|
(11) | EP 0 588 325 A1 |
| (12) | EUROPEAN PATENT APPLICATION |
|
|
|
|
|||||||||||||||||||||||||||
| (54) | Heat-developing diffusion transfer color photographic material |
| (57) Disclosed is a heat-developing diffusion transfer color photographic material having
on a support at least one layer containing therein a light-sensitive silver halide,
a binder and a non-diffusive dye donor compound capable of releasing or forming a
diffusive dye in correspondence or reverse correspondence to a reduction reaction
of the silver halide to silver. The non-diffusive dye donor compound has been added
to the material as an emulsified dispersion thereof having a mean grain size of 0.3
µmm or less. |
FIELD OF THE INVENTION
[0001] The present invention relates to a heat-developing diffusion transfer color photographic material and, in particular, to that forming a color image of good discrimination.
BACKGROUND OF THE INVENTION
[0002] Since photographic methods of using a silver halide are superior to any other photographic method, such as an electro-photographic method or a diazophotographic method, with respect to photographic characteristics such as sensitivity and gradation adjustment, they have heretofore been utilized most widely in this technical field. In particular, since color hard copies with a highest image quality can be obtained by such silver halide photography, this type of photography has been studied and developed increasingly in recent times.
[0003] Recently, a system for simply and rapidly obtaining a photographic image has been developed, by converting the conventional wet processing treatment with a developer or the like in a method for forming a photographic image in a silver halide-containing photographic material, into an instant photographic system containing a developer in the photographic material itself, or into a dry heat-development processing treatment by heating or the like. In simple and rapid processing methods, an image forming system by a diffusion transfer process is frequently employed for the purpose of preventing stains of the printed images, which stains often occur during the printing-out step of the developed silver halide materials.
[0004] A diffusion transfer method is such that a diffusive dye is imagewise formed or released. The diffusive dye is then transferred to an image-receiving material having a mordant agent with water or a solvent. The details of the method are described in Angew. Chem. Int. Ed. Engl., 22 (1983), 191. The photographic material to be processed by a system of forming a photographic image in accordance with such a diffusion transfer method contains dye donor compound(s). The dye(s) derived from the compound(s) is/are transferred onto an image-receiving material in the development step to form an intended photographic image. In the system, various methods have heretofore been employed for incorporating dye donor compound(s) into a photographic material. The most popular method is one in which an oil-soluble dye donor compound is dissolved in a high-boiling organic solvent and emulsified and dispersed in an aqueous dispersion medium to give an oil-in-water dispersion and the dispersion is incorporated into a photographic material along with a water-soluble binder.
[0005] The present inventors have continued to study and develop a heat-developing diffusion transfer color photographic material of the above-mentioned type and have investigated the above-mentioned emulsifying and dispersing technology as a method of uniformly dispersing an oil-soluble ingredient such as a dye donor compound in a water-soluble binder. As a result, we have found that the discrimination of the photographic image to be formed by the diffusion transfer method is insufficient and, in particular, the maximum density of the image is low, when the photographic material contains an emulsified dispersion of the oil-soluble dye donor compound having a large grain (oil droplet) size.
SUMMARY OF THE INVENTION
[0006] An object of the present invention is to provide a heat-developing diffusion transfer color photographic material which forms an image of good discrimination.
[0007] This and other objects have been attained by a heat-developing diffusion transfer color photographic material having on a support a light-sensitive silver halide, a binder and a non-diffusive dye donor compound capable of releasing or forming a diffusive dye in correspondence or reverse correspondence to a reduction reaction of the silver halide to silver, in which the non-diffusive dye donor compound has been added to the material as an emulsified dispersion thereof having a mean grain (oil droplet) size of 0.3 µm or less. Alternatively, the present invention may also be stated as a method of producing a heat-developing diffusion transfer color photographic material having on a support a light-sensitive silver halide, a binder and a non-diffusive dye donor compound capable of releasing or forming a diffusive dye in correspondence or reverse correspondence to a reduction reaction of the silver halide to silver, in which the non-diffusive dye donor compound has been added to the material as an emulsified dispersion of the compound having a mean grain (oil droplet) size of 0.3 µm or less.
DETAILED DESCRIPTION OF THE INVENTION
[0010] For emulsifying and dispersing the non-diffusive dye donor compound to form an emulsified dispersion thereof for use in the present invention, any method known in this technical field can be employed. The details of the background of the fundamental theory thereof are explained in, for example, F. Kitahara et al's Chemistry of Emulsification and Dispersion. For instance, emulsification and dispersion of non-diffusive dye donor compounds for use in the present invention may be effected in accordance with the process mentioned below.
[0011] First, organic materials are dissolved in a suitable low-boiling point solvent (having a boiling point of not higher than 160°C). Other organic materials (for example, reducing agent, high-boiling point solvent, high polymer compound, etc.) may be dissolved therein together with those organic materials. The low-boiling point solvent to be used in this step may be any ordinary organic solvent. Preferred examples of suitable low-boiling point solvents include ethyl acetate, MEK, cyclohexanone and DMF. Preferred examples of suitable high-boiling point solvents include carboxylates and phosphates such as those described in, for example, JP-A-59-83154, 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. The term "JP-A" as used herein means an "unexamined published Japanese patent application".
