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(11) | EP 0 418 743 A2 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | Heat-developable light-sensitive material |
| (57) A heat-developable light-sensitive material is disclosed 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;
wherein Ri, R2, R3, and R4 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and X represents a substituted alkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a group shown by the following formula (wherein Z represents a divalent linkage group bonded to the phthalide nucleus via an oxygen atom; n represents 0 or 1; L represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, 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; and m represents 0 or an integer of from 1 to 4), or a group shown by the following formula (wherein M represents (wherein p represents 2 or 3; R" represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, or an alkoxy group; and R'2 and R13 each represents a hydrogen atom, a halogen atom, an alkyl group, a phenyl group; said R12 and R13 may close ring together to form a benzene ring); and Q represents a hydroxy group, or R16 (wherein R14 represents a hydrogen atom, an aryl group, or an alkyl group; R15 represents a hydrogen atom or an acyl group; and R16 represents a hydrolyzable group)). |
FIELD OF THE INVENTION
[0001] 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.
BACKGROUND OF THE INVENTION
[0002] 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).
[0004] For example, a process of forming color images by the combination of the oxidation product of the color developing agent and a coupler is proposed in U.S. Patents 3,531,286, 3,761,270, and 4,021,240, Belgian Patent 802,519, and Research Disclosure , (hereinafter, is referred to as RD ), pages 31 to 32, sept., 1975.
[0005] However, since 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.
[0006] For correcting these defects, a process of imagewise forming or releasing diffusible dyes by heating and then transferring the diffusible dyes onto an iamge-receiving material containing a mordant with a solvent such as water, etc., is disclosed in U.S. Patents 4,500,626, 4,483,914, 4,503,137 and 4,559,290 and JP-A-59-165054 (the term "JP-A" as used herein means an "unexamined published Japanese patent application").
[0007] However, in the aforesaid process, the developing temperature is still high and the storage stability of the light-sensitive materials is insufficient.
[0008] Thus, a process of performing the acceleration of development, the reduction of a developing temperature and simplification of processing by heat- developing in the existence of a base or a base precursor and a slight amount of water to transfer dyes formed is disclosed in JP-A-59-218443, JP-A-61-238056, and EP-A-210660.
[0009] For obtaining positive color images by heat development, various processes have been proposed.
[0010] For example, 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. Also, EP-A-220746 and Kokai Giho , Vol. 12, No. 22 describe a heat-developable color photographic light-sensitive material using a compound of releasing a diffusible dye by a reductive cleavage of an N-X bond (wherein X represents an oxygen atom, a nitrogen atom or a sulfur atom) as a compound of releasing a diffusible dye by the similar mechanism to above.
[0011] It is known by 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.
[0012] For solving the aforesaid problem, a technique of blocking the active site of a reducing agent and using the blocked reducing agent as a precursor is disclosed in JP-A-59-182449, JP-A-59-182450, JP-A-61-34540, and JP-A-1-138558. Also, a technique of using a reducing agent and a reducing agent precursor is disclosed in JP-A-1-138556.
SUMMARY OF THE INVENTION
[0013] As the result of various investigations on the use of reducing agent precursors for heat-developable light-sensitive materials, the inventors have discovered that if the melting point of a reducing agent precursor is high in a heat development system, the discrimination of images formed is deteriorated. It has also been discovered that when a precursor of a 1-phenyl-3-pyrazolidinone derivative is used, the discrimination is greatly deteriorated.
[0014] 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.
[0015] It has now been discovered that the aforesaid object can be attained by the present invention as described hereinbelow.
[0016] That is according to this invention, there is provided 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;
[0018] In the aforesaid formulae, R , R2, R3, and R4 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; Rs represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and X represents a substituted alkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a group shown by the following formula
(wherein Z represents a divalent linkage group bonded to the phthalide nucleus via an oxygen atom; n represents 0 or 1; L represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, 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; and m represents 0 or an integer of from 1 to 4), or a group shown by the following formula
(wherein M represents
(wherein p represents 2 or 3; R11 represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, or an alkoxy group; and R12 and R13 each represents a hydrogen atom, a halogen atom, an alkyl group, or a phenyl group; said groups may close ring at R12 and R13 to form a benzene ring) and Q represents a hydroxy group,
or R16 (wherein R14 represents a hydrogen atom, an aryl group, or an alkyl group; R15 represents a hydrogen atom or an acyl group; and R'6 represents a hydrolyzable group)).
DETAILED DESCRIPTION OF THE INVENTION
[0019] Then, the reducing agent precursors represented by formulae (I) and (II) described above are described in detail.
[0020] In the above formulae, R, to R4 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 unsubstituted heterocyclic group (preferably 5, 6, 9, 10, 13, 14-membered ring containing as a hetero atom O, N, S, etc., having not more than 20 carbon atoms, for example, pyridyl, quinonyl, methylpyridyl, thiophenyl, furyl).
[0021] R5 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 Ri to R4.
[0022] X represents a substituted alkyl group, preferably -CH2-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 sulfamoyl group, a substituted sulfamoyl group, a group represented by the following formula
(wherein Z represents a divalent linkage group bonded to the phthalide nucleus via an oxygen atom; n represents 0 or 1; L represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, 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; and m represents 0 or an integer of from 1 to 4), or a group represented by the following formula
(wherein M represents
(wherein p represents 2 or 3; R11 represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, or an alkoxy; R12 and R13 each represents a hydrogen atom, a halogen atom, an alkyl group, or a phenyl group, said groups may close ring at R12 and R13 to form a benzene ring; and Q represents a hydroxy group,
or R'6 (wherein R14 represents a hydrogen atom, an aryl group, or an alkyl group; R15 represents a hydrogen atom or an acyl group; and R16 represents hydrolyzable group)).
[0023] Examples of the hydrolyzable group shown by R'6 are
(wherein R17 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; R18 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 R18 and R'9 may be the same or different; and the aliphatic group shown by R17, R'8 or R19 may be substituted or unsubstituted, chain like, or cyclic).
[0024] 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 group, and an alkoxycarbonylamino group.
[0025] When R17, R18, and R19 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 chain. 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.
[0026] When R17, R18, and R19 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.
[0027] Specific examples of the compound represented by formula (I) are described in JP-A-1-138556, pages 14 to 22 and in this invention, the compounds having a melting point of not higher than 120° C are used.
[0028] Then, specific examples of the reducing agent precursors for use in this invention are illustrated below but the reducing agent precursors which can be used in this invention are not limited to them.
[0029] In addition, the numeral value in the following parentheses is a melting point of each compound.
[0030] In this invention, a reducing agent can be used together with the aforesaid reducing agent precursor. In this case, 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.
[0031] As 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. Also, 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).
