sensitive emulsion layer]
  • Solutions (I) and (II) each having the compositions shown in Table 45 were added to an aqueous solution having the composition shown in Table 44 in a manner that the solution (II) was added first, and 10 seconds later, the solution (I) was added over a period of 30 minutes each with sufficient stirring. 2 minutes after completion of the addition of the (I) solution, a solution (V) was added, and 5 minutes after completion of the addition of the solution (II), a solution (IV) was added over a period of 28 minutes, and 10 seconds later, a solution (III) was added over a period of 27 minutes and 50 seconds.
  • the mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 1230 g of lime-processed ossein gelatin and 2.8 mg of a compound (b) were added to control pH to 6.1 and pAg to 8.4 before addition of 24.9 mg of sodium thiosulfate, and the mixture was chemically sensitized at 60°C, then, after 13.1 g of a dye (c) and 118 ml of a compound (c) were added successively, the resulting mixture was cooled.
  • the halide particles in the resulted emulsion were potato-like particles, and had an average particle size of 0.53 ⁇ m, and the yield was 30700 g.
  • Gelatin dispersions of a yellow dye-forming coupler, a magenta dye-forming coupler, a cyan dye-forming coupler, and a developing agent were prepared respectively according to formulations shown in Table 46. Namely, oil phase components were heated to about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
  • a gelatin dispersion of an anti-fogging agent (4) and reducing agent (1) was prepared according to the formulation shown in Table 47. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.
  • a dispersion of a polymer latex (a) was prepared according to the formulation shown in Table 48. Namely, to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 48 was added an anionic surfactant (6) over a period of 10 minutes while stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using an ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth. Dispersion composition Polymer latex (a) aqueous solution (solid content: 13%) 108ml Surfactant (5) 20g Surfactant (6) 600ml Water 1232ml
  • a gelatin dispersion of zinc hydroxide was prepared according to the formulation shown in Table 49. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using glass beads having an average particle size of 0.75 mm by a mill. Further, the glass beads were separated and removed, to give a uniform dispersion. Dispersion composition Zinc hydroxide 15.9g Carboxymethylcellulose 0.7g Sodium polyacrylate 0.07g Lime-processed gelatin 4.2g Water 100ml Preservative (2) 0.4g
  • a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described.
  • a solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed.
  • methylene chloride was removed by a vacuum solvent removing apparatus to give a uniform dispersion having an average particle size of 4.3 ⁇ m.
  • heat developing photosensitive materials 302 to 321 were produced in the same manner as described above, except that the developing agent, coupler and the compounds of the present invention represented by the general formulae (II) and (III) were added to the 1st, 3rd and 5th layers or 2nd, 4th and 6th layers in the amounts shown in Tables 52 and 53.
  • image output was conducted using the above-described heat developing photosensitive elements 301 to 321 and image receiving element R101, as in Example 1 in heating conditions of 80°C for 30 seconds or 75°C for 30 seconds by PICTOSTAT 330 manufactured by Fuji Photo Film Co., Ltd.
  • the image output on a dye fixing material was a clear color image. ⁇ Maximum density and minimum density were measured by using a reflection density meter X-lite 304 manufactured by X-lite Corp. ⁇
  • d-value (Minimum density/Maximum density) (when d value is low, discrimination is excellent).
  • Each heat developing photosensitive material was left for 5 days under 60°C -60%RH, then image formation was conducted in conditions of 80°C for 30 seconds as described above, and preservability of the heat developing photosensitive material was evaluated.
  • the heat developing photosensitive material of the present invention could provide a clear color image even after storage.
  • Image receiving elements (dye fixing materials) were produced in the same manner as in Example 1.
  • Photosensitive silver halide emulsion (1) [emulsion for 5th layer (680 nm photosensitive layer)]
  • Solutions (I) and (II) each having the compositions shown in Table 55 were simultaneously added to an aqueous solution having the composition shown in Table 54 with sufficient stirring over a period of 13 minutes, and 10 minutes later, solutions (III) and (IV) each having the compositions shown in Table 55 were added over a period of 33 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 4.1 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 6.0 and pAg to 7.9, and the mixture was chemically sensitized at 60°C.
  • the compound used in the chemical sensitization is shown in Table 56.
  • the resulting emulsion (630 g) was a monodispersed cubic silver chloride bromide emulsion having a variation coefficient of 10.2%, and an average particle size of 0.20 ⁇ m.
  • Drug used in chemical sensitization Amount added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.36g Sodium thiosulfate 6.75mg
  • Anti-fogging agent (1) 0.11g Preservative (1) 0.07g Preservative (2) 3.31g
  • Photosensitive silver halide emulsion (2) [emulsion for 3rd layer (750 nm photosensitive layer)]
  • Solutions (I) and (II) each having the compositions shown in Table 58 were simultaneously added to an aqueous solution having the composition shown in Table 57 with sufficient stirring over a period of 18 minutes. 10 minutes after the addition, solutions (III) and (IV) each having the compositions shown in Table 58 were added over a period of 24 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 3.9 using a flocculating agent b) by ordinary methods, then 22 g of lime-processed ossein gelatin which had been subjected to de-calcium treatment (calcium content: 150 PPM or less) was added, and the mixture was dispersed at 40°C, and 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to control pH to 5.9 and pAg to 7.8. Then, the mixture was chemically sensitized at 70°C using chemicals shown in Table 59.
