EP0418743A2 - Wärmeentwickelbares lichtempfindliches Material - Google Patents

Wärmeentwickelbares lichtempfindliches Material Download PDF

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Publication number
EP0418743A2
EP0418743A2 EP90117690A EP90117690A EP0418743A2 EP 0418743 A2 EP0418743 A2 EP 0418743A2 EP 90117690 A EP90117690 A EP 90117690A EP 90117690 A EP90117690 A EP 90117690A EP 0418743 A2 EP0418743 A2 EP 0418743A2
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EP
European Patent Office
Prior art keywords
group
substituted
unsubstituted
dye
sensitive material
Prior art date
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EP90117690A
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English (en)
French (fr)
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EP0418743A3 (en
Inventor
Toshiki Fuji Photo Film Co. Ltd. Taguchi
Takeshi Fuji Photo Film Co. Ltd. Nakamine
Takayuji Fuji Photo Film Co. Ltd. Ito
Koki Fuji Photo Film Co. Ltd. Nakamura
Hisashi Fuji Photo Film Co. Ltd. Mikoshiba
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP24096389A external-priority patent/JPH03102345A/ja
Priority claimed from JP26955689A external-priority patent/JP2612206B2/ja
Priority claimed from JP30107689A external-priority patent/JP2612207B2/ja
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Publication of EP0418743A2 publication Critical patent/EP0418743A2/de
Publication of EP0418743A3 publication Critical patent/EP0418743A3/en
Withdrawn legal-status Critical Current

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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

Definitions

  • This invention relates to a heat-developable light-sensitive material and more particularly to a heat-developable light-sensitive material having excellent shelf life and capable of obtaining images having good discrimination.
  • a heat-developable light-sensitive material is known in the field of the art and heat-developable light-sensitive materials and processes for them are described in Shashin Kogaku no Kiso (Foundation of Photographic Engineering) , Chapter of Non-Silver Salt Photography, pages 242 to 255 (published by Corona Sha, 1982).
  • the aforesaid heat-developable light-sensitive material obtaining color images is of a non-fixing type, a silver halide remains after the formation of images and hence when the color images are exposed to intense light or stored for a long period of time, there occurs a serious problem that the background portion is gradually colored. Furthermore, the aforesaid processes have defects that a relatively long period of time is required for the development and the images obtained have high fog and a low image density.
  • the developing temperature is still high and the storage stability of the light-sensitive materials is insufficient.
  • U.S. Patent 4,559,290 provides a process of heat developing in the existence of a so-called DRR compound which has been converted into an oxidized type having no dye-releasing faculty, and a reducing agent or a precursor thereof to oxidize the reducing agent or the precursor in accordance with the exposed amount of silver halide and reducing the aforesaid compound with the reducing agent or the precursor remaining without being oxidized to release a diffusible dye.
  • EP-A-220746 and Kokai Giho Vol. 12, No.
  • JP-A-1-138556 and JP-A-1-177029 that when a reducing agent having a faculty of reducing silver halide exists in the binder in the heat-developable light-sensitive material as described above, the reducing agent is oxidized by oxygen in air during the preservation of the light-sensitive material, whereby the content of the reducing agent is decreased.
  • the decrease of the reducing agent during the storage of the light-sensitive material before use results in the decrease the developing speed of the silver halide into silver at processing and the decrease of the total developed silver amount to deteriorate the discrimination of images formed.
  • JP-A-59-182449 JP-A-59-182450, JP-A-61-34540, and JP-A-1-138558.
  • JP-A-1-138556 a technique of using a reducing agent and a reducing agent precursor is disclosed in JP-A-1-138556.
  • the object of this invention is, therefore, to provide a heat-developable light-sensitive material having excellent shelf life and capable of giving images showing a good discrimination.
  • a heat-developable light-sensitive material comprising a support having thereon at least a light-sensitive silver halide, a binder, and a reducing agent precursor represented by following formula (I) or (II) and having a melting point of not higher than 120° C;
  • R , R 2 , R 3 , and R 4 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group;
  • R s represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group;
  • R, to R 4 each represents a hydrogen atom, a substituted or unsubstituted alkyl group (preferably having not more than 20 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, hexyl, octyl, t-octyl, decyl, dodecyl, hexadecyl, octadecyl, alkoxymethyl, hydroxymethyl, chloromethyl, bromomethyl, acyloxymethyl), a substituted or unsubstituted aryl group (preferably having not more than 20 carbon atoms, for example, phenyl, tolyl, xylyl, cumyl, halogenophenyl, nitrophenyl, sulfophenyl, carboxyphenyl, alkoxyphenyl, alkylphenyl, naphthyl, anthryl), or a substituted or unsubsti
  • R 5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted hetero cyclic group and practical examples of these groups are same as those illustrated above in regard to R i to R 4 .
  • X represents a substituted alkyl group, preferably -CH 2 -K (wherein K represents a halogen atom an alkoxy group, an aryloxy group, an acyloxy group, a carbonic acid ester group, an amino group, a carbonamido group, a sulfonamido group, a ureido group, an aminosulfonamido group a carbamate group, a carboxy group, an oxycarbonyl group, a carbamoyl group, an acyl group, a sulfo group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, a cyano group, or a nitro group), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoy
  • Examples of the hydrolyzable group shown by R' 6 are (wherein R 17 represents an aliphatic group having from 1 to 22 carbon atoms, an aromatic group having from 6 to 10 carbon atoms or a heterocyclic group; R 18 and R' 9 each represents a hydrogen atom, an aliphatic group having from 1 to 22 carbon atoms, an aromatic group having from 6 to 10 carbon atoms, or a heterocyclic group; said R 18 and R' 9 may be the same or different; and the aliphatic group shown by R17, R' 8 or R 19 may be substituted or unsubstituted, chain like, or cyclic).
  • Preferred examples of the substituent for the aliphatic group shown by the aforesaid groups are an alkoxy group, an aryloxy group, an acylamino group, a carbamoyl group, a halogen atom, a sulfonamido group, a sulfamoyl group, a carboxy group, an alkanoyloxy group, a benzoyloxy group, a cyano group, a hydroxy group, a ureido group, a carbonyl group, an aryl group, an alkylsulfonyl group, an alkoxycarbonyl group, an alkylureido group, an imidazolyl group, a furyl group, a nitro group, a phthalimido group, a thiazolyl group, an alkanesulfonamido group, an alkanesulfamoyl group, an arylcarbonyl group, an imido
  • R 17 , R 18 , and R 19 each represents an aromatic group (in particular, a phenyl group)
  • the aromatic group may be substituted. That is, the aromatic group such as a phenyl group, etc., may be substituted by a halogen atom, a nitro group, a hydroxy group, a cyano group, a carboxy group, an alkyl group having from 1 to 32 carbon atoms, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an alkanoyloxy group, an alkoxycarbonylamino group, an aliphatic amido group, an alkylsulfamoyl group, an alkylsulfonamido group, an alkylureido group, an alkylsulfonyl group, an alkyl-substituted succinimido group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene, etc., in
  • the phenylene group may be substituted by an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamido group, an arylureido group, etc., and the aryl moiety of the substituent may be further substituted by at least one alkyl group having the total carbon atom number of from 1 to 22.