[0032] Examples of the reducing agent being used in this invention are described in U.S. Patents 4,500,626, columns 49 to 50, 4,483,914, columns 30 to 31, 4,330,617, and 4,590,152, JP-A-60-140335, pages 17 and 18, JP-A-57-40245, JP-A-56-138736, JP-A-59-178458, JP-A-59-53831, JP-A-59-182449. JP-A-59-182450, JP-A-60-119555, JP-A-60-128436, JP-A-60-128437, JP-A-60-128438, JP-A-60-128439, JP-A-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-244044, JP-A-62-131253, JP-A-61-131254, JP-A-62-131255, and JP-A-62-131256, EP-A-220746, pages 78 to 96.
[0033] The combinations of various reducing agents as disclosed in U.S. Patent 3,039,896 can be also used in this invention.
[0034] In the case of using a nondiffusible reducing agent being used with the reducing agent precursor, 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. If necessary, an electron transferring agent (of a non-precursor type) can be used as a combination therewith.
[0035] 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).
[0036] 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.
[0037] As the nondiffusible reducing agent (electron donor) 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.
[0038] 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.
[0039] Also, it is preferred that the amount of the diffusible reducing agent is not more than about 40 mol% of the amount of the total reducing agents.
[0040] 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.
[0041] In the case of forming color images of a wide range of colors in the chromaticity diagram using the three primary colors of yellow, magenta, and cyan, a combination of at least 3 layers each composed of each silver halide emulsion having a light sensitivity in each different spectral region is used.
[0042] For example, there are a combination of a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer and a combination of a green-sensitive emulsion layer, a red-sensitive emulsion layer, and an infrared-sensitive emulsion layer. These light-sensitive emulsion layers may disposed in various orders known in an ordinary color photographic light-sensitive material. Also, if necessary, each light-sensitive layer may be composed of two or more layers.
[0043] For the 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.
[0044] The silver halide for use in this invention may be silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide.
[0045] The silver halide emulsion for use in this invention may be a surface latent image type emulsion or an internal latent image type emulsion.
[0046] The internal latent image type emulsion is used as a direct reversal emulsion by combination with a nucleating agent or a light fogging method. Also, 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.
[0047] The silver halide emulsion may be a monodisperse emulsion or a polydisperse emulsion or a mixture of monodisperse emulsions may be used.
[0048] 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.
[0049] The crystal form of the silver halide grains may be cubic, octahedral, tetradecahedral, tabular grains of a high aspect ratio, etc.
[0050] Practical examples of the silver halide emulsion for use in this invention are described in U.S. Patents 4,500,626 and 4,628,021, RD , Vol. 17029 (June, 1978), and JP-A-62-253159.
[0051] The silver halide emulsion may be used as a primitive emulsion but is usually chemically sensitized. For the chemical sensitization, 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.
[0052] The coating amount of the light-sensitive silver halide for use in this invention is in the range of from 1 mg/m2 to 10 g/M2, calculated in terms of silver.
[0053] In this invention, an organic metal salt can be used with a light-sensitive silver halide as an oxidizing agent. In these organic metal salts, an organic silver salt is particularly preferably used.
[0054] 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.
[0055] 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/m2 to 10 g/m2, calculated in terms of silver.
[0056] In this invention, 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.
[0057] 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.
[0058] Practically, there are sensitizing dyes described in U.S. Patent 4,617,257, JP-A-59-180550, JP-A-60-140335, and RD , Vol. 17029, pages 12 to 13 (June, 1978).
[0059] These 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.
[0060] 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.
[0061] These 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.
[0062] As the binders for the constitution layers of the light-sensitive material and a dye-fixing material, hydrophilic binders are preferably used. Examples thereof are described in JP-A-62-253159, pages 26 to 28.
[0063] Practically, transparent or translucent 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. Also, the high water-absorptive polymers described in JP-A-62-245260, i.e., the homopolymer of a vinyl monomer having -COOM or -S03M' (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.
[0064] In the case of employing the system of carrying out the heat development by supplying a slight amount of water, the absorption of water can be quickly carried out by using the aforesaid high water-absorptive polymer. Also, when 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.
[0065] In this invention, 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.
[0066] 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.
[0067] In particular, when the polymer latex having a low glass transition point (not higher than 40 C) is used for a mordant layer, 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.
[0069] Also, 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.
[0070] As an example of the dye-providing compound which can be used in this invention, a compound (coupler) forming a dye by an oxidative coupling reaction can be used.
[0071] 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.
[0072] Practical examples of a color developing agent and the coupler are described in detail in T.H. James, The Theory of the Photographic Process , pages 291 to 334 and pages 354 to 361, JP-A-58-123533, JP-A-58-149046, JP-A-58-149047, JP-A-59-111148, JP-A-59-124399, JP-A-59-174835, JP-A-59-231539, JP-A-59-231540, JP-A-60-2950, JP-A-60-2951, JP-A-60-14242, JP-A-60-23474, and JP-A-60-66249.
[0073] Also, as other example of 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.
[0074] Practical examples of the dye-providing compound shown by formula (LI) described above include the following compounds (1) to (5). In addition, the following compounds (1) to (3) each forms a diffusible dye image (positive dye image) counter-corresponding to the development of silver halide, and the compound (4) and (5) each forms a diffusible dye image (negative dye image) corresponding to the development of silver halide.
(1) Dye developing agents wherein a hydroquinone series developing agent and a dye
component are bonded with each other described in U.S. Patents 3,134,764, 3,362,819,
3,597,200, 3,544,545, and 3,482,972.
The dye developing agent is diffusible under an alkaline circumstance but becomes
nondiffusible on reacting with silver halide.
(2) Nondiffusible compound which release a diffusible dye under an alkaline circumstance
but looses the faculty on reacting with silver halide described in U.S. Patent 4,503,137.
Examples thereof include a compound releasing a diffusible dye by an intramolecular
nucleophilic displacement reaction described in U.S. patent 3,980,479 and a compound
releasing a diffusible dye by an intramolecular rearrangement reaction of an isooxazolone
ring described in U.S. patent 4,199,354.
(3) Nondiffusible compound (reducible dye-providing compound) releasing a diffusible dye by reacting with a reducing agent remained without being oxidized by development as described in U.S. Patents 4,559,290 and 4,783,396, European Patent 220,746A2, and Kokai Giho 87-6199.
[0075] 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. Patents 4,343,893 and 4,619,884, and a nitro compound releasing a diffusible dye after receiving electron described in U.S. Patent 4,450,223, and a compound releasing a diffusible dye after receiving electron described in U.S. Patent 4,609,610.
[0076] Also, more preferred examples of 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 S02-X (wherein X is the same as defined above) and an electron attractive group in one molecule described in Japanese Patent Application No. 62-106885 (corresponding to 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 -S02-) and an electron attractive group in one molecule described in JP-A-63-271341.