  • sensitizing dye was added in the form of a methanol solution (solution having the composition shown in Table 60). Further, after chemical sensitization, the solution was cooled down to 40°C, to this was added 200 g of a gelatin dispersion of a stabilizer (1) described later, and they were sufficiently stirred before being stored. The resulting emulsion was a monodispersion cubic silver chloride iodide having a variation coefficient of 12.6% and an average particle size of 0.25 ⁇ m, and the yield was 938 g. The emulsion for 750 nm photosensitive layer had J-band type spectral sensitivity.
  • Drug used in chemical sensitization Amount added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.39g Triethyl thiourea 3.3mg Nucleic acid decomposed material 0.39g NaCl 0.15g KI 0.12g Anti-fogging agent (2) 0.10g Preservative (1) 0.07g Composition of dye solution Amount added Sensitizing dye (2) 0.19g Methanol 18.7cc
  • Photosensitive silver halide emulsion (3) [emulsion for 1st layer (810 nm photosensitive layer)]
  • Solutions (I) and (II) each having the composition shown in Table 62 were added to an aqueous solution having the composition shown in Table 61 over a period of 18 minutes with sufficient stirring, and 10 minutes later, solutions (III) and (IV) each having the compositions shown in Table 62 were added over a period of 24 minutes.
  • the mixture was washed with water and desalted (conducted at a pH of 3.8 using a flocculating agent a) by ordinary methods, then 22 g of lime-processed ossein gelatin was added to control pH to 7.4 and pAg to 7.8 before chemical sensitization at 60°C.
  • the compounds used in the chemical sensitization are shown in Table 63.
  • the resulting emulsion was a monodispersion cubic silver chloride bromide emulsion having a variation coefficient of 9.7% and an average particle size of 0.32 ⁇ m, and the yield was 680 g.
  • Drug used in chemical sensitization Amount added 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene 0.38g Triethyl thiourea 3.1mg Anti-fogging agent (2) 0.19g Preservative (1) 0.07g Preservative (2) 3.13g
  • Gelatin dispersions of a yellow coupler, a magenta coupler, a cyan coupler, and a developing agent were prepared respectively according to the formulations shown in Table 66. Namely, oil phase components were heated to about 70°C to be dissolved to form a uniform solution, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes. To this was added water, and the solution was stirred to give a uniform dispersion.
  • a gelatin dispersion of an anti-fogging agent (4) and a reducing agent (1) was prepared according to the formulation shown in Table 67. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion.
  • a gelatin dispersion of a reducing agent (2) was prepared according to the formulation shown in Table 68. Namely, oil phase components were heated to about 60°C to be dissolved, to this solution were added aqueous phase components heated to about 60°C, and the solution was stirred and mixed, then was di000spersed at 10000 rpm by a homogenizer for 10 minutes to give a uniform dispersion. Further, ethyl acetate was removed from the resulting dispersion using a vacuum organic solvent removing apparatus.
  • a dispersion of a polymer latex (a) was prepared according to the formulation shown in Table 69. Namely, an anionic surfactant (6) was added to a mixture of a polymer latex (a), surfactant (5) and water in amounts shown in Table 31 over a period of 10 minutes while stirring to give a uniform dispersion. Further, the resulting dispersion was repeatedly diluted with water and concentrated using a ultrafiltration module (ultrafiltration module manufactured by Asahi Chemical Industry Co., Ltd.: ACV-3050) to decrease salt concentration in the dispersion to one-ninth. Dispersion composition Polymer latex (a) aqueous solution (solid content: 13%) 108ml Surfactant (5) 20g Surfactant (6) 600ml Water 1232ml
  • a gelatin dispersion of a stabilizing agent (1) was prepared according to the formulation shown in Table 70. Namely, oil phase components were dissolved at room temperature, to this solution were added aqueous phase components heated to about 40°C, and the solution was stirred and mixed, then was dispersed at 10000 rpm by a homogenizer for 10 minutes to give a dispersion. Further, water added and the mixture was stirred to give a uniform dispersion.
  • a gelatin dispersion of zinc hydroxide was prepared according to a formulation shown in Table 71. Namely, components were mixed and dissolved, and then dispersed for 30 minutes using glass beads having an average particle size of 0.75 mm by a mill. Further, the glass beads were separated and removed, to give a uniform dispersion.
  • Dispersion composition Zinc hydroxide 15.9g Carboxymethylcellulose 0.7g Sodium polyacrylate 0.07g Lime-processed gelatin 4.2g Water 100ml Preservative (2) 0.4g
  • a method for preparing a gelatin dispersion of a matting agent added to a protective layer is described.
  • a solution obtained by dissolving PMMA in methylene chloride was added to gelatin together with a small amount of a surfactant, and the mixture was stirred at high speed to be dispersed.
  • methylene chloride was removed by a vacuum solvent removing apparatus to give a uniform dispersion having an average particle sized of 4.3 ⁇ m.
  • heat developing photosensitive materials 402 to 412 were prepared in the same manner as for the heat developing photosensitive material 401, except that the developing agents were changed to developing agents of yellow, magenta and cyan and the compounds of the present invention as shown in Tables 74 and 75.
  • image output was conducted using the heat developing photosensitive materials 201 to 212 and image receiving elements under heating conditions of 83°C for 35 seconds or 78°C for 35 seconds by a digital color printer FIJIX PICTOGRAPHY PG-3000 manufactured by Fuji Photo Film Co., Ltd.
  • the output image was a clear color image.
  • ⁇ Maximum density and minimum density were measured by using a reflection density meter X-lite 304 manufactured by X-lite Corp. ⁇
  • the heat developing photosensitive material of the present invention can provide an excellent image even under low temperature developing conditions.
  • Each heat developing photosensitive material was left for 5 days under 45°C -80%RH, then image formation was conducted under conditions of 83°C for 35 seconds as described above.
  • the heat developing photosensitive material of the present invention provided a clear color image.
  • the heat developing color photosensitive material of the present invention can provide an excellent image in a short developing time and is not easily affected by variations in processing conditions. Further, the heat developing color photosensitive material is able to provide an image under lower temperature processing conditions.