[0012] The high polymer compound for use in the present invention may be any which is soluble in organic solvents. In particular, preferred are homopolymers or copolymers of, for example, polyesters or polyamides such as those described in JP-B-51-39853 and JP-A-51-59943. The term "JP-B" as used herein means an "examined Japanese patent publication". The solution of the non-diffusive dye donor compound thus formed by dissolving it in an organic solvent is called an oily phase solution. On the other hand, an aqueous solution of a water-soluble high polymer is generally used as a dispersion medium. This is called an aqueous phase solution. As the high polymer, preferably used are, for example, gelatin, polyvinyl alcohol, dextran, pullulan, carboxymethyl cellulose, hydroxyethyl cellulose and cellulose ether which are known in this technical field.
[0013] Regarding the time for dissolving the water-soluble high polymer in water, the polymer may be previously formed into its aqueous solution prior to emulsification of the dye donor compound or the polymer which is solid may be dissolved in water simultaneously with the emulsification of that compound. A surfactant is dissolved in the oily phase solution and/or the aqueous phase solution thus formed, and the two are blended, imparting mechanical energy thereto, to prepare an emulsified dispersion. The surfactant to be used in the step may be any known anionic, cationic, betainic or nonionic surfactant. One or more of them may be used singly or in combination. In view of the coatability of the coating liquid containing the dispersion, anionic surfactants are preferably used. Preferred examples of the surfactants to be used in the emulsification and dispersion are described in, for example, JP-A-59-157639, pages 37 and 38. As an emulsifying machine for the emulsification and dispersion, any machine known in this technical field can be employed. Preferred examples include a high-pressure homogenizer, a dissolver, a rodstat emulsifying machine and a stirring homogenizer.
[0014] In the present invention, the emulsified dispersion of a dye donor compound(s) is to have a mean grain size of 0.3 µmm or less. Specifically, an emulsified dispersion of a dye donor compound(s) having a mean grain size of 0.3 µmm or less is prepared in accordance with the above-mentioned emulsifying and dispersing method, and a heat-developing photographic material is prepared using the dispersion. For preparing the emulsified dispersion having a smaller mean grain size than conventional dispersions, the rotation number of the emulsifying machine to be used is increased most commonly. The mean grain size of the emulsified dispersion for use in the present invention is preferably 0.2 µmm or less, more preferably 0.15 µmm or less. The lowermost limit of the size is not specifically defined but is preferably about 0.01 µmm.
[0015] The mean grain size of the emulsified dispersion for use in the present invention is determined in accordance with the method mentioned below.
Method of Measuring Grain Size of Emulsion:
[0016] A 2 % solution of phosphotungstic acid dissolved in a buffer solution having pH of 7.4 and an emulsion to be measured, which has been diluted with water to have a 1/3 concentration, are mixed in a ratio of 1/1, and the mixture is left to stand for 2 minutes. One drop of the mixture is dropped on a hydrophilicated carbon-deposited mesh (which was prepared by applying a collodion membrane to a fine copper mesh followed by vapor deposition of carbon onto the membrane and hydrophilication of the coated mesh), and the excess liquid is removed with a filter paper. The sample thus prepared is dried and observed with a 100C transmission electronic microscope (manufactured by Nippon Electronic Co.), whereupon an image (× 10,000) of the sample was taken by photography. Two hundred of the emulsified grains in the photograph were sampled out at random, and the diameter of each was individually measured. From the measured data, a mean value thereof is determined. The thus obtained mean value is the intended mean grain size of the emulsion.
[0017] The amount of the dye donor compound in the photographic material of the present invention depends upon the molar extinction coefficient (ε) of the dye from the compound. When the compound gives a dye having ε of 10,000 or more, it amount may be from 0.01 to 10 g, preferably from 0.05 to 5 g, per m² of the photographic material. The amount of the high-boiling point organic solvent to be used for dissolving the dye donor compound may be 10 g or less, preferably 5 g or less, per gram of the dye donor compound. It may be 1 cc or less, preferably 0.5 cc or less, especially preferably 0.3 cc or less, per gram of the binder in the photographic material of the present invention.
[0018] Where any organic material other than the dye donor compounds are incorporated into the photographic material of the present invention, they may also be added to the material by the same emulsifying and dispersing method mentioned above. In addition to the above-mentioned method, they may also be dispersed in a binder as their fine grains. In the case, surfactants such as those described in JP-A-59-157636, the technique at pages 37 and 38 may be employed.
[0019] The heat-developing diffusion transfer color photographic material of the present invention basically has a light-sensitive silver halide, a dye donor compound (which may act also as a reducing agent in the manner mentioned below) and a binder. Optionally it may further contain an organic metal salt oxidizing agent and the like. These components are generally in the same layer, while they may be in different layers provided that they may react with each other. For instance, a colored dye donor compound may be in a layer below a silver halide emulsion layer whereby lowering of the sensitivity of the emulsion layer may be prevented. The reducing agent is preferably contained in the photographic material, while it may be supplied from the outside, for example, by diffusing it from a dye fixing material containing the agent, which dye fixing material will be mentioned below.