  • R 17 , R 18 , and R 19 each represents a heterocyclic group
  • the heterocyclic group is bonded to a linkage group having an auxiliary developing agent bonded thereto via one of the carbon atoms forming the ring.
  • Examples of such a heterocyclic ring are thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine.
  • These heterocyclic rings may further have a substituent on the ring.
  • a reducing agent can be used together with the aforesaid reducing agent precursor.
  • the reducing agent which is released from the reducing agent precursor may be same or different from the reducing agent being used together with the reducing agent precursor.
  • the reducing agent which can be used with the reducing agent precursor in this invention, reducing agents known in the field of heat-developable light-sensitive material can be used.
  • the reducing agents include dye-providing compounds having a reductive property as will be described later (in this case, the dye-providing compound can be used with other reducing agent).
  • the reducing agent released from the reducing agent precursor for use in this invention functions as an electron transferring agent accelerating the electron transfer between the nondiffusible reducing agent and a developable silver halide.
  • an electron transferring agent (of a non-precursor type) can be used as a combination therewith.
  • the electron transferring agent can be selected from the aforesaid reducing agents. It is preferred that the mobility of the electron transferring agent is larger than that of the nondiffusible reducing agent (electron donor).
  • Particularly useful diffusible reducing agent such as an electron transferring agent are 1-phenyl-3-pyrazolidinones and preferred examples thereof are described in JP-A-64-13546, pages 49 to 63.
  • the nondiffusible reducing agent which is used as a combination with a diffusible reducing agent
  • the aforesaid reducing agents which do not substantially transfer in the layer of the light-sensitive material can be used and preferred examples thereof are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, the electron donors described in JP-A-53-110827, and dye-providing compounds having a nondiffusible property and a reductive property, which will be described hereinbelow.
  • the total addition amounts of the reducing agent including the reducing agent precursor in this invention are from 0.001 to 20 mols, and preferably from 0.01 to 10 mols per mol of silver.
  • the amount of the diffusible reducing agent is not more than about 40 mol% of the amount of the total reducing agents.
  • the heat-developable light-sensitive material of this invention has fundamentally a light-sensitive silver halide, a binder, and the aforesaid reducing agent precursor on a support and if necessary, the light-sensitive material can further contain a dye-providing compound, a base precursor, etc. These components exist generally in one layer but they may separately exist in separate layer(s) if they are in the states of causing reaction. For example, when a colored dye-providing compound exists in a layer under a silver halide emulsion layer, the occurrence of the decrease of sensitivity can be prevented.
  • each light-sensitive layer may be composed of two or more layers.
  • heat-developable light-sensitive material may form various auxiliary layers such as a protective layer, a subbing layer, interlayers, a yellow filter layer, an antihalation layer, a back layer, etc.
  • the silver halide for use in this invention may be silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide.
  • the silver halide emulsion for use in this invention may be a surface latent image type emulsion or an internal latent image type emulsion.
  • the internal latent image type emulsion is used as a direct reversal emulsion by combination with a nucleating agent or a light fogging method.
  • the silver halide emulsion for use in this invention may be a so-called core/shell emulsion of silver halide grains having a different phase between the inside of the grain and the surface of the grain.
  • the silver halide emulsion may be a monodisperse emulsion or a polydisperse emulsion or a mixture of monodisperse emulsions may be used.
  • the mean grain size of the silver halide grains is preferably from 0.1 to 2 um, and particularly preferably from 0.2 to 1.5 um.
  • the crystal form of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular grains of a high aspect ratio, etc.
  • the silver halide emulsion may be used as a primitive emulsion but is usually chemically sensitized.
  • a sulfur sensitization, a reduction sensitization, and a noble metal sensitization which are known for silver halide emulsion for ordinary silver halide light-sensitive materials can be used singly or as a combination thereof.
  • the chemical sensitization can be carried out in the existence of a nitrogen-containing heterocyclic compound as disclosed in JP-A-62-253159.
  • the coating amount of the light-sensitive silver halide for use in this invention is in the range of from 1 mg/m 2 to 10 g/ M 2 , calculated in terms of silver.
  • an organic metal salt can be used with a light-sensitive silver halide as an oxidizing agent.
  • an organic silver salt is particularly preferably used.
  • organic silver salt oxidizing agent As an organic compound which is used for forming the aforesaid organic silver salt oxidizing agent, there are benzotriazoles described in U.S. Patent 4,500,626, columns 52 to 53, fatty acids, and other compounds. Also, silver salts of a carboxylic acid having an alkinyl group, such as silver phenylpropiolate, etc., described in JP-A-60-113235 and acetylene silver described in JP-A-61-249044 are useful in this invention. Organic silver salts may be used singly or as a combination of them.
  • the organic silver salt can be used in an amount of from 0.01 to 10 mols, and preferably from 0.01 to 1 mol per mol of the light-sensitive silver halide.
  • the total coating amount of the light-sensitive silver halide and the organic silver salt is from 50 mg/m 2 to 10 g/m 2 , calculated in terms of silver.
  • various antifoggants or photographic stabilizers can be used. Examples of them are azoles and azaindenes described in RD , Vol. 17643, pages 24 to 25 (Dec., 1978), nitrogen-containing carboxylic acids and nitrogen-containing phosphoric acids described in JP-A-59-168442, mercapto compounds and the metal salts thereof described in JP-A-59-111636, and acetylene compounds described in JP-A-62-87957.
  • the silver halide emulsion for use in this invention may be spectrally sensitized by methine dyes, etc.
  • the dyes which are used for the spectral sensitization include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
  • sensitizing dyes may be used singly or as a combination thereof and a combination of sensitizing dyes is frequently used for the purpose of super-sensitization.
  • the silver halide emulsion for use in this invention may contain a dye having a spectral sensitizing action by itself but showing a super-sensitization, or a compound absorbing substantially no visible light but showing a supersensitization together with a sensitizing dye as described in U.S. Patent 3,615,641 and JP-A-63-23145.