[0077] Also, the compounds releasing a diffusible dye by the cleavage of a single bond after being reduced by a 7r bond conjugated with an electron-acceptive group described in Japanese Patent Application Nos. 62-319989 and 62-320771 (corresponding to JP-A-1-161237 and JP-A-1-161342, respectively) can be utilized in this invention as the dye-providing compound.
[0078] In the aforesaid compounds, 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).
[0079] (4) Compound (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. Practical examples thereof are described in British Patent 1,330,524, 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.
[0080] (5) Compound (DRR compound) which has a reductive property to a silver halide or an organic silver salt and releases a diffusible dye by reducing the aforesaid component. Since the compound does not need the use of other reducing agent, the use of the compound is preferred because of causing no problem of staining images by the oxidation decomposed product of a reducing agent. Practical examples thereof are described in U.S. Patents 3,928,312, 4,053,312, 4,055,428, and 4,336,322, JP-A-59-65839, JP-A-59-69839, JP-A-53-3819, and JP-A-51-104343, RD , Vol. 17465, U.S. 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.
[0081] Furthermore, as other dye-providing compounds than the aforesaid couplers and the dye-providing compounds shown by aforesaid formula (LI), 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.
[0082] In a preferred embodiment of this invention, there is provided 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.
[0083] In this case, 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.
wherein R31 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., phenoxy, 4-methylphenoxy, 4-methoxyphenoxy, 3-methanesulfonyl phenoxy, 3-chlorophenoxy, 4-n-butoxyphenoxy), an amino group which may be substituted (e.g., N,N-dimethylamino, N,N-diethylamino, N,N-diisopropylamino, N,N-di-n-butylamino, N-methyl-N-octadecylamino, N-methyl-N-hexadecylamino, N-methylamino, N-ethylamino, N-isopropylamino, N-n-butylamino, N-octadecylamino, n-hexadecylamino, N,N-di-(2-cyanoethylamino), N,N-di-(methoxyethyl)amino), or an anilino group which may be substituted (e.g., anilino, 4-methylanilino, 4-methoxyanilino, 4-methanesulfonylanilino, 3-chloroanilino, 4-ethoxyanilino); R32, R33, and R34 each represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, and iodine), a cyano group, a sulfonyl group (e.g., methanesulfonyl, ethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl), an acyl group (e.g., acetyl, propionyl, n-butanoyl, benzyl), a carbamoyl group (e.g., dimethylcarbamoyl, diethylcarbamoyl, dicyclohexylcarbamoyl, di-n-octylcarbamoyl), a sulfamoyl group (e.g., dimethylsulfamoyl, diethylsulfamoyl, di-n-octylsulfamoyl), an alkoxycarbonyl group which may be substituted (e.g., methoxycarbonyl, ethoxycarbonyl, n-butoxycarbonyl, n-octyloxycarbonyl, n-lauroyloxycarbonyl, n-hexadecyloxycarbonyl), an aryloxycarbonyl group which may be substituted (e.g., phenoxycarbonyl, 4-methylphenoxycarbonyl, 3-chloro phenoxycarbonyl, 4-methoxyphenoxycarbonyl), an alkyl group which may be substituted (e.g., methyl, ethyl, iso-propyl, n-butyl, cyclohexyl, n-octyl, n-lauryl, n-hexadecyl), an aryl group which may be substituted (e.g., phenyl, 4-tolyl, 4-methoxyphenyl, 3-methanesulfonylphenyl, 3-chlorophenyl, 4-butoxyphenyl), an alkoxy group which may be substituted (e.g., methoxy, ethoxy, n-butoxy, cyclohexyloxy, n-octyloxy), an amido group which may be substituted (e.g., acetamido, n-propionylamido, benzoylamido), an imido group which may be substituted (e.g., succinic acid imido, 3-laurylsuccinic acid imido, phthalic acid imido), a sulfonamido group which may be substituted (e.g., methanesulfonamido, ethanesulfonamido, n-butanesulfonamido, benzenesulfonamido, toluenesulfonamido), or a heterocyclic residue which may be substituted (e.g., morpholino, imidazoyl, pyrazoyl, oxazoyl, thiazoyl); said R32, R33, and R34 may be the same or different; and at least one of said R32, R33, and R34 is selected from a halogen atom, a cyano group, a sulfonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
[0084] R22, R23, R24 and R25 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-dihydroxy-4-tert-butylphenyl)lauryl, N-methyldodecylsulfonylaminoethyl), an aryl group which may be substituted (e.g., phenyl, 3-hexadecyloxyphenyl, 3-methoxyphenyl, 3-sulfophenyl, 3-chlorophenyl, 2-carboxyphenyl, 3-dodecanoylaminophenyl), an alkylthio group which may be substituted (e.g., n-butylthio, methylthio, tert-octylthio, n-dodecylthio, 2-hydroxyethylthio, n-hexadecylthio, 3-ethoxycarbonylpropiothio), an arylthio group which may be substituted (e.g., phenylthio, 4-chlorophenylthio, 2-n-octyloxy-5-t-butylphenylthio, 4-dodecyloxyphenylthio, 4-hex- adecanoylaminophenylthio), a sulfonyl group which may be substituted (e.g., methanesulfonyl, butanesulfonyl, p-toluenesulfonyl, 4-dodecyloxyphenylsulfonyl, 4-acetylaminophenylsulfonyl), a sulfo group, a halogen atom (e.g., fluorine, chlorine, bromine, and iodine), a cyano group, a carbamoyl group (e.g., methylcarbamoyl, diethylcarbamoyl, 3-(2,4-di-t-pentylphenyloxy)propylcarbamoyl, cyclohexylcarbamoyl, di-n-octylcarbamoyl), a sulfamoyl group (e.g., diethylsulfamoyl, di-n-octylsulfamoyl, n-hexadecylsulfamoyl, 3-iso-hex- adecanoylaminophenylsulfamoyl), an amido group which may be substituted (e.g., acetamido, iso- butyroylamido, 4-tetradecyloxyphenylbenzamido, 3-hexadecanoylaminobenzamido), an imido group which may be substituted (e.g., succinic acid imido, 3-laurylsuccinic acid imido, phthalic acid imido), a carboxy group, or a sulfonamido group which may be substituted (e.g., methanesulfonamido, octanesulfonamido, hexadecanesulfonamido, benzenesulfonamido, toluenesulfonamido, 4-lauryloxybenzenesulfonamido).
[0085] The sum of the carbon atoms of said R22, R23, R24 and R25 is, however, at least 8. Also, in formulae (A) and (B), said R22 and R23 and/or said R24 and R25 may combine with each other to form a saturated or unsaturated ring.