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EP98100400A 1997-01-13 1998-01-12 Matériau photosensible en couleurs développable à la chaleur Expired - Lifetime EP0853255B1 (fr)

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EP0930528A1 (fr) * 1998-01-16 1999-07-21 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent sensible à la lumière
US6251576B1 (en) 1997-01-13 2001-06-26 Fuji Photo Film Co., Ltd. Photosensitive composition and color photosensitive materials
US6380258B2 (en) * 1997-03-04 2002-04-30 G. D. Searle, L.L.C. Sulfonyl divalent aryl or heteroaryl hydroxamic acid compounds
EP1284440A1 (fr) * 2001-08-13 2003-02-19 Eastman Kodak Company Un élément photothermographique couleur comprenant un système formant colorant pour former un colorant infrarouge nouveau
US6683078B2 (en) 2001-07-19 2004-01-27 Pharmacia Corporation Use of sulfonyl aryl or heteroaryl hydroxamic acids and derivatives thereof as aggrecanase inhibitors
US6696449B2 (en) 1997-03-04 2004-02-24 Pharmacia Corporation Sulfonyl aryl hydroxamates and their use as matrix metalloprotease inhibitors
US6794511B2 (en) 1997-03-04 2004-09-21 G. D. Searle Sulfonyl aryl or heteroaryl hydroxamic acid compounds
US7115632B1 (en) 1999-05-12 2006-10-03 G. D. Searle & Co. Sulfonyl aryl or heteroaryl hydroxamic acid compounds

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
US6251576B1 (en) 1997-01-13 2001-06-26 Fuji Photo Film Co., Ltd. Photosensitive composition and color photosensitive materials
US6423485B1 (en) 1997-01-13 2002-07-23 Fuji Photo Film Co., Ltd. Photosensitive composition and color photosensitive materials
US6380258B2 (en) * 1997-03-04 2002-04-30 G. D. Searle, L.L.C. Sulfonyl divalent aryl or heteroaryl hydroxamic acid compounds
US6656954B2 (en) 1997-03-04 2003-12-02 Pharmacia Corporation Sulfonyl divalent aryl or heteroaryl hydroxamic acid compounds
US6696449B2 (en) 1997-03-04 2004-02-24 Pharmacia Corporation Sulfonyl aryl hydroxamates and their use as matrix metalloprotease inhibitors
US6794511B2 (en) 1997-03-04 2004-09-21 G. D. Searle Sulfonyl aryl or heteroaryl hydroxamic acid compounds
EP0930528A1 (fr) * 1998-01-16 1999-07-21 Fuji Photo Film Co., Ltd. Matériau photographique à l'halogénure d'argent sensible à la lumière
US7115632B1 (en) 1999-05-12 2006-10-03 G. D. Searle & Co. Sulfonyl aryl or heteroaryl hydroxamic acid compounds
US6683078B2 (en) 2001-07-19 2004-01-27 Pharmacia Corporation Use of sulfonyl aryl or heteroaryl hydroxamic acids and derivatives thereof as aggrecanase inhibitors
EP1284440A1 (fr) * 2001-08-13 2003-02-19 Eastman Kodak Company Un élément photothermographique couleur comprenant un système formant colorant pour former un colorant infrarouge nouveau

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DE69801530D1 (de) 2001-10-11
EP0853255B1 (fr) 2001-09-05
DE69801530T2 (de) 2002-05-08
ATE205306T1 (de) 2001-09-15
EP0853255A3 (fr) 1998-07-22

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