  • sensitizing dyes may be added to a silver halide emulsion, before, during, or after chemical ripening of the emulsion. Also, the sensitizing dyes may be added to the silver halide emulsion before or after the nucleation of the silver halide grains as described in U.S. Patents 4,183,756 and 4,225,666. The addition amount of the sensitizing dye is from about 1 x1 0-8 to 1 x1 0-2 mol per mol of the silver halide.
  • hydrophilic binders are preferably used as the binders for the constitution layers of the light-sensitive material and a dye-fixing material. Examples thereof are described in JP-A-62-253159, pages 26 to 28.
  • hydrophilic binders are preferred and specific examples are proteins such as gelatin, gelatin derivatives; cellulose derivatives; polysaccharides such as starch, gum arabic, dextran, pullulan, or other natural compounds; and synthetic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, acrylamide polymer, etc.
  • the high water-absorptive polymers described in JP-A-62-245260 i.e., the homopolymer of a vinyl monomer having -COOM or -S0 3 M' (wherein M represents a hydrogen atom or an alkali metal) or copolymers of such vinyl monomers each other or the vinyl monomer and other vinyl monomer (e.g., sodium methacrylate, ammonium methacrylate, and Sumica Get L-5H, trade name, made by Sumitomo Chemical Company, Limited) can be used. These binders may be used singly or as a combination of them.
  • the absorption of water can be quickly carried out by using the aforesaid high water-absorptive polymer.
  • the high water-absorptive polymer is used for a dye-fixing layer or a protective layer therefor, the dyes transferred to a dye-fixing material can be prevented from re-transferring therefrom to other layer or materials.
  • the coating amount of the binder is peferably not more than 20 g, more preferably not more than 10 g, and particularly preferably not more than 7 g per square meter.
  • the layers (including back layers) constituting the light-sensitive material or the dye-fixing material can contain various polymer latexes for dimensional stabilization, curling prevention, sticking prevention, cracking prevention of layers, prevention of pressure sensitization or desensitization, etc. Practically, the polymer latexes described in JP-A-62-245258, JP-A-62-136648, and JP-A-62-110066 can be used.
  • the polymer latex having a low glass transition point (not higher than 40 C)
  • the occurrence of cracking of the mordant layer can be prevented and when the polymer latex having a high glass transition point is used for the back layer, a curling prevention effect is obtained.
  • silver As an image-forming substance, silver can be used.
  • a dye-providing compound i.e., a compound of forming or releasing a mobile dye corresponding or conter-corresponding to a reaction at the case of reducing a silver ion to silver at a high-temperature state can be used.
  • a compound (coupler) forming a dye by an oxidative coupling reaction can be used as an example of the dye-providing compound which can be used in this invention.
  • the coupler may be a four-equivalent coupler or a two-equivalent coupler. Also, a two-equivalent coupler having a nondiffusible dye as the releasable group and forming a nondiffusible dye by an oxidative coupling reaction can be preferably used.
  • the nondiffusible group may form a polymer chain.
  • the dye-providing compound there is a compound having a function of imagewise releasing or diffusing a diffusible dye.
  • the compound of this type can be shown by the following formula (Ll): wherein Dye represents a dye group, a dye group temporarily shifted to a short wave side, or a dye precursor group; Y represents a single bond or a linkage group; Z represents a group having a property of giving a difference in diffusibility of the compound shown by (Dye-Y) n -Z corresponding or counter-corresponding to the light-sensitive silver salt imagewise having latent images, or releasing Dye and giving a difference of diffusibility between Dye and (Dye-Y) n -Z; and n represents 1 or 2, when n is 2, two Dye-Y's may be the same or different.
  • the dye-providing compound shown by formula (LI) described above include the following compounds (1) to (5).
  • the following compounds (1) to (3) each forms a diffusible dye image (positive dye image) counter-corresponding to the development of silver halide
  • the compound (4) and (5) each forms a diffusible dye image (negative dye image) corresponding to the development of silver halide.
  • Examples thereof include a compound releasing a diffusible dye by an intramolecular nucleophilic displacement reaction after being reduced described in U.S. Patents 4,139,389 and 4,139,379, JP-A-59-185333 and JP-A-57-84453, a compound releasing a diffusible dye by an intramolecular electron transfer reaction after being reduced described in U.S. Patent 4,232,107, JP-A-59-101649 and JP-A-61-88257, and RD 24025 (April, 1984), a compound releasing a diffusible dye by the cleavage of a single bond after being reduced described in DE-A-3008588, JP-A-56-142530, and U.S.
  • the dye-providing compound include a compound an N-X bond (wherein X represents oxygen, sulfur or nitrogen) and an electron attractive group in one molecule described in EP-A-220746, Kokai Giho 87-6199, U.S. Patent 4,783,396, JP-A-63-201653 and JP-A-63-201654, a compound having S0 2 -X (wherein X is the same as defined above) and an electron attractive group in one molecule described in Japanese Patent Application No.
  • JP-A-1-26842 a compound having a PO-X bond (wherein X is the same as defined above) and an electron attractive group in one molecule described in JP-A-63-271344, and a compound having a C-X bond (wherein X has the same meaning as X or -S0 2 -) and an electron attractive group in one molecule described in JP-A-63-271341.
  • the compounds releasing a diffusible dye by the cleavage of a single bond after being reduced by a 7 r bond conjugated with an electron-acceptive group described in Japanese Patent Application Nos. 62-319989 and 62-320771 can be utilized in this invention as the dye-providing compound.
  • the compound having an N-X bond and an electron attractive group in one molecule are particularly preferred.
  • Practical examples of these compounds are described in EP-A-220746 and U.S. Patent 4,783,396 as compounds (1) to (3), (7) to (10), (12), (13), (15), (23) to (26), (31 (32), (35), (36), (40), (41 (44), (53) to (59), (64), and (70), and Kokai Giho , 87-6199 as compounds (11) to (23).
  • DDR coupler which is a coupler having a diffusible dye as a releasable group and releases the diffusible dye by the reaction with the oxidation product of a reducing agent.
  • DDR coupler is a coupler having a diffusible dye as a releasable group and releases the diffusible dye by the reaction with the oxidation product of a reducing agent.
  • JP-B-48-39165 the term "JP-B” as used herein means an "examined Japanese patent publication", U.S. Patents 3,443,940, 4,474,867, and 4,483,914.
  • Patents 3,725,062, 3,728,113, and 3,443,939, JP-A-58116537 and JP-A-57-179840, and U.S. Patent 4,500,626 As specific examples of the DRR compound, there are the compounds described in U.S. Patent 4,500,626, columns 22 to 44 but in these compounds, the compounds (1) to (3), (10) to (13), (16) to (19), (28) to (30), (33) to (35), (38) to (40), and (42) to (64) described in the aforesaid U.S. Patent are preferred. Also, the compounds described in U.S. Patent 4,639,408, columns 37 to 39 are also useful.