[0086] R26 in formula (A) described above represents a hydrogen atom or
and R27 in formula (B) represents a hydrogen atom or
(wherein R31 to R34 are same as defined above).
[0087] It is preferred that in the electron donor precursors shown by the aforesaid formula (A) or (B), at least two of R22, R23, R24 and R25 are other substituent than hydrogen atom. Also, it is particularly preferred that in the electron donor precursor shown by formula (A) or (B), at least one of said R22 and R23 and at least one of said R24 and R25 are other substituent than hydrogen atom.
[0088] In this invention, 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). Furthermore, the electron donor precursor shown by following formula (C) is more preferred:
wherein R35 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); R22, R23, and R24 are same as defined above; and R28 represents a hydrogen atom or a group shown by
(wherein R35 is the same as defined above).
[0089] Then, specific examples of the electron donor precursors represented by formula (A) (including formula (C)) and formula (B) described above are illustrated below but the electron donor precursors for use in this invention are not limited to these compounds.
[0090] An electron donor precursor the hydroxy group of which is protected by an acyl group (e.g., an acetyl group, a propionyl group) is known as disclosed, e.g., in JP-A-63-262647. However, in these precursors, the de-protecting speed at development is insufficient and a high image density is not obtained.
[0091] On the other hand, in this invention, by using an acyl group, wherein the α-position of the carbonyl group is substituted by at least one electron attractive group, as
(wherein R31 to R34 are the same as defined above), the de-protecting speed at development is greatly improved and images having a sufficiently high image density can be obtained.
[0092] Also, as compared to the electron donors described in JP-A-63-262647 described above, 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.
[0093] 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,
[0094] The electron donor precursor for use in this invention may be used together with an electron donor.
[0095] 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.
[0096] 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.
[0097] In the aforesaid embodiment of this invention, the reducible dye-providing compound, the electron donor precursor, and the electron transferring agent precursor shown by formula (I) or (II) (these three components are preferably co-emulsified) are combined with a binder and a silver halide emulsion to provide a light-sensitive layer of one unit.
[0098] 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.
[0099] Then, specific examples of the reducible dye-providing compound which can be used in this invention are illustrated below but the invention is not limited to these compounds.
[0100] These compounds can be synthesized by the methods described in the patent specifications cited above.
[0101] The amount of the dye-providing compound depends upon the extinction coefficient of the dye but is generally from 0.05 to 5 millimols/m2, and preferably from 0.1 to 3 millimols/m2.
[0103] Also, for obtaining black images or images having different colors, 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.
[0104] 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. In this case, 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.
[0105] 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.
[0106] For the aforesaid purpose, a dispersion method by a polymer described in JP-B-51-39853 and JP-A-51-59943 can be also used.
[0107] 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.
[0108] When a hydrophobic compound is dispersed in a hydrophilic colloid, various kinds of surface active agents can be used. For example, the surface active agents described in JP-A-59-157636, pages 37 to 38 can be used.
[0109] In this invention, 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.
[0110] In the system of forming an images by the diffusion transfer of dye(s), 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 relation of the light-sensitive material and the dye-fixing material, the relation with supports, and the relation with a white reflection layer, which can be used in this invention, are described in U.S. Patent 4,500,626, column 57.
[0111] The dye-fixing material which is preferably used in this invention has at least one layer containing a mordant and a binder.
[0112] As the 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.
[0113] For 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.
[0114] 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.
[0115] Furthermore, for the aforesaid purpose, various kinds of silicone oils (e.g., dimethylsilicone oil and denatured silicone oils formed by introducing various organic groups to dimethylsiloxane) can be used. 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.)
[0117] For the light-sensitive material and the dye-fixing material may be used a discoloration inhibitor. As the discoloration inhibitors, there are, for example, antioxidants, ultraviolet absorbents, and certain kinds of metal complexes.
[0118] Examples of the antioxidant are 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.
[0119] As the 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.
[0120] As the metal complexes, there are the compounds described in U.S. Patents 4,241,155, 4,245,018, columns 3 to 36, and 4,254,195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages 27 to 29, JP-A-63-199248, Japanese Patent Application Nos. 62-234103 and 62-230595 (corresponding to JP A 1-75568 and JP-A-1-74272, respectively).
[0121] Examples of the useful discoloration inhibitor which can be used in this invention are described in JP-A-62-215272, pages 125 to 137.
[0122] 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.
[0123] The aforesaid antioxidant, the ultraviolet absorbent and the metal complex may be used as a combination thereof.
[0124] For the light-sensitive material and the dye-fixing material may be used a brightening agent. In this case, it is preferred that 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.
[0126] For the layers constituting the light-sensitive material and the dye-fixing material, a hardening agent is used 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.
[0127] Specific examples of the hardening agent are 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.
[0128] For the layers constituting the light-sensitive material and the dye-fixing material, 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.
[0129] Also, for the layers constituting the light-sensitive material and the dye-fixing material, organic fluoro compounds may be used for sliding property improvement, static prevention, releasability improvement, etc.
[0130] Typical examples of the organic fluoro compound are 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).
[0131] Furthermore, for the light-sensitive material and the dye-fixing material may be used a matting agent. As the 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).
[0132] Still further, 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.
[0133] In this invention, 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.
[0134] From the physicochemical function, 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. However, 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.
[0135] As 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.
[0136] In the system of simultaneously carrying out the heat development and the transfer of dyes formed in the existence of a small amount of water, it is preferred that 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.
[0137] Furthermore, 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.
[0138] 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.
[0139] The term "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.
[0140] Practical examples thereof are an acid precursor releasing an acid by heating, an electrophilic compound causing a displacement reaction with an existing base by heating, a nitrogen-containing heterocyclic compound, and a mercapto compound or a precursor therefor.
[0142] As 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. In general, there are papers and synthetic polymer films.
[0143] Practical examples thereof are films of polyethylene terephthalate, polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, or celluloses (e.g., triacetyl cellulose), the aforesaid films containing 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.
[0144] 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.
[0146] Also, a 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.
[0147] As 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.
[0148] As 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.
[0149] Also, 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. As the non-linear optical material, there are inorganic compounds such as lithium niobate, potassium dihydrogenphosphate (KDP), lithium iodate, BaB204, 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.
[0150] As the wavelength conversion element, a single crystal light waveguide type, a fiber type, etc., are known and they are useful.
[0151] Also, as the aforesaid image information, 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.
[0152] 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. In this case, a transparent or opaque heating element described in JP-A-61-145544 can be utilized. These electroconductive layers also function as static prevention layers.
[0153] 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.
[0154] The diffusion transfer step of dyes may be performed simultaneously with the heat development or may be performed after finishing the heat development step. In the latter case, 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 100 C lower than the temperature in the heat development step is particularly preferred.
[0155] The transfer of dyes is carried out by heat only but a solvent may be used for accelerating the transfer of dyes.