[0020] Examples of the dye donor compounds to be employed in the present invention include compounds (couplers) capable of releasing or forming a dye by an oxidative coupling reaction. The coupler may be either a 4-equivalent or a 2-equivalent coupler. 2-Equivalent couplers which have a non-diffusive group as the releasable group and which form a diffusive dye by oxidative coupling reaction are also preferred. The non-diffusive group may be in the form of a polymer chain. Examples of color developing agents and couplers for use in the present invention are described in detail in T.H. James, The Theory of the Photographic Process, 4th Ed., pages 291 to 334 and 354 to 361 and in JP-A-58-123533, JP-A-58-149046, 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.
[0021] Further examples of the dye donor compounds include compounds adapted to imagewise release or spread a diffusive dye. Compounds of this type can be represented by formula (LI):
(Dye - Y)n - Z (LI)
wherein Dye represents a dye group or a dye precursor group whose wavelength has been shortened temporarily; Y represents a chemical bond or a linking group; Z represents a group which either causes an imagewise differential in the diffusibility of the compound (Dye-Y)n-Z in correspondence or reverse correspondence with the photosensitive silver salt carrying a latent image or releases the Dye and causes a differential in diffusibility between the released Dye and (Dye-Y)n-Z; and n represents 1 or 2, and when n is equal to 2, the two Dye-Y groups may be the same or different.
[0022] Specific examples of the dye donor compounds of the formula (LI) include the following compounds (1) through (5). Compounds (1) through (3) are those capable of forming a diffusive color image (positive color image) in reverse correspondence to development of silver halide; and compounds (4) and (5) are those of forming a diffusive color image (negative color image) in correspondence to development of silver halide.
(1) Color-developing agents comprising a combination of a hydroquinone developing agent and a dye component, as described in U.S. Patents 3,134,764, 3,362,819, 3,597,200, 3,544,545 and 3,482,972. The color-developing agents are diffusive under an alkaline condition but become non-diffusive after reacting with a silver halide.
(2) Non-diffusive compounds which may release a diffusive dye under an alkaline condition but which lose that capacity when reacted with a silver halide can also be used, as described in U.S Patent 4,503,137. Examples of such compounds include compounds capable of releasing a diffusive dye by intramolecular nucleophilic substitution reaction, as described in U.S. Patent 3,980,479; and compounds capable of releasing a diffusive dye by intramolecular rearrangement reaction of the isoxazolone ring in the molecule, as described in U.S. Patent 4,199,354.
(3) Non-diffusive compounds capable of reacting with a reducing agent which has remained
without being oxidized by development to release a diffusive dye can also be used,
as described in U.S. Patent 4,559,290, European Patent 220,746A2, U.S. Patent 4,783,396,
and Disclosure Bulletin 87-6199.
Examples of such compounds include compounds capable of releasing a diffusive dye
by intramolecular nucleophilic substitution reaction after reduction, as described
in U.S. Patent 4,139,389 and 4,139,379 and JP-A-59-185333 and JP-A-57-84453; compounds
capable of releasing a diffusive dye by an intramolecular electron-migrating reaction
after reduction, as described in U.S. Patent 4,232,107, JP-A-59-101649 and JP-A-61-88257
and RD No. 24025 (1984); compounds capable of releasing a diffusive dye by cleavage of the
single bond after reduction, as described in German Patent 3,003,588A, JP-A-56-142530
and U.S. Patents 4,343,893 and 4,619,884; nitro compounds capable of releasing a diffusive
dye after electron reception, as described in U.S. Patent 4,450,223; and compounds
of releasing a diffusive dye after electron reception, as described in U.S. Patent
4,609,610.
More preferred are compounds having an N-X bond (where X means an oxygen, sulfur or
nitrogen atom) and an electron-attracting group in one molecule, as described in European
Patent 220,746A2, Disclosure Bulletin 87-6199, U.S. Patent 4,783,396, and JP-A-63-201653
and JP-A-63-201654; compounds having an SO₂-X (where X has the same meaning as mentioned
above) and an electron-attracting group in one molecule, as described in JP-A-1-26842;
compounds having a PO-X bond (where X has the same meaning as mentioned above) and
an electron-attracting group in one molecule, as described in JP-A-63-271344; and
compounds having a C-X' bond (where X' has the same meaning as X or means -SO₂-) and
an electron-attracting group in one molecule, as described in JP-A-63-271341.
Also suitable are compounds capable of releasing a diffusive dye by cleavage of the
single bond after reduction due to the π-bond conjugating an electron-receiving group,
such as those described in Japanese Patent Application No. 62-106887.
Above all, especially preferred are compounds having an N-X bond and an electron-attracting
group in one molecule. Specific examples of such compounds include Compounds (1) to
(3), (7) to (10), (12), (13), (15), (23) to (26), (31), (32), (35), (36), (40), (41),
(53) to (59), (64) and (70) described in European Patent 220,746A2 and U.S. Patent
4,783,396, and Compounds (11) to (23) described in Disclosure Bulletin 87-6199.
(4) Compounds (DDR couplers) which have a diffusive dye as the releasing group and release the diffusive dye by reaction with an oxidation product of a reducing agent are also used. Examples of such compounds are described in British Patent 1,330,524, JP-B-48-39165 and U.S. Patents 3,443,940, 4,474,877 and 4,483,914.