  • dye silver compounds each formed by the combination of an organic silver salt and a dye as described in RD , pages 54 to 58 (May, 1978), azo dyes which are used for a heat development silver dye bleaching process described in U.S. Patent 4,235,957 and RD , pages 30 to 32 (April, 1976), and the leuco dyes described in U.S. Patents 3,985,565 and 4,022,617 can be used in this invention.
  • a heat-developable color photographic light-sensitive material comprising a support having thereon at least a light-sensitive silver halide, a binder, the reducing agent precursor represented by the aforesaid formula (I) or (II), a dye-providing substance releasing a mobile dye counter-curresponding to the reaction of reducing silver ions to silver (the dye-providing compound of the aforesaid (3)), and an electron donor precursor represented by formula (A) or (B) shown below.
  • the reducing agent precursor shown by formula (I) or (II) functions as an electron transferring agent precursor. That is, the reducing agent precursor shown by formula (I) or (II) is de-blocked under the heat development condition to obtain a faculty of functioning as a reducing agent.
  • the reducing agent reduces an exposed silver halide and the reducing agent itself becomes an oxidized product.
  • the oxidized product cross-oxidizes the electron donor released from the electron donor precursor shown by formula (A) or (B) to inactivate the function of reducing the reducible dye-providing substance.
  • R 31 represents a hydroxy group, an alkyl group which may be substituted (e.g., methyl, ethyl, isopropyl, n-butyl, cyclohexyl, t-butyl, n-octyl, n-lauryl, n-hexadecyl), an aryl group which may be substituted (e.g., phenyl, 4-toluyl, 4-methoxyphenyl, 3-methanesulfonylphenyl, 3-chlorophenyl, 4-n-butoxyphenyl), an alkoxy group which may be substituted (e.g., methoxy, ethoxy, isopropoxy, n-butoxy, cyclohexyloxy, t-butoxy, n-octyloxy, n-lauroxy, n-hexadecyloxy), an aryloxy group which may be substituted (e.g.,
  • R 22 , R 23 , R 24 and R 25 in the aforesaid formulae each represents a hydrogen atom, an alkyl group which may be substituted (e.g., methyl, ethyl, n-butyl, cyclohexyl, n-octyl, allyl, sec-octyl, n-dodecyl, n-pentadecyl, n-hexadecyl, tert-octadecyl, 3-lauroylaminophenylmethyl, 3-hexadecanoylaminophenylmethyl, 4-hexadecylsulfonylaminophenylmethyl, 2-ethoxycarbonylethyl, 3-carboxypropyl, N-ethylhexadecylsul- fonylaminomethyl, 2-hydroxy-3,5-di-tert-butylphenylmethyl, 1-(2,5
  • R 22 , R 23 , R 24 and R 25 are, however, at least 8. Also, in formulae (A) and (B), said R 22 and R 23 and/or said R 24 and R 25 may combine with each other to form a saturated or unsaturated ring.
  • R 26 in formula (A) described above represents a hydrogen atom or and R 27 in formula (B) represents a hydrogen atom or (wherein R 31 to R 34 are same as defined above).
  • the use of the electron donor precursor shown by formula (A) is more preferred than the use of the electron donor precursor shown by formula (B).
  • the electron donor precursor shown by following formula (C) is more preferred: wherein R 35 represents an alkyl group which may be substituted (e.g., methyl, ethyl, isopropyl, n-butyl, cyclohexyl, t-butyl, n-octyl, n-lauryl, n-hexadecyl), or an aryl group which may be substituted (e.g., phenyl, 4- methylphenyl, 4-methoxyphenyl, 3-methanesulfonylphenyl, 3-chlorophenyl, 4-n-butoxyphenyl); R 22 , R 23 , and R 24 are same as defined above; and R 28 represents a hydrogen atom or a group shown by (wherein R 35 is the same as defined above).
  • An electron donor precursor the hydroxy group of which is protected by an acyl group e.g., an acetyl group, a propionyl group
  • an acyl group e.g., an acetyl group, a propionyl group
  • the electron donor precursor for use in this invention shows, as a matter of course, lower Dmin since the release of a dye by the reaction with the dye-providing compound in the case of being protected is restrained.
  • the amount of the electron donor precursor in this invention is selected in a wide range but is preferably from 0.01 to 50 mols, and particularly preferably from 0.1 to 5 mols per mol of the reducible dye-providing substance. Also, the amount thereof is preferably from 0.001 to 5 mols, and particularly preferably from 0.01 to 1.5 mols per mol of a silver halide,
  • the electron donor precursor for use in this invention may be used together with an electron donor.
  • An electron donor which is released from the electron donor precursor for use in this invention may be the same or different from the electron donor which is used together with the electron donor precursor.
  • the electron donor precursor and the electron donor may exist in the silver halide emulsion layer or other layer or layers but it is preferred that they exist in the silver halide emulsion layer.
  • the reducible dye-providing compound, the electron donor precursor, and the electron transferring agent precursor shown by formula (I) or (II) are combined with a binder and a silver halide emulsion to provide a light-sensitive layer of one unit.
  • the reducible dye-providing compound may exist in the same layer as the silver halide emulsion but may exist to a layer adjacent to the silver halide emulsion layer. In the latter case, it is preferable that the layer of the reducible dye-providing compound is disposed under the silver halide emulsion layer in the point of sensitivity. In this case, the electron transferring agent and the electron donor can exist in any of the silver halide emulsion layer and the layer of the reducible dye-providing compound.
  • reducible dye-providing compound which can be used in this invention are illustrated below but the invention is not limited to these compounds.
  • the amount of the dye-providing compound depends upon the extinction coefficient of the dye but is generally from 0.05 to 5 millimols/m 2 , and preferably from 0.1 to 3 millimols/m 2 .
  • the dye-providing compounds can be used singly or as a combination thereof.
  • two or more kinds of dye-providing substances each releasing a mobile dye having a different color can be used, for example, in such a manner that each of the cyan dye-providing substance, the magenta dye-providing substance, and the yellow dye-providing substance is incorporated in each silver halide emulsion layer or a layer adjacent to the emulsion layer as described in JP-A-60-162251.
  • Hydrophobic additives such as the dye-providing compound, the nondiffusible reducing agent, etc., can by introduced into layers of the light-sensitive material by the method described, for example, in U.S. Patent 2,322,027.