[0156] Also, as described in detail in JP-A-59-218443 and JP-A-61-238056, a method of simultaneously or successively performing the development and the dye transfer by heating in the existence of a small amount of a solvent (in particular, water) is useful. In the system, 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.
[0157] As examples of 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.
[0158] 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).
[0159] As a methods of applying the solvent to the light-sensitive layer or the dye-fixing layer, there is a method described in JP-A-61-147244, page 26. Also, the solvent may be previously incorporated in the light-sensitive material and/or the dye-fixing material as a form of being encapsulated.
[0160] Also, for accelerating the dye transfer, 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. Also, 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.
[0161] Examples of the hydrophilic thermal solvent are ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and heterocyclic compounds.
[0162] Also, for accelerating the dye transfer, a high-boiling organic solvent may be incorporated in the light-sensitive material and/or the dye-fixing material.
[0163] As 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.
[0164] The pressure condition and the manner of applying pressure in the case of superposing the light-sensitive material on the dye-fixing material are described in JP-A-61-147244, page 27.
[0165] 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").
[0166] The following examples are intended to illustrate the present invention in more detail but not to limit it in any way. All the ports and percents are given by weight unless otherwise indicated.
EXAMPLE 1
[0168] 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)
Dye-Providing Compound (3)
Electron Donor (1)
High-Boiling Solvent (2)
[0171] To an aqueous gelatin solution (containing 20 g of gelatin, 3 g of potassium bromide, and 0.3 g of HO-(CH2)2S(CHz)2S(CH2)20H in 800 ml of water kept at 55 C) with stirring well were simultaneously added Solution (1) and Solution (2) shown below over a period of 30 minutes. Thereafter, Solution (3) and Solution (4) shown below were simultaneously added thereto over a period of 20 minutes. In this case, 5 minuutes after intiation of the addition of the solution (3), a solution of the dye shown below was added thereto over a period of 18 minutes.
[0172] After washing with water and desalting, 20 g of lime-processed ossein gelatin was added to the emulsion thus formed, and after adjusting the pH and pAg thereof to 6.2 and 8.5, respectively, sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, and chloroauric acid were added thereto to perform the optimum chemical sensitization. Thus, 600 g of a monodisperse tetradecahedral silver iodobromide emulsion having a mean grain size of 0.40 µm was obtained.
[0176] To an 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) with stirring well were simultaneously added Solution (I) and Solution (II) shown below at a same flow rate over a period of 60 minutes. After finishing the addition of the Solution (I), a methanol solution (III) of the sensitizing dye C shown below was added to the mixture. Thus, a dye-adsorbed monodisperse cubic silver halide emulsion having a mean grain size of 0.45 µm was obtained.
[0177] After washing with water and desalting, 20 g of gelatin was added to the emulsion, and after adjusting the pH and pAg thereof to 6.4 and 7.8, respectively, the emulsion was chemically sensitized at 60.0 C. In 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.
[0181] To an aqueous gelatin solution (a solution formed by adding 20 g of gelatin, 1 g of potassium bromide, and 0.5 g of HO(CH2)2S(CH2)20H to 800 ml of water and kept at 50°C) with stirring well were simultaneously added Solution (I), Solution (II), and Solution (III) of dye (a) and dye (b) shown below at a same flow rate over a period of 30 minutes to provide a dye-adsorbed monodisperse silver bromide emulsion having a mean grain size of 0.42 um.
[0182] After washing with water and desalting, 20 g of lime-processed ossein gelatin was added to the emulsion and after adjusting the pH and pAg thereof to 6.4 and 8.2, respectively, 9 mg of sodium thiosulfate, 6 ml of an aqueous solution of 0.01% chloroauric acid, and 190 mg of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene were added thereto with kept at 60°C to perform a chemical sensitization for 45 minute. The amount of the emulsion obtained was 635 g.
Dye (b):
[0184] To 100 ml of an aqueous 4% gelatin solution were added 12.5 g of zinc hydroxide having a mean grain size of 0.2 um, 1 g of carboxymethyl cellulose as a dispersing agent, and 0.1 g of sodium polyacrylate and the mixture was ground in a mill using glass beads having a mean particle size of 0.75 mm for 30 minutes. By separating the glass beads, a dispersion of zinc hydroxide was obtained.
[0186] To 100 ml of an aqueous 5% gelatin solution were added 2.5 g of 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 µm was obtained.
[0188] To 100 ml of an aqueous 5% gelatin solution were added 10 g of the electron transferring agent shown below, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersing agent, and 0.5 g of the anionic surface active agent shown below as a dispersing agent, and the mixture was ground in a mill for 60 minutes using glass beads having a mean particle size of 0.75 mm. By separating the glass brands, a dispersion of the electron transferring agent having a mean grain size of 0.3 u.m was obtained.
[0191] Then, a method of preparing a gelatin dispersion of electron donor (4) for interlayer is explained.
[0192] To 30 ml of ethyl acetate were added 23.6 g of the electron donor (4) shown below and 8.5 g of the high-boiling solvent (2) shown above to form a uniform solution. After mixing the solution with 100 g of an aqueous solution of 10% lime-processed gelatin, 0.25 g of sodium hydrogensulfite, 0.3 g of sodium dodecylbenzenesulfonate, and 30 ml of water, the resultant mixture was dispersed using a homogenizer at 10,000 r.p.m. for 10 minutes. The dispersion thus obtained is called a gelatin dispersion of the electron donor (4).
[0194] Then, a heat-developable color light-sensitive material 101 of a multilayer structure having the following layer structures was prepared using the compositions prepared above.
[0195] The layer structures are shown from the upper-most layer and the numerals are coated amounts shown by mg/m2.
Support
[0196] Polyethylene terephthalate film of 96 µm in thickness (coated with carbon black as the back layer).
[0198] (*1): Polyvinyl Alcohol (molecular weight: 2,000)
(*2): Surface Active Agent (5)
(*3): Surface Active Agent (6)
(*4): Water-Soluble Polymer
(*5): Antifoggant (7)
(*6): Surface Active Agent (8)
(*7): Surface Active Agent (9)
(*8): Electron Transferring Agent (10)
(*9): Hardening Agent (11) 1,2-Bis(vinylsulfonylacetamido)ethane
(*10): Antifoggant (12)
[0199] Then, a method of making a dye-fixing material is explained. A dye-fixing material R-1 having the following layer structure was prepared.
Support
[0201] The support was composed of a wood free paper (LBKP/NBKP = 1:1, density 1.080) having a thickness of 92.6 um. The front surface thereof was coated with a glossy polyethylene layer having a thickness of 45.0 µm 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 µm.