(5) Compounds (DRR compounds) which have a property of reducing silver halides and organic silver salts and which release a diffusive dye after having reduced the halides or salts can also be used. Because the compounds of this type may function even in the absence of any other reducing agent, they are advantageously free from the problem of stain of images by the oxidized and decomposed product of a reducing agent. Specific examples of the compounds are described in U.S. Patents 3,928,312, 4,053,312, 4,055,423 and 4,336,322, JP-A-59-65839, JP-A-59-69839, JP-A-53-3819 and JP-A-51-104343, RD No. 17643, U.S. Patents 3,725,062, 3,728,113 and 3,443,939, JP-A-58-116537 and JP-A-57-179840 and U.S. Patent 4,500,626. Preferred examples of such DRR compounds are the compounds described in the above-mentioned U.S. Patent 4,500,626, columns 22 to 44. Above all, 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 said U.S. Patent are preferred. In addition, the compounds described in U.S. Patent 4,639,408, columns 37 to 39 are also useful.
[0023] As dye donor compounds other than the above-mentioned couplers and the compounds of formula (LI), dye-silver compounds comprising an organic silver salt and a dye bonded to each other (RD of May 1978, pages 54 to 58), azo dyes employable in a heat-developing silver dye bleaching method (U.S. Patent 4,235,957, RD of April 1976, pages 30 to 32) and leuco dyes (U.S. Patents 3,985,565 and 4,022,617) can also be employed in the present invention.
[0024] In order to obtain colors over a broad range in a chromaticity diagram by using three primary colors of yellow, magenta and cyan, a combination of at least three silver halide emulsion layers each having a light-sensitivity in a different spectral region is used. For instance, one may use a combination of three layers of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, and a combination of a green-sensitive layer, a red-sensitive layer and an infrared sensitive layer. The respective light-sensitive layers may be arranged in any desired sequence as generally employed in ordinary color photographic materials. These layers each may have two or more layers each having a different sensitivity degree.
[0025] The photographic material of the present invention may have other various auxiliary layers, such as a protective layer, a subbing layer, an interlayer, an anti-halation layer and a backing layer. In addition, various filter dyes may be added to the material so as to improve the color separatability of the material.
[0026] The silver halide for use in the present invention may be any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide.
[0027] The silver halide emulsion for use in the present invention may be either a surface latent image type emulsion or an internal latent type emulsion. The latter internal latent type emulsion is used as a direct reversal emulsion, in combination with a nucleating agent or with light fogging. The emulsion may also be a so-called core/shell emulsion in which the inside phase and the surface phase of each grain are different from each other. The silver halide emulsion may be either monodispersed or polydispersed. A mixture of several monodispersed emulsions may also be used. The silver halide grain size of the emulsion may be from 0.1 to 2 µmm, especially preferably from 0.2 to 1.5 µmm. The crystal habit of silver halide grains may be anyone of a cubic, octahedral or tetradecahedral shape, or a tabular shape having a high aspect ratio.
[0028] Specifically, all silver halide emulsions described in U.S. Patents 4,500,626 (column 50) and 4,628,021, Research Disclosure (hereinafter referred to as RD), No. 17,029 (1978), and JP-A-62-253159 can be used in the present invention.
[0029] Silver halide emulsions may be used as primitive ones. In general, however, they are chemically sensitized before use. For instance, any known sulfur sensitization, reduction sensitization and noble metal sensitization, which are generally applied to emulsions of ordinary photographic materials, can be employed singly or in a combination thereof. Such chemical sensitization may also be effected in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).
[0030] The amount of light-sensitive silver halides to be coated in preparing the photographic material for use in the present invention may be from 1 mg/m² to 10 g/m² as silver.
[0031] Silver halides to be used in the present invention may be color-sensitized with methine dyes or others. Suitable dyes for the purpose include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
[0032] Specifically mentioned are sensitizing dyes described in U.S. Patent 4,617,257, JP-A-59-180550 and JP-A-60-140335, and RD No. 17029 (1978), pages 12 and 13.
[0033] These sensitizing dyes may be used singly or in a combination thereof. Combination of plural sensitizing dyes is often used for the purpose of super-color sensitization.
[0034] Dyes which do not have a color-sensitizing activity by themselves or compounds which do not substantially absorb visible rays but which show a super-color sensitizing activity may be incorporated into emulsions along with sensitizing dyes. (For instance, such dyes or compounds are those described in U.S. Patent 3,615,641 and JP-A-63-23145.)
[0035] The time of adding such sensitizing dyes into emulsions may be before or after chemical ripening of emulsions. As the case may be, it may be before or after formation of nuclei of silver halide grains, in accordance with U.S. Patents 4,183,756 and 4,225,666. The amount of the dyes to be added is generally from 10⁻⁸ to 10⁻² mol or so, per mol of silver halide.
[0036] In the present invention, an organic metal salt may be used as an oxidizing agent along with light-sensitive silver halides. In particular, incorporation of an organic metal salt into a heat-developing photographic material is preferred. Of such organic metal salts, especially preferred are organic silver salts.