  • the high-boiling organic solvents as described in JP-A-59-93154, JP-A-59-178451, JP-A-59-178452, JP-A-59-178453, JP-A-59-178454, JP-A-59- 178455, and JP-A-59-178457 can be used together with, if necessary, a low-boiling organic solvent having a boiling point of from 50 C to 160° C.
  • the amount of the high-boiling organic solvent is not more than 10 g, and preferably not more than 5 g per gram of the dye-providing compound.
  • the amount thereof is also, not more than 1 ml, preferably not more than 0.5 ml, and more preferably not more than 0.3 ml per gram of the binder.
  • a dispersion method by a polymer described in JP-B-51-39853 and JP-A-51-59943 can be also used.
  • the compound being incorporated When the compound being incorporated is substantially insoluble in water, the compound can be dispersed in a binder as fine particles as other method than above.
  • hydrophobic compound When a hydrophobic compound is dispersed in a hydrophilic colloid, various kinds of surface active agents can be used.
  • the surface active agents described in JP-A-59-157636, pages 37 to 38 can be used.
  • a compound which can activate the development and at the same time stabilize the images formed can be used for the light-sensitive material.
  • practical examples of the preferred compounds are described in U.S. Patent 4,500,626, columns 51 to 52.
  • a dye-fixing material is used with the light-sensitive material.
  • the dye-fixing material may be a type that the dye-fixing layer is formed on other support than that in the light-sensitive material or a type that the dye-fixing layer is formed on the same support as that in the light-sensitive material.
  • the dye-fixing material which is preferably used in this invention has at least one layer containing a mordant and a binder.
  • mordant those known in the field of photography can be used and practical examples of the mordant are described in U.S. Patent 4,500,626, columns 58 to 59, JP-A-61-88256, pages 32 to 41, JP-A-62-244043, and JP-A-62-244036. Also, the dye-acceptive polymers described in U.S. Patent 4,463,079 can be also used in this invention.
  • the dye-fixing material can be formed, if necessary, a protective layer, a release layer, a curling prevention layer, etc. It is particularly preferable to form a protective layer.
  • the layers constituting the light-sensitive material and the dye-fixing material may contain a plasticizer, a lubricant, etc. Also, for improving the releasing property of the light-sensitive material and the dye-fixing material, a high-boiling organic solvent can be used. Practical examples of these additives are described in JP-A-62-253159, page 25 and JP-A-62-245253.
  • silicone oils e.g., dimethylsilicone oil and denatured silicone oils formed by introducing various organic groups to dimethylsiloxane
  • silicone oils e.g., dimethylsilicone oil and denatured silicone oils formed by introducing various organic groups to dimethylsiloxane
  • Specific examples thereof are various silicone oils described in Denatured Silicone Oil , P6-18B published by Shin-Etsu Silicone K.K. and, in particular, carboxydenatured silicone (X-22-3710,trade name, made by Shin-Etsu Silicone K.K.)
  • silicone oils described in JP-A-62-215953 and JP-A-63-46449 are effective.
  • a discoloration inhibitor for the light-sensitive material and the dye-fixing material may be used a discoloration inhibitor.
  • the discoloration inhibitors there are, for example, antioxidants, ultraviolet absorbents, and certain kinds of metal complexes.
  • antioxidants examples include chroman series compounds, coumaran series compounds, phenolic compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane series compounds. Also, the compounds described in JP-A-61-159644 are effective.
  • ultraviolet absorbent there are benzotriazole series compounds described in U.S. Patent 3,533,794, 4-thiazolidone series compounds described in U.S. Patent 3,352,681, benzophenone series compounds described in JP-A-46-2784, and the compounds described in JP-A-54-48535, JP-A-62-136641, and JP-A-61-88256. Also, the ultraviolet absorptive polymers described in JP-A-62-260152 are effective.
  • the discoloration inhibitor for inhibiting the dye(s) transferred into the dye-fixing material may previously exist in the dye-fixing material or may be supplied to the dye-fixing material from outside such as the light-sensitive material, etc.
  • the aforesaid antioxidant, the ultraviolet absorbent and the metal complex may be used as a combination thereof.
  • the light-sensitive material and the dye-fixing material may be used a brightening agent.
  • the brightening agent is incorporated in the dye-fixing material or supplied to the dye-fixing material from outside such as the light-sensitive material, etc. Examples of such a brightening agent are described in K. Veenkataraman, The Chemistry of Synthetic Dyes , Vol. V, Chapter 8, and JP-A-61-143752. Specific examples thereof are stilbene series compounds, coumarin series compounds, biphenyl series compounds, benzoxazolyl series compounds, naphthalimido series compounds, pyrazoline series compounds, and carbostyryl series compounds.
  • the brightening agent can be used as a combination with a discoloration inhibitor.
  • a hardening agent is used for the layers constituting the light-sensitive material and the dye-fixing material and examples thereof are described in U.S. Patent 4,678,739 column 41, JP-A-59-116655, JP-A-62-245261, and JP-A-61-18942.
  • the hardening agent examples include aldehyde series hardening agents (e.g., formaldehyde), aziridine series hardening agents, epoxy series hardening agents (e.g., vinylsulfone series hardening agents (e.g., N,N'-ethylenebis(vinylsulfonylacetamido)ethane), N-methylol series hardening agents (e.g., dimethylolurea), and polymer hardening agents described in JP-A-62-234157.
  • aldehyde series hardening agents e.g., formaldehyde
  • aziridine series hardening agents e.g., epoxy series hardening agents (e.g., vinylsulfone series hardening agents (e.g., N,N'-ethylenebis(vinylsulfonylacetamido)ethane)
  • N-methylol series hardening agents e.g., dimethylolurea
  • various kinds of surface active agents can be used for the purposes of coating aid, releasability improvement, sliding property improvement, static prevention, development acceleration, etc. Practical examples of the surface active agents are described in JP-A-62-173463 and JP-A-62-183457.
  • organic fluoro compounds may be used for sliding property improvement, static prevention, releasability improvement, etc.
  • organic fluoro compound examples include the fluorine series surface active agents described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944, and JP-A-62-135826, oily fluorine series compounds such as fluorine oil, etc., and hydrophobic fluorine compounds such as solid fluorine compound resins (e.g., tetrafluoroethylene resin).
  • the light-sensitive material and the dye-fixing material may be used a matting agent.
  • a matting agent there are silicon dioxide, polyolefin, and polymethacrylate as described in JP-A-61-88256, page 29 as well as benzoguanamine resin beads, polycarbonate resin beads, and AS resin beads described in Japanese Patent Application Nos. 62-110064 and 62-110065 (corresponding to JP-A-63-274944 and JP-A-63-274952, respectively).