[0202] Also, the back surface thereof was coated with matting surface having a thickness of 36.0 µm composed of high-density polyethylene (density 0.960), and with a subbing layer composed of a gelatin layer of 0.05 µm thick and a colloidal silica layer of 0.05 µm thick.
[0204] The compounds used for the dye-fixing material were as follows.
Silicon Oil (1):
Surface Active Agent (1):
Surface Active Agent (2):
Surface Active Agent (3):
Surface Active Agent (4):
[0206] Surface Active Agent (5):
Water-Soluble Polymer (1):
Sumica Gel L5-H (trade name, made by Sumitomo Chemical Company, Limited)
[0210] Then, by following the same procedure as the case of preparing the light-sensitive material 101 except that the electron transferring agent precursor was changed as shown in Table 1 below, light-sensitive materials 102 to 110 were prepared.
[0211] 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.
[0212] While sending the exposed light-sensitive material at a line speed of 20 mm/sec, 15 ml/m2 of water was supplied to the emulsion surface with a wire bar and then the light-sensitive material was immediately superposed on the image-receiving (fixing) material so that the emulsion layer was in contact with the image-fixing layer.
[0213] 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.
[0214] The maximum densities (Dmax) and the minimum densities (Dmin) of cyan, magenta, and yellow at the gray portion were measured and the results obtained are also shown in Table 1 below.
[0216] As is clear from the results shown in Table 1 above, by using the reducing agent precursors (electron transferring agent precursors) defined in this invention, positive images having low Dmin and a good discrimination can be obtained.
[0217] In addition, in the light-sensitive materials 102, 103, and 105, white spot-like unevenness was observed on the images. This is considered to show that when a precursor having a high melting point (M.P.) is used, the precursor is liable to deposit in the light-sensitive material.
EXAMPLE 2
[0218] Using the same emulsions, dye-providing compounds, electron donors as those in the color light-sensitive material 101 in Example 1, multilayer color light-sensitive material 201 having the layer structures shown below was prepared.
[0219] In addition, the additives were, unless otherwise indicated, same as those for the light-sensitive material 101.
[0221] In a mixture of 1,000 ml of an aqueous 0.1% sodium hydroxide solution and 200 t of methanol were dissolved 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropionic acid and the solution obtained was stirred at 40° C. To the solution was added a solution of 4.5 g of silver nitrate dissolved in 200 ml of water over a period of 5 minutes and then the excessive salt was removed by flocculation method. Thereafter, the pH thereof was adjusted to 6.3 to provide 300 g of the organic silver salt emulsion.
[0222] The layer structures are also shown from the uppermost layer. In addition, the numerals shown below are the coated amounts shown by mg/m2.
Support
[0223] Polyethylene terephthalate film of 100 µm in thickness.
The compounds newly used for the above light-sensitive material were as follows.
[0224] Electron Transferring Agent Precursor C (comparison):
(*1): Electron Transferring Agent (13)
(*2): Thermal Solvent (14) Benzenesulfonamide
(*3): Base Precursor (15) 4-Chlorophenylsulfonylacetic acid guanidine
(*4): Reducing Agent (16)
Then, a method of making a dye-fixing material R-2 is explained.
[0225] In 200 ml of water was dissolved 10 g of poly(methylacrylate-co-N,N,N-trimethyl-N-vinylbenzylammonium chloride) (the ratio of methyl acrylate : vinylbenzylammonium chloride was 1:1) and the solution was uniformly mixed with 100 g of an aqueous solution of 10% lime-processed gelatin. After adding thereto a hardening agent, the mixture was uniformly coated on a paper support coated with polyethylene having titanium dioxide dispersed therein at a wet thickness of 90 urn. The sample was dried and used as the dye-fixing material R-2 having a mordant layer.
[0226] Then, by following the same procedure as the light-sensitive material 201 except that the electron transferring agent precursor was changed as shown in Table 2 below, light-sensitive materials 202 to 205 were prepared.
[0227] 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.
[0228] After applying 20 ml/m2 of water to the mordant layer side of the dye-fixing material R-2, 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.
[0229] Thereafter, after passing the assembly through a laminator heated to 80° C at a line speed of 12 mm/sec, both the materials were separated from each other, whereby a positive image was obtained on the dye-fixing material in each case. Then, Dmax and Dmin at the gray portion were measured and the results are also shown in Table 2 below.
[0230] From the results shown in Table 2 above, it can be seen that by using the electron transferring agent precursors defined in this invention, positive images having low Dmin and a good discrimination are obtained.
EXAMPLE 3
[0232] To 50 ml of ethyl acetate were added 16 g of an electron donor (17) having the structure shown below, 6.5 g of a high-boiling solvent (2) shown above, and 1.2 g of the electron transferring agent precursor D shown below and the mixture was heated to about 60° C to form a uniform solution. After mixing the solution with 100 g of an aqueous 10% lime-processed gelatin solution, 0.6 g of sodium dodecylbenzene sulfonate and 50 ml of water, the mixture was dispersed in a homogenizer for 10 minutes at 10,000 r.p.m. The dispersion is called a gelatin dispersion of electron donor.
[0234] By using the aforesaid dispersion and Emulsion (III) and other materials as used in Example 1, a double layer black-and-white light-sensitive material having the following layer structures was prepared.
[0235] In addition, unless otherwise indicated, the additives used were same as those for the light-sensitive material 101 in Example 1.
Support
[0238] Using the materials for the image-receiving material R-1 in Example 1, an alkali-generating sheet R-3 shown below was prepared.
Support
[0240] By following the same procedure as the light-sensitive material 301 except that the electron transferring agent precursor D was changed as shown in Table 3 below (equimolar amount), light-sensitive materials 302 and 303 were prepared.
[0241] 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.
[0242] While sending the exposed light-sensitive material at a line speed of 20 mm/sec, 15 ml/m2 of water was supplied to the emulsion surface with a wire bar and then the light-sensitive material was immediately superposed on the alkali-generating sheet such that the emulsion layer was in contact with the layer of the sheet.
[0243] 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.
[0244] The transmission density of the silver images formed was measured on Dmax and Dmin and the results are shown in Table 3 below.
[0245] From the results shown in Table 3, it can be seen that by using the reducing agent precursors defined by this invention, negative images having high Dmax and a good discrimination are obtained.
EXAMPLE 4
[0247] To an 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(CH2)2S(CH2)2S(CH2)20H to 800 ml of water and kept at 50 C) with stirring well were simultaneously added Solution (1) and Solution (2) shown below over a period of 30 minutes. Thereafter, Solution (3) and Solution (4) shown below were simultaneously added thereto over a period of 20 minutes. Also, 5 minutes after initiating the addition of the solution (3), a solution of the dye shown below was added over a period of 18 minutes.