[0037] Organic compounds to be used for forming such organic silver salt oxidizing agents include, for example, benzotriazoles, fatty acids and other compounds described in U.S. Patent 4,500,626 (columns 52 to 53). In addition, silver salts of alkynyl group-containing carboxylic acids such as silver phenylpropiolate, as described in JP-A-60-113235, as well as acetylene silver as described in JP-A-61-249044 are also useful. Two or more kinds of organic silver salts may be employed in combination.
[0038] The amount of the above-mentioned organic silver salt may be added to the emulsion in an amount of from 0.01 to 10 mols, preferably from 0.01 to 1 mol, per mol of the light-sensitive silver halide in the emulsion. The total amount of the light-sensitive silver halide and the organic silver salt to be coated is suitably from 50 mg/m² to 10 g/m², as silver.
[0039] Various antifoggants and photographic stabilizers may be used in the present invention. Examples thereof include azoles and azaindenes described in RD No. 17643 (1978), pages 24 and 25; nitrogen-containing carboxylic acids and phosphoric acids described in JP-A-59-168442; mercapto compounds and metal salts thereof, as described in JP-A-59-11166; and acetylene compounds described in JP-A-62-87957.
[0040] The photographic material of the present invention can contain a compound having a function of activating the developability thereof and of stabilizing the image formed. Examples of such compounds which can preferably be employed in the present invention are described in U.S. Patent 4,500,626, columns 51 and 52.
[0041] In the system of the present invention of forming an image by diffusion and transfer of dye(s), a dye-fixing material is employed together with a light-sensitive photographic material. The system may be classified into two major categories, a format in which a light-sensitive material and a dye-fixing material are separately disposed on two independent supports, and a format in which the two materials are provided as coating layers on the same support. As regards the relation between the light-sensitive photographic material and the dye-fixing material, the relation thereof to supports and the relation thereof to white reflective layers, the relations described in U.S. Patent 4,500,626, column 57 are applicable to the present invention.
[0042] The dye-fixing material which is preferably used in the present invention has at least one layer containing a mordant agent and a binder. As the mordant agent, any known in the photographic field can be employed, and specific examples thereof include mordant compounds described in U.S. Patent 4,500,626, columns 58 and 59, and JP-A-61-88256, pages 32 to 41; and those described in JP-A-62-244043 and JP-A-62-244036. In addition, dye-receiving high polymer compounds, for example, those described in U.S. Patent 4,463,079 can also be employed.
[0043] The dye-fixing material may optionally have, if desired, auxiliary layers such as a protective layer, a peeling layer and a curling preventing layer. In particular, provision of a protective layer is helpful.
[0044] The binder for the layers constituting the light-sensitive material and the dye-fixing material is preferably a hydrophilic one. Examples of it are those described in JP-A-62-253159, pages 26 to 28. Specifically, preferred are transparent or semitransparent hydrophilic binders, for example, natural compounds such as proteins (e.g., gelatin, gelatin derivatives) and polysaccharides (e.g., cellulose derivatives, starch, gum arabi, dextran, pullulan), as well as synthetic polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone and acrylamide polymers. In addition, the high water-absorbing polymers described in JP-A-62-245260 may also be used, for example, homopolymers of vinyl monomers having -COOM or -SO₃M (where M is a hydrogen atom or an alkali metal) or copolymers of such vinyl monomers or of such vinyl monomers and other vinyl monomers (e.g., sodium methacrylate, ammonium methacrylate, Sumikagel L-5H produced by Sumitomo Chemical Co.). These binders may be used in combination of two or more kinds thereof.
[0045] Where a system of effecting heat development while supplying a small amount of water thereto is employed, use of the above-mentioned high water-absorbing polymers is desired as rapid absorption of water by the processed materials is possible. Where such a high water-absorbing polymer is incorporated into the dye-fixing layer or its protective layer, re-transference of the dye as transferred and fixed to the dye-fixing material to any others may be prevented.
[0046] In the present invention, the amount of the binder to be coated is preferably 20 g/m² or less, especially preferably 10 g/m² or less, further preferably 7 g/m² or less.
[0047] The layers constituting the light-sensitive material and the dye-fixing material can contain a hardening agent. Examples thereof include hardening agents described in U.S. Patent 4,678,739 (column 41) and JP-A-59-116655, JP-A-62-245261 and JP-A-61-18942. Specifically, there are aldehyde hardening agents (e.g., formaldehyde), aziridine hardening agents, epoxy hardening agents, vinylsulfone hardening agents (e.g., N,N'-ethylene-bis(vinylsulfonylacetamino)ethane), N-methylol hardening agents (e.g., dimethylolurea) and high polymer hardening agents (e.g., compounds described in JP-A-62-234157).
[0048] In accordance with the present invention, the light-sensitive material and/or the dye fixing material can contain an image formation accelerator. The image formation accelerators include those which promote the redox reaction between a silver salt oxidizing agent and a reducing agent, those which promote the reactions forming a dye from a dye donor substance or decomposing a dye or releasing a diffusive dye, and those which promote the migration of a dye from the photosensitive layer to the dye-fixing layer. Classified by physicochemical function, the image formation accelerators can be classified into bases or base precursors, nucleophilic compounds, high-boiling point organic solvents (oils), hot-melting solvents, and surfactants and compounds which interact with silver or silver ions, for instance. However, each of these substances generally has several functions and provides several of the above-mentioned effects. A detailed discussion on these substances can be found in U.S. Patent 4,678,739, columns 38 to 40.