  • the layers constituting the light-sensitive material and the dye-fixing material may further contain a thermal solvent, a defoaming agent, an antibacterial agent, an antifungal agent, colloidal silica, etc. Practical examples thereof are described in JP-A-61-88256, pages 26 to 32.
  • an image formation accelerator for the light-sensitive material and/or the dye-fixing material can be used an image formation accelerator.
  • An image formation accelerator has functions of accelerating the oxidation reduction reaction of the silver salt oxidizing agent and the reducing agent, accelerating the reactions such as the formation of dyes from dye-providing substances, the decomposition of dyes, the release of diffusible dyes, etc., as well as accelerating the transfer of dyes from the layers of the light-sensitive material into the dye-fixing layer.
  • the image formation accelerator is classified into bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surface active agents, and compounds having a co-action with silver or a silver ion.
  • these substances each generally has composite functions, i.e., has two or more aforesaid acceleration effects. Details of these compounds are described in U.S. Patent 4,678,739, columns 38 to 40.
  • the base precursor there are a salt of an organic acid and a base, said salt causing the decarboxylation by heat and compounds releasing amines by an intramolecular nucleophilic displacement reaction, a Lossen rearrangement, or a Backmann rearrangement. Practical examples thereof are described in U.S. Patent 4,511,493 and JP-A-62-65038.
  • the base and/or the base precursor exists in the dye-fixing material from the point of improving the storage stability of the light-sensitive material.
  • a combination of a sparingly soluble metal compound and a compound (a complex-forming compound) capable of causing a complex-forming reaction with the metal ion constituting the sparingly soluble metal compound described in EP-A-210660 and U.S. Patent 4,749,445, and the compound forming a base by electrolysis described in JP-A-61-232451 can be also used as the base precursor in this invention.
  • the former combination is particularly effective. It is advantageous that the sparingly soluble metal compound and the complex-forming compound are separately incorporated in the light-sensitive material and the dye-fixing material, respectively.
  • a development stopping agent can normally be used in the light-sensitive material and/or dye-fixing material of this invention in order to obtain a given image regardless of variation in the development processing temperature or processing time.
  • development stopping agent in this invention means a compound of quickly neutralizing the base or reacting with the base after the adequate development to reduce the concentration of the base in the layer to stop the development, or a compound of reacting with silver or a silver salt to restrain the development.
  • the support for the light-sensitive material and the dye-fixing material in this invention a support capable of enduring the processing temperature is used.
  • a pigment such as titanium oxide
  • synthetic papers prepared by using polyporpylene, etc. papers formed by a mixture of a synthetic resin pulp such as polyethylene pulp and a natural pulp, papers made by Yankee paper machine, baryta-coated papers, resin-coated papers (in particular, cast coated papers), metal plates, cloths, glass sheets, etc.
  • the aforesaid support can be used as it is or a paper one surface or both surfaces of which are coated with a synthetic polymer such as polyethylene, etc., can be used.
  • hydrophilic binder and an antistatic agent such as a semiconductive metal oxide (e.g., alumina sol, tin oxide) and carbon black may be coated on the surface of the support.
  • a semiconductive metal oxide e.g., alumina sol, tin oxide
  • carbon black may be coated on the surface of the support.
  • a method of recording image on the light-sensitive material of this invention by light-exposure there are a method of directly photographing a scene or a person using a camera, a method of exposing through a reversal film or a negative film using a printer or an enlarger, a method of scanning-exposing an original through a slit using an exposure device of a copying machine, a method of exposing by emitting light from a light emitting diode or a laser by sending an image information as electric signals, and a method of displaying an image information on CRT, a liquid crystal display, an electroluminescence display, or a plasma display and exposing the displayed image directly or through an optical system.
  • a light source for recording images on the light-sensitive material there are natural light, a tungsten lamp, a light emitting diode, a laser light source, a CRT light source, etc., as described in U.S. Patent 4,500,626, column 56.
  • the image exposure can be carried out by using a wavelength conversion element composed of a combination of a non-linear optical material and a coherent light source such as laser light.
  • the non-linear optical material is a material capable of causing a non-linear property between the polarization and an electric field appearing in the case of applying an intense photoelectric field such as laser light.
  • non-linear optical material there are inorganic compounds such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate, BaB 2 0 4 , etc., urea derivatives, nitroaniline derivatives, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N- oxide (POM), and the compounds described in JP-A-61-53462, and JP-A-62-210432.
  • KDP potassium dihydrogenphosphate
  • Li iodate lithium iodate
  • BaB 2 0 4 0 4
  • urea derivatives nitroaniline derivatives
  • nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N- oxide (POM)
  • POM 3-methyl-4-nitropyridine-N- oxide
  • wavelength conversion element a single crystal light waveguide type, a fiber type, etc., are known and they are useful.
  • image signals obtained from a video camera, an electronic still camera, etc. television signals represented by Nippon Television Signal Code (NTSC), image signals obtained by splitting an original into many picture elements such as scanners, or image signals formed by using a computer such as CG and CAD can be utilized.
  • NSC Nippon Television Signal Code
  • the light-sensitive material and/or the dye-fixing material may have an electric conductive heating layer as a heating means for the heat development or the diffusion transfer of dyes formed.
  • an electric conductive heating layer as a heating means for the heat development or the diffusion transfer of dyes formed.
  • a transparent or opaque heating element described in JP-A-61-145544 can be utilized.
  • These electroconductive layers also function as static prevention layers.
  • the heating temperature for the heat development step is from about 50 C to about 250 C but is particularly from about 80 C to about 180 C.
  • the diffusion transfer step of dyes may be performed simultaneously with the heat development or may be performed after finishing the heat development step.
  • the heating temperature in the transfer step may be from room temperature to the temperature in the heat development step but the temperature of 50° C or higher and about 10 0 C lower than the temperature in the heat development step is particularly preferred.
  • the transfer of dyes is carried out by heat only but a solvent may be used for accelerating the transfer of dyes.
  • the heating temperature is preferably from 50° C to the boiling point of the solvent, for example, when the solvent is water, the heating temperature is preferably from 50 C to 100° C.
  • the solvent which is used for the acceleration of the development and/or the transfer of diffusible dyes onto the dye-fixing layer there are water and a basic aqueous solution containing an inorganic alkali metal salt or an organic base (as the base, those described above on the image-forming accelerator can be used). Also, a low-boiling organic solvent or a mixture of a low-boiling organic solvent and water or a basic aqueous solution can be used. Furthermore, the solvent may contain a surface active agent, an antifoggant, a sparingly soluble metal salt, or a complex forming compound.
  • the solvent can be used by a method of applying to at least one of the dye-fixing material and the light-sensitive material.