[0248] After washing with water and desalting, 20 g of lime-processed ossein gelatin was added to the emulsion, and adjusting the pH and pAg thereof to 6.2 and 8.5, respectively, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and chloroauric acid were added thereto to perform the optimum chemical sensitization. Thus, 600 g of a monodisperse cubic silver chlorobromide emulsion having a mean grain size of 0.40 µm was obtained.
[0249] The dye solution was a solution dissolving the following dyes in 160 ml of methanol.
Compound (1):
[0251] To an 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) with stirring well were simultaneously added Solution (I) and Solution (II) shown below at a same flow rate over a period of 60 minutes. After finishing the addition of the solution (I), the methanol solution (III) of the sensitizing dye C shown below was added. Thus, a dye-adsorbed monodisperse cubic silver halide emulsion having a grain size of 0.45 um was prepared.
[0252] After washing with water and desalting, 20 g of gelatin was added to the emulsion, and after adjusting the pH and pAg thereof to 6.4 and 7.8, respectively, the emulsion was chemically sensitized at 60.0 C. In 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.
[0255] To an 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) with stirring well were simultaneously added Solution (I) and Solution (II) shown below at a same flow rate over a period of 30 minutes. Thereafter, Solution (III) and Solution (IV) were further simultaneously added thereto over a period of 30 minutes. Also, 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.
[0256] After washing with water and desalting, 22 g of lime-processed ossein gelatin was added thereto, and after adjusting the pH and pAg thereof to 6.2 and 7.7, respectively, sodium thiosulfate, 4-hydroxy-6-methyl 1,3,3a,7-tetraazaindene, and chloroauric acid were added thereto to perform the optimum chemical sensitization at 60° C. Thus, a monodisperse cubic silver chlorobromide emulsion having a mean grain size of 0.38 µm was obtained. The amount thereof was 635 g.
[0257] 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.
[0259] To 100 ml of an aqueous 4% gelatin solution were added 12.5 g of zinc hydroxide having a mean grain size of 0.2 um, 1 g of carboxymethyl cellulose as a dispersing agent, and 0.1 g of sodium polyacrylate, and the mixture was ground in a mill for 30 minutes using glass beads having a mean particle size of 0.75 mm. By separating glass beads, a dispersion of zinc hydroxide was obtained.
[0261] To 100 ml of an aqueous 5% gelatin solution were added 2.5 g of 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 µm was obtained.
[0263] To 100 ml of an aqueous 5% gelatin solution were added 10 g of the electron transferring agent (X-22) shown below, 0.5 g of polyethylene glycol nonylphenyl ether as a dispersing agent, and 0.5 g of the anionic surface active agent shown below, and the mixture was ground in a mill for 60 minutes using glass beads having a mean particle size of 0.75 mm. By separating glass beads, a dispersion of the electron transferring agent having a mean grain size of 0.3 u.m was obtained.
[0267] In 50 ml of ethyl acetate was dissolved each of the yellow, magenta, and cyan dye-providing compounds shown below by heating to about 60. C to form a uniform solution and after mixing the solution with 100 g of an aqueous solution of 10% lime-processed gelatin, 0.6 g of sodium dodecylbenzenesulfonate, and 50 ml of water, the mixture was dispersed by a homogenizer for 10 minutes at 10,000 r.p.m. The dispersion was called a gelatin dispersion of the dye-providing compound.
High-Boiling Solvent (1):
[0269] Electron Transferring Agent Precursor (2) (XP-5)
(1) Yellow Dye-Providing Compound
(2) Magenta Dye-Providing Compound
(3) Cyan Dye-Providing Compound
[0270] Then, a method of preparing a gelatin dispersion of Electron Donor (3) for interlayer is explained.
[0271] To 30 ml of ethyl acetate were added 23.6 g of the electron donor (3) shown below and 8.5 g of the high-boiling solvent (1) shown above to form a uniform solution. After mixing the solution with 100 g of an aqueous solution of 10% lime-processed gelatin, 0.25 g of sodium hydrogensulfite, and 0.3 g of sodium dodecylbenzenesulfonate, and 30 ml of water with stirring, the mixture was dispersed with a homogenizer for 10 minutes at 10,000 r.p.m. The dispersion was called as a gelatin dispersion of the electron donor (3).
[0273] A multilayer heat-developable color light-sensitive material 401 having the layer structures shown below was prepared using the aforesaid compositions.
[0274] The layer structures are shown from the upper-most layer. In addition, the numerals are coating amounts in mg/m2.
Support
[0275] A polyethylene terephthalate film of 96 µm in thickness containing carbon black in a back layer.
[0276] The compounds used above were as follows.
(*1): Surface Active Agent (4)
(*2): Surface Active Agent (5)
(*3): Water-soluble Polymer
(*4): Antifoggant (6)
(*5): Surface Active Agent (7)
(*6): Surface Active Agent (8)
(*7): Hardening Agent (9) 1,2-Bis(vinylsulfonylacetamido)ethane
(*8): Antifoggant (10)
(*9): Polyvinyl Alcohol (molecular weight: 2000)
[0277] Then, by following the same procedure as the case of preparing the light-sensitive material 401 except that the electron donor was changed as shown in Table 4 below, light-sensitive materials 402 to 420 were prepared.
[0278] 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.
[0279] While sending the exposed light-sensitive material at a line speed of 20 mm/sec, 15 ml/m2 of water was supplied to the emulsion layer surface with a wire bar and then the light-sensitive material was immediately superposed on the image-receiving material R-1 as in Example 1 such that the layers were in contact relation.
[0280] Then, 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.
[0281] The maximum density (Dmax) and the minimum density (Dmin) of each of the cyan, magenta, and yellow colors in the gray portion were measured and the results thus obtained are shown in Table 5 below.
[0282] 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.
[0283] 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.
[0284] On the other hand, in the samples 408 and 409 using the electron donor precursor shown by formula (A) or (B), images having low Dmin and sufficiently high Dmax are obtained.
[0285] In the system of using an electron donor and an electron donor precursor, 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.
EXAMPLE 5
[0286] 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.
[0287] In addition, unless otherwise indicated, the same additives as those of the light-sensitive material 401 were used.
[0289] In a mixture of 1,000 ml of an aqueous 0.1% sodium hydroxide solution and 200 ml of ethanol were dissolved 20 g of gelatin and 5.9 g of 4-acetylaminophenylpropionate, and the solution was stirred at 40 C. To the solution was added a solution of 4.5 g of silver nitrate dissolved in 200 ml of water over a period of 5 minutes. Then, excessive salts were removed by flocculation method and thereafter, the pH thereof was adjusted to 6.3 to provide 300 g of the organic silver salt emulsion.
[0290] The layer structures are shown from the uppermost layer. In addition, the numerals are the coating amounts in mg/m2.
Support
[0292] By following the same procedure as the case of preparing the light-sensitive material 501 except that each of the compounds of this invention was added as shown in Table 6 below, light-sensitive materials 502 to 509 were prepared.