[0049] As the base precursor, there are mentioned salts of an organic acid which may be decarboxylated under heat and a base, as well as compounds capable of releasing an amine by an intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in U.S. Patent 4,511,493 and JP-A-62-65038.
[0050] In the system where heat-development and dye transfer are effected simultaneously in the presence of a small amount of water, it is preferred to incorporate the base and/or base precursor into the dye-fixing material for the purpose of improving the storage stability of the light-sensitive material.
[0051] In addition, the combination of a hardly soluble metal compound and a compound capable of complexing with the metal ion which constitutes the said hardly soluble metal compound (hereinafter referred to as a "complex-forming compound") as described in European Patent Application Laid-Open No. 210,660 and U.S. Patent 4,740,445; as well as compounds capable of giving a base by electrolysis as described in JP-A-61-232451 can also be used as the base precursor. Use of the former is especially effective. The hardly soluble metal compound and the complex-forming compound are advantageously separately added to different light-sensitive material and dye-fixing material.
[0052] The light-sensitive material and/or the dye-fixing material of the present invention can contain various development terminating agents for the purpose of always obtaining constant images despite variation of the development temperature and the processing time in development.
[0053] The terminology "development terminating agent" as used herein means a compound which, after proper development, quickly neutralizes a base or reacts with a base to lower the base concentration in the layer and thereby terminates the development, or a compound which interacts with silver and a silver salt to arrest development. Specifically, there are mentioned acid precursors which release an acid under heat, electrophilic compounds which react with the existing base by a substitution reaction under heat, as well as nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. More precisely, specific examples of these compounds are described in JP-A-62-253159 (pages 31 and 32).
[0054] The layers constituting the light-sensitive material or the dye-fixing material (including backing layer) of the present invention may contain various polymer latexes for the purpose of improving the film properties, such as dimension stability, anti-curling property, anti-sticking property, anti-cracking property and prevention of pressure sensitization and desensitization. Specifically, any polymer latex described in JP-A-62-245258, JP-A-62-136648 and JP-A-62-110066 may be used for the purpose. In particular, where a polymer latex having a low glass transition point (40°C or lower) is incorporated into the mordant layer, cracking of the layer may be prevented. On the other hand, where a polymer latex having a high glass transition point is incorporated into the backing layer, an anti-curling effect may be imparted to the layer.
[0055] The layers constituting the light-sensitive material and the dye-fixing material of the present invention may contain a plasticizer, a slipping agent as well as a high-boiling point organic solvent as an agent for improving the peelability between the light-sensitive material and the dye-fixing material. Suitable are those described in JP-A-62-253159, page 25, and JP-A-62-245253.
[0056] In addition, for the above-mentioned purposes, various silicone oils (including all silicone oils from dimethylsilicone oil to modified silicone oils formed by introducing various organic groups into dimethylsiloxane) can be used. Suitable examples thereof are various modified silicone oils as described in a technical reference of Modified Silicone Oils (published by Shin-Etsu Silicone Co.), page 6-18B. Of them, especially effective is a carboxy-modified silicone (X-22-3710, trade name).
[0057] In addition, also effective are silicone oils as described in JP-A-62-215953 and JP-A-62-23687.
[0058] The light-sensitive material and the dye-fixing material can contain an anti-fading agent. Such an anti-fading agents include an antioxidant and an ultraviolet absorbent as well as various kinds of metal complexes.
[0059] Examples of the antioxidant include chroman compounds, coumaran compounds, phenol compounds (e.g., hindered phenols), hydroquinone derivatives, hindered amine derivatives and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.
[0060] Examples of the ultraviolet absorbent include benzotriazole compounds (U.S. Patent 3,533,796), 4-thiazolidone compounds (U.S. Patent 3,352,681), benzophenone compounds (JP-A 46-2784) and other compounds described in JP-A-54-48535, JP-A-62-136641 and JP-A-61-38256. Further, ultraviolet-absorbing polymers described in JP-A-62-260152 are also effective.
[0061] Examples of the metal complexes include the compounds described in U.S. Patents 4,241,155, 4,245,013 (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, JP-A-1-75568 and JP-A-1-74272.
[0063] The anti-fading agent for preventing the dye which has transferred to the dye-fixing material from fading may be previously incorporated into the dye-fixing material or, alternatively, it may be supplied to the dye-fixing material from an external source of a light-sensitive material containing the agent.
[0064] The above-mentioned antioxidant, ultraviolet absorbent and metal complex can be employed in the present invention in the form of a combination thereof.
[0065] The light-sensitive material and the dye-fixing material can contain a brightening agent. In particular, it is preferred to incorporate a brightening agent into the dye-fixing material or to supply the same to the material from an external source of a light-sensitive material containing the agent. Examples of the agent include the compounds described in K Veenkataraman, The Chemistry of Synthetic Dyes, Vol. V, Chap. 8, and JP-A-61-143752. Specifically, there are mentioned stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds and carbostyryl compounds.
[0067] The layers constituting the light-sensitive material and the dye-fixing material of the present invention can contain various surfactants for various purposes, such as coating aid, improvement of peeling property, improvement of slide property, prevention of static charges and enhancement of developability. Specific examples of such surfactants are described in JP-A-62-173463 and JP-A-62-183457.