  • the amount of the solvent may be less than the weight of the solvent corresponding to the maximum swelled volume of the whole coated layers (in particular, less than the amount obtained by subtracting the weight of the whole coated layers from the weight of the solvent corresponding to the maximum swelled volume of the whole coated layers).
  • the solvent may be previously incorporated in the light-sensitive material and/or the dye-fixing material as a form of being encapsulated.
  • a system of incorporating a hydrophilic thermal solvent which is a solid at normal temperature and is melted at high temperature in the light-sensitive material or the dye-fixing material can be employed.
  • the hydrophilic thermal solvent may be incorporated in the light-sensitive material and/or the dye-fixing material.
  • the layer containing the aforesaid thermal solvent may be an emulsion layer, an interlayer, a protective layer, or a dye-fixing layer but it is preferred to incorporate the thermal solvent in the dye-fixing layer or a layer adjacent to the dye-fixing layer.
  • hydrophilic thermal solvent examples include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and heterocyclic compounds.
  • a high-boiling organic solvent may be incorporated in the light-sensitive material and/or the dye-fixing material.
  • a heating method in the development step and/or the dye transfer step there are a method of contacting with a heated block or plate, a method of contacting with a hot plate, a hot pressor, a hot roller, a halogen lamp heater, or an infrared or far infrared lamp heater, and a method of passing through a high-temperature atmosphere.
  • JP-A-59-75247 For processing the photographic elements of this invention, various kinds of heat development apparatus can be used. For examples, these apparatus are described in JP-A-59-75247. JP-A-59-177547, JP-A-59-181353, JP-A-60-18951, and JP-A-U-62-25944 (the term "JP-A-U” as used herein means an "unexamined published Japanese utility model application").
  • Each of the yellow, magenta, and cyan dye-providing compounds shown below was added to 50 ml of ethyl acetate together with other components shown in the following table, the chemical formulae of these components being shown below, and they were dissolved by heating to about 60 C to form a uniform solution.
  • the solution was mixed with 100 g of an aqueous solution of 10% lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate, and 50 ml of water with stirring, and thereafter the mixture was dispersed by means of a homogenizer for 10 minutes at 10,000 r.p.m. The dispersion is called a gelatin dispersion of the dye-providing compound.
  • Dye-Providing Compound (1) Dye-Providing Compound (2)
  • Electron Transferring Agent Precursor A (Comparison Example):
  • aqueous solution a solution obtained by adding 20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride, and 0.015 g of Chemical A shown below to 730 ml of water and kept at 60.0 C
  • Solution (I) and Solution (II) shown below were simultaneously added to 730 ml of water and kept at 60.0 C.
  • a methanol solution (III) of the sensitizing dye C shown below was added to the mixture.
  • a dye-adsorbed monodisperse cubic silver halide emulsion having a mean grain size of 0.45 ⁇ m was obtained.
  • the emulsion was chemically sensitized at 60.0 C.
  • the chemical sensitization 1.6 mg of triethylthiourea and 100 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazain- dene were used and the ripening time was 55 minutes. Also, the amount of the emulsion was 635 g.
  • aqueous gelatin solution a solution formed by adding 20 g of gelatin, 1 g of potassium bromide, and 0.5 g of HO(CH 2 ) 2 S(CH 2 ) 2 0H to 800 ml of water and kept at 50°C
  • an active carbon powder (reagent, highest quality) made by Wako Pure Chemical Industries, Ltd., 1 g of a dispersing agent, Demol N (trade name, made by Kao Corporation), and 0.25 g of polyethylene glycol nonylphenyl ether, and then the mixture was ground in a mill using glass beads having a mean particle size of 0.75 mm for 120 minutes. By separating the glass beads, a dispersion of active carbon having a mean grain size of 0.5 ⁇ m was obtained.
  • a heat-developable color light-sensitive material 101 of a multilayer structure having the following layer structures was prepared using the compositions prepared above.
  • the layer structures are shown from the upper-most layer and the numerals are coated amounts shown by mg /m2.
  • Polyethylene terephthalate film of 96 ⁇ m in thickness (coated with carbon black as the back layer).
  • a dye-fixing material R-1 having the following layer structure was prepared.
  • the front surface thereof was coated with a glossy polyethylene layer having a thickness of 45.0 ⁇ m composed of 89.2 parts of low-density polyethylene (density 0.923), 10.0 parts of surface treated titanium oxide, and 0.8 part of ultramarine blue, and with a gelatin subbing layer having a thickness of 0.1 ⁇ m.
  • the back surface thereof was coated with matting surface having a thickness of 36.0 ⁇ m composed of high-density polyethylene (density 0.960), and with a subbing layer composed of a gelatin layer of 0.05 ⁇ m thick and a colloidal silica layer of 0.05 ⁇ m thick.
  • the total thickness of the support was 173.8 ⁇ m.
  • the compounds used for the dye-fixing material were as follows.
  • Mordant (1) High-Boiling Solvent (1): Hardening Agent (1): Matting Agent (1)*:
  • Each of the multilayer color light-sensitive materials 101 to 110 was exposed to a tungsten lamp for 1/10 second at 5,000 lux through a color separation filter of blue (B), green (G), red (R), and gray having a continuously changing density.
  • the assembly was heated for 15 seconds using a heat roller having a controlled temperature such that the temperature of the water-absorbed layers became 85 C. Then, the image-receiving material was separated, whereby blue, green, red, and gray images were obtained on the image-receiving material corresponding to the B, G, R, and gray color separation filter.
  • additives were, unless otherwise indicated, same as those for the light-sensitive material 101.
  • organic silver salt emulsion was prepared as follows.
  • the layer structures are also shown from the uppermost layer.
  • the numerals shown below are the coated amounts shown by mg/m 2 .
  • Polyethylene terephthalate film of 100 ⁇ m in thickness The compounds newly used for the above light-sensitive material were as follows.
  • Electron Transferring Agent Precursor C (comparison):
  • Each of the light-sensitive materials was exposed as in Example 1 and then uniformly heated for 30 seconds on a heat block heated to 140 C.
  • the light-sensitive material thus heat-treated was superposed on the image-fixing material so that the emulsion layer was contact in the mordant layer.
  • Electron Donor 17 Electron Transferring Agent Precursor D:
  • Each of the light-sensitive materials 301 to 303 was exposed for 1/10 second using a tungsten lamp at 1,000 lux through a gray filter having continuously changing density.