[0293] 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.
[0294] After supplying 20 ml/m2 of water to the layer surface side of the dye-fixing material R-2 as in Example 2, the aforesaid heat-treated light-sensitive material was superposed on the image-fixing material such that the layers were in contact relation.
[0295] Then, the assembly was passed through a laminator heated to 800 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.
[0296] Dmax and Dmin of each of the cyan, magenta, and yellow colors in the gray portion were measured and the results are shown in Table 7 below.
1. 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;
wherein R1, R2, R3, and R4 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and X represents a substituted alkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a group shown by the following formula
(wherein Z represents a divalent linkage group bonded to the phthalide nucleus via an oxygen atom; n represents 0 or 1; L represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, 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; and m represents 0 or an integer of from 1 to 4), or a group shown by the following formula
(wherein M represents
(wherein p represents 2 or 3; R" represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, or an alkoxy group; and R12 and R13 each represents a hydrogen atom, a halogen atom, an alkyl group, a phenyl group; said R12 and R13 may close ring together to form a benzene ring); and Q represents a hydroxy group,
or R16 (wherein R'4 represents a hydrogen atom, an aryl group, or an alkyl group; R15 represents a hydrogen atom or an acyl group; and R'6 represents a hydrolyzable group)).
wherein R1, R2, R3, and R4 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group; R5 represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group; and X represents a substituted alkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, a sulfamoyl group, a substituted sulfamoyl group, a group shown by the following formula
(wherein Z represents a divalent linkage group bonded to the phthalide nucleus via an oxygen atom; n represents 0 or 1; L represents a halogen atom, an alkyl group, an alkenyl group, an aryl group, 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; and m represents 0 or an integer of from 1 to 4), or a group shown by the following formula
(wherein M represents
(wherein p represents 2 or 3; R" represents a hydrogen atom, an alkyl group, a phenyl group, a halogen atom, or an alkoxy group; and R12 and R13 each represents a hydrogen atom, a halogen atom, an alkyl group, a phenyl group; said R12 and R13 may close ring together to form a benzene ring); and Q represents a hydroxy group,
or R16 (wherein R'4 represents a hydrogen atom, an aryl group, or an alkyl group; R15 represents a hydrogen atom or an acyl group; and R'6 represents a hydrolyzable group)).
2. A heat-developable light-sensitive material as claimed in claim 1, wherein R1, R2 R3, and R4 each represents a hydrogen atom, a substituted or unsubstituted alkyl group having
not more than 20 carbon atoms, a substituted or unsubstituted aryl group having not
more than 20 carbon atoms, or a substituted or unsubstituted 5, 6, 9, 10, 13, 14-membered
heterocyclic group containing as a hetero atom at least one of O, N and S, having
not more than 20 carbon atoms.
3. A heat-developable light-sensitive material as claimed in claim 1, wherein R5 represents a substituted or unsubstituted aryl group having not more than 20 carbon
atoms or a substituted or unsubstituted 5, 6, 9, 10, 13, 14-membered heterocyclic
group containing as a hetero atom at least one of 0, N and S, having not more than
20 carbon atoms.
4. A heat-developable light-sensitive material as claimed in claim 1, wherein the
substituted alkyl group shown by X is represented by -CH2-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.
5. A heat-developable light-sensitive material as claimed in claim 1, wherein the
hydrolyzable group shown by R16 is
or
wherein R17 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; R18 and R19 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 R18 and R19 may be the same or different; and the aliphatic group shown by R17, R18 or R19 may be substituted or unsubstituted, chain like, or cyclic.
or
wherein R17 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; R18 and R19 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 R18 and R19 may be the same or different; and the aliphatic group shown by R17, R18 or R19 may be substituted or unsubstituted, chain like, or cyclic.
6. A heat-developable light-sensitive material as claimed in claim 1, wherein said
heat-developable light-sensitive material further comprises a reducing agent.
7. A heat-developable light-sensitive material as claimed in claim 6, wherein the
total addition amounts of the reducing agent and the reducing agent precursor are
from 0.001 to 20 mols per mol of silver.
8. A heat-developable light-sensitive material as claimed in claim 7, wherein the
total addition amounts are from 0.01 to 10 mols per mol of silver.
9. A heat-developable light-sensitive material as claimed in claim 1, wherein said
heat-developable light-sensitive material is a heat-developable color photographic
light-sensitive material.
10. A heat-developable light-sensitive material as claimed in claim 9, wherein said
heat-developable light-sensitive material further comprises a dye- providing substance
releasing a mobile dye counter-corresponding to the reaction of reducing silver ions
to silver and an electron donor precursor represented by formula (A) or (B);
wherein R3, represents a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted amino group or a substituted or unsubstituted anilino group; R32, R33 and R34 each represents a hydrogen atom, a halogen atom, a cyano group, a sulfonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amido group, a substituted or unsubstituted imido group, a substituted or unsubstituted sulfonamido group or a substituted or unsubstituted heterocyclic residue; said R32 R33, and R34 may be the same or different; at least one of said R32, R33, and R34 is selected from a halogen atom, a cyano group, a sulfonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group; R22, R23, R24 and R25 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted imido group, a carboxy group or a substituted or unsubstituted sulfonamido group; the sum of the carbon atoms of said R22, R23, R24 and R25 is at least 8; said R22 and R23 and/or said R24 and R25 may combine with each other to form a saturated or unsaturated ring; R26 represents a hydrogen atom or
wherein R31 is the same as defined above; and R27 represents a hydrogen atom or
wherein R32 to R34 are the same as defined above.
wherein R3, represents a hydroxy group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted amino group or a substituted or unsubstituted anilino group; R32, R33 and R34 each represents a hydrogen atom, a halogen atom, a cyano group, a sulfonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted amido group, a substituted or unsubstituted imido group, a substituted or unsubstituted sulfonamido group or a substituted or unsubstituted heterocyclic residue; said R32 R33, and R34 may be the same or different; at least one of said R32, R33, and R34 is selected from a halogen atom, a cyano group, a sulfonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, and an aryloxycarbonyl group; R22, R23, R24 and R25 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted sulfonyl group, a sulfo group, a halogen atom, a cyano group, a carbamoyl group, a sulfamoyl group, a substituted or unsubstituted amido group, a substituted or unsubstituted imido group, a carboxy group or a substituted or unsubstituted sulfonamido group; the sum of the carbon atoms of said R22, R23, R24 and R25 is at least 8; said R22 and R23 and/or said R24 and R25 may combine with each other to form a saturated or unsaturated ring; R26 represents a hydrogen atom or
wherein R31 is the same as defined above; and R27 represents a hydrogen atom or
wherein R32 to R34 are the same as defined above.