[0068] The layers constituting the light-sensitive material and the dye-fixing material of the present invention can contain organic fluorine compounds for the purpose of improvement of slide property, prevention of static charges and improvement of peeling property. Specific examples of such organic fluorine compounds include the fluorine surfactants described in JP-B-57-9053 (columns 8 to 17) and JP-A-61-20944 and JP-A-62-135826, as well as hydrophobic fluorine compounds such as fluorine oils and similar oily fluorine compounds and ethylene tetrafluoride resins and similar solid fluorine compound resins.
[0069] The light-sensitive material and the dye-fixing material can contain a mat agent. As the mat agent, one may use silicon dioxide and the compounds described in JP-A-61-88256 (page 29) such as polyolefins or polymethacrylates, as well as the compounds described in JP-A-63-274944 and JP-A-63-274952 such as benzoguanamine resin beads, polycarbonate resin beads and AS resin beads.
[0070] In addition, the layers constituting the light-sensitive material and the dye-fixing material may further contain a hot-melting solvent, a defoaming agent, a microbiocidal and fungicidal agent, a colloidal silica and other additives. Examples of such additives are described in JP-A-61-88256 (pages 26 to 32).
[0071] The support which is employable in preparing the light-sensitive material and the dye-fixing material of the present invention may be any support that withstands the processing temperature. In general, paper and synthetic high polymer films are used as the support. Specifically, the support includes films of polyethylene terephthalate (PET), polycarbonates, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (e.g., triacetyl cellulose) and those films containing a pigment such as titanium oxide; synthetic paper made of polypropylene by a filming method; mixed paper made of a synthetic resin pulp (e.g., polyethylene) and a natural pulp; as well as Yankee paper, baryta paper, coated paper (especially cast-coated paper), metals, clothes and glasses.
[0072] These supports may be used directly as they are or may be used in a form coated with a synthetic high polymer substance (e.g., polyethylene) on one surface or both surfaces thereof. In addition, the supports described in JP-A-62-253159, pages 29 to 31 can also be employed in the present invention.
[0073] The surface of the support may be coated with a hydrophilic binder and a semiconductive metal oxide (e.g., alumina sol or tin oxide) or an antistatic agent such as carbon black.
[0074] The light source to be used for exposure of the color photographic material of the present invention may be a light emission diode or a semiconductor laser. Examples of suitable light emission diodes include GaAsP (red), GaP (red, green), GaAsP:N (red, yellow, GaAs (infrared), GaAlAs (infrared, red), GaP:N (red, green, yellow), GaAsSi (infrared), GaN (blue), and SiC (blue).
[0075] An infrared-visible conversion element capable of converting the infrared ray as emitted from an infrared emission diode into a visible ray with a phosphor substance may also be used. Preferred phosphor substances suitable for the purpose are rare earth-activated phosphor substances. Rare earth elements suitable for the purpose include Er³⁺, Tm³⁺ and Yb³⁺.
[0076] Examples of semiconductor lasers to be used in the present invention include lasers to be derived from semiconductor materials of In1-xGaxP (up to 700 nm), GaAs1-xPx (610 to 900 nm), Ga1-xAlxAs (690 to 900 nm), InGaAsP (1100 to 1670 nm), and AlGaAsSb (1250 to 1400 nm). For exposing the color photographic material of the present invention with light, a YAG laser (1064 nm) derived by exciting Nd:YAG crystals with a light emission diode of GaAsxP1-x may also be used in addition to the above-mentioned semiconductor lasers.
[0077] Also applicable to the color photographic material of the present invention is a second harmonic generating element (SHG element), which may convert the wavelength of a laser ray to 1/2 by utilizing the non-linear optical effect thereof. For instance, there are mentioned CD*A and KD*P as non-linear optical crystals suitable in the system (refer to Laser Handbook, edited by Laser Association, published on December 15, 1982, pages 122 to 139). In addition, an LiNbO₃ optical waveguide element in which H⁺ ion-exchanged optical waveguide is formed into LiNbO₃ crystals may also be used (refer to Nikkei Electronics, published on July 14, 1986, No. 399, pages 89 and 90).
[0078] Other light sources also suitable in the present invention are a natural light, a tungsten lamp and a CRT light source.
[0079] For imagewise exposing the photographic material of the present invention, various methods can be employed, which include, for example, a method of directly photographing a scene or portrait with a camera and a method of exposing an image through a reversal film or negative film by the use of a printer or an enlarger.
[0080] As the image information suitable for the photographic material of the present invention, one may use any of image signals obtained from a video camera or electronic still camera; television signals as standardized by Nippon Television Signal Standard Commission (NTSC); image signals obtained by dividing an original into a plurality of pixels with a scanner; and image signals formed by the use of a computer such as CG or CAD.
[0081] Where the heat-developing photographic material of the present invention is processed under heat, the heating temperature in the heat-development step may be from about 50°C to about 250°C. Especially suitable, the temperature is from about 80°C to about 180°C. The step of diffusing and transferring the dye formed by the development may be effected simultaneously with the heat-development step or after the same. In the latter case, the heating temperature in the transfer step may be anywhere from the temperature in the previous heat-development step to room temperature. Preferably, it is from 50°C to a temperature about 10°C lower than the temperature in the heat-development step.