  • the assembly was heated for 15 seconds using a heat roller having a controlled temperature such that the temperature of the water-absorbed layers became 85 C. Then, the alkali-generating sheet was separated and the light-sensitive material was fixed for 5 minutes using a fix solution (Fuji Fix, trade name, made by Fuji Photo Film Co., Ltd.), washed for 20 minutes, and dried to provide a negative image having no unevenness.
  • a fix solution Fluji Fix, trade name, made by Fuji Photo Film Co., Ltd.
  • the transmission density of the silver images formed was measured on Dmax and Dmin and the results are shown in Table 3 below.
  • Emulsion (I) for Layer 5 A method of preparing Emulsion (I) for Layer 5 was explained.
  • aqueous gelatin solution a solution formed by adding 20 g of gelatin, 3 g of potassium bromide, 0.03 g of the compound (1) shown below, and 0.25 g of HO(CH 2 ) 2 S(CH 2 ) 2 S(CH 2 ) 2 0H to 800 ml of water and kept at 50 C
  • Solution (1) and Solution (2) shown below were simultaneously added thereto over a period of 20 minutes.
  • Solution (3) and Solution (4) shown below were simultaneously added thereto over a period of 20 minutes.
  • a solution of the dye shown below was added over a period of 18 minutes.
  • the dye solution was a solution dissolving the following dyes in 160 ml of methanol.
  • Emulsion (II) for Layer 3 is explained.
  • aqueous gelatin solution a solution formed by adding 20 g of gelatin, 0.30 g of potassium bromide, 6 g of sodium chloride, and 0.015 g of the chemical A shown below to 730 ml of water and kept at 60.0° C
  • Solution (I) and Solution (II) shown below were simultaneously added.
  • Solution (III) of the sensitizing dye C shown below was added.
  • a dye-adsorbed monodisperse cubic silver halide emulsion having a grain size of 0.45 um was prepared.
  • the emulsion was chemically sensitized at 60.0 C.
  • the chemical sensitization 1.6 mg of triethylthiourea and 100 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazain- dene were used and the ripening time was 55 minutes. Also, the amount of the emulsion was 635 g.
  • Emulsion (III) for Layer 1 is explained.
  • aqueous gelatin solution a solution formed by adding 20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride, and 30 mg of the Chemical A shown below to 800 ml of water and kept at 50° C
  • Solution (I) and Solution (II) shown below were simultaneously added thereto over a period of 30 minutes.
  • Solution (III) and Solution (IV) were further simultaneously added thereto over a period of 30 minutes.
  • 3 minutes after the initiation of the addition of the Solutions (III) and (IV) the following dye solution was added thereto over a period of 20 minutes.
  • the dye solution was a solution formed by dissolving 67 mg of Dye (a) shown below and 133 mg of Dye (b) shown below in 100 ml of methanol.
  • an active carbon powder (reagent, highest quality) made by Wako Pure Chemical Industries, Ltd., 1 g of Demol N, trade name, made by Kao Corporation as a dispersing agent and 0.25 g of polyethylene glycol nonylphenyl ether, and the mixture was ground in a mill for 120 minutes using glass beads having a mean particle size of 0.75 mm. By separating the glass beads, a dispersion of active carbon having a mean grain size of 0.5 ⁇ m was obtained.
  • Electron Donor ED-15
  • a multilayer heat-developable color light-sensitive material 401 having the layer structures shown below was prepared using the aforesaid compositions.
  • the layer structures are shown from the upper-most layer.
  • the numerals are coating amounts in mg/m 2 .
  • a polyethylene terephthalate film of 96 ⁇ m in thickness containing carbon black in a back layer containing carbon black in a back layer.
  • Each of the multilayer color light-sensitive materials 401 to 420 was exposed for 1/10 sec using a tungsten lamp at 5,000 lux through a B, G, R and gray color separation filter having a continuously changing density.
  • the assembly was heated for 15 seconds using a heat roller having an adjusted temperature such that the temperature of the water-absorbed layers became 85 * C. Then, when the image-receiving material R-1 was separated, clear blue, green, red, and gray images having no unevenness were obtained on the image-receiving material corresponding to the B, G, R, and gray color separation filter.
  • the light-sensitive materials 401 to 404 were samples using the electron donor (ED-15) described in JP-A-63-262647. Samples 401 and 402 show sufficiently high Dmax but show high Dmin. In Samples 402 and 403, Dmin is reduced by decreasing the amount of the electron donor but in this case, Dmax is also decreased.
  • ED-15 electron donor
  • the light-sensitive materials 405 to 407 were samples using the conventionally known electron donor precursor. In these samples, when the amount thereof is increased for obtaining sufficiently high Dmax, Dmin tends to increase.
  • the samples 414 to 420 of this invention using the electron donor precursor shown by formula (A) or (B) show lower Dmin and higher Dmax than the samples 410 to 413.
  • a multilayer color light-sensitive material 501 having the layer structures shown below was prepared using the same silver halide emulsions and the dye-providing compounds as those of the color light-sensitive material 401 in Example 4.
  • organic silver salt emulsion was prepared as follows.
  • the layer structures are shown from the uppermost layer.
  • the numerals are the coating amounts in mg/m 2 .
  • Each of the light-sensitive materials was exposed as in Example 4 and uniformly heated for 30 seconds on a heat block heated to 140° C.
  • the assembly was passed through a laminator heated to 80 0 C at a line speed of 12 mm/sec and they were separated from each other, whereby with respect to each light-sensitive material, positive image having good discrimination was obtained on the dye-fixing material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
EP19900117690 1989-09-18 1990-09-13 Heat-developable light-sensitive material Withdrawn EP0418743A3 (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP24096389A JPH03102345A (ja) 1989-09-18 1989-09-18 熱現像感光材料
JP240963/89 1989-09-18
JP269556/89 1989-10-17
JP26955689A JP2612206B2 (ja) 1989-10-17 1989-10-17 カラー感光材料
JP30107689A JP2612207B2 (ja) 1989-11-20 1989-11-20 熱現像カラー感光材料
JP301076/89 1989-11-20

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EP0418743A2 true EP0418743A2 (de) 1991-03-27
EP0418743A3 EP0418743A3 (en) 1991-05-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0695968A3 (de) * 1994-08-01 1996-07-10 Eastman Kodak Co Viskositätsverminderung in einer photographischen Schmelze

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3839696A1 (de) * 1987-11-26 1989-06-29 Fuji Photo Film Co Ltd Waermeentwickelbares farbphotographisches material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3839696A1 (de) * 1987-11-26 1989-06-29 Fuji Photo Film Co Ltd Waermeentwickelbares farbphotographisches material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0695968A3 (de) * 1994-08-01 1996-07-10 Eastman Kodak Co Viskositätsverminderung in einer photographischen Schmelze

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