[0082] In the heat-development color photographic material of the present invention, the total thickness of all the layers to be coated on the support is 15 µmm or less as a dry thickness. By defining the thickness of the coated layers in this range, the transfer of the dye formed may be accelerated so that an image having an excellent sharpness can be obtained. In such a photographic material, however, a problem of poor color separatability would often occur. The present invention is free from that problem.
[0083] For accelerating migration of the dye formed, a solvent may be used in the present invention.
[0084] Further, as described in detail in JP-A-59-213443 and JP-A-61-238056, a method where development and transfer are carried out in the presence of a small amount of a solvent (especially, water) under heat, either at the same time or in a continuous sequence, can be advantageously utilized in processing the heat-developing photographic material of the present invention. In this method, the heating temperature is preferably not lower than 50°C and not higher than the boiling point of the solvent used. For instance, where the solvent is water, the temperature is desirably from 50°C to 100°C.
[0085] Examples of the solvents to be used for acceleration of development and/or migration of the diffusive dye formed to the dye-fixing material include water and an aqueous basic solution containing an inorganic alkali metal salt or an organic base. As the bases, those mentioned hereinbefore for the image formation accelerators can be employed. In addition, a low-boiling point solvent or a mixed solvent comprising a low-boiling point solvent and water or an aqueous basic solution can also be used. Further, surfactants and antifoggants, as well as hardly soluble metals and complex-forming compounds, can be incorporated into the solvents.
[0086] The solvent can be used by applying the same to either the dye-fixing material or the light-sensitive photographic material or to both. The amount thereof to be used may be a small amount of less than the weight of the solvent corresponding to the maximum swollen volume of the total coated layers (especially less than the amount obtained by subtracting the weight of the total coated layers from the weight of the solvent corresponding to the maximum swollen volume of the total coated layers).
[0087] As a method of applying the solvent to the light-sensitive layer or the dye-fixing layer, for example, the method described in JP-A-61-147244 (page 26) can be employed. Apart from this, the solvent can be incorporated into either the light-sensitive photographic material or the dye-fixing material or into both in the form of solvent-containing microcapsules.
[0088] In order to accelerate migration of the dye formed, a system of incorporating a hydrophilic hot-melting solvent, which is solid at room temperature but may melt at a high temperature, into a light-sensitive photographic material or into a dye-fixing material may also be employed in the present invention. In employing the system, the hydrophilic hot-melting solvent may be incorporated into either the light-sensitive photographic material or the dye-fixing material or into both. The layer to which the solvent is added may be any of the emulsion layer, interlayer, protective layer and dye-fixing layer, but the solvent is preferably added to the dye-fixing layer and/or the adjacent layer(s).
[0089] Examples of the hot-melting solvent to be employed in the system include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes and other heterocyclic compounds. Also, for accelerating migration of the dye formed, a high-boiling point organic solvent may be incorporated into the light-sensitive photographic material and/or the dye-fixing material.
[0090] For heating the material and/or the element in the development step and/or the transfer step, the material and/or the element may be contacted with a heated block or plate, or with a hot plate, hot presser, hot roller, halogen lamp heater or infrared or far-infrared lamp heater or may be passed through a high temperature atmosphere. If desired, an electric heating element layer may be provided in the photographic material or in the dye fixing material, with which the material may be electrically heated. As such an electric heating element, one as described in JP-A-61-145544 may be used.
[0091] Where the light-sensitive photographic material is attached to the dye-fixing material and combined together under pressure, a method described in JP-A-61-174244 (page 27) is applicable with respect to the pressure condition and the means of pressing the combined materials.
[0092] For processing the photographic material of the present invention, various known heat-developing apparatuses can be utilized. For instance, for processing the heat-developing photographic material of the present invention, the apparatuses described in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353 and JP-A-60-18951 and Japanese Utility Model Application Laid-Open No. 62-25944 are preferably employed.
[0093] The present invention will be explained in more detail with reference to the following examples, which, however, are not intended to restrict the scope of the present invention.
EXAMPLE 1
[0094] Silver Halide Emulsion (I) for a fifth layer of a photographic material was prepared as described below.
[0095] Precisely, Solution (I) and Solution (II) each having the composition mentioned in Table 2 below were added to a well stirred aqueous solution having the composition mentioned in Table 1 below, over a period of 10 minutes. Then Solution (III) and Solution (IV) each having the composition mentioned in Table 2 were added thereto over a period of 25 minutes.
TABLE 1
| Components | Amount |
| H₂O | 780 cc |
| Gelatin | 20 g |
| KBr | 0.3 g |
| NaCl | 2.4 g |
| Compound (1) | 0.030 g |
| H₂SO₄ (1 N) | 16 cc |
| Temperature | 45°C |
TABLE 2
| Components | Solutions | |||
| I | II | III | IV | |
| K₂IrCl₆(IV) (g) | - | - | - | 3.9×10⁻⁵ |
| AgNo₃(g) | 30 | - | 70 | - |
| KBr (g) | - | 13.7 | - | 44.5 |
| NaCl (g) | - | 3.6 | - | 1.7 |
| Water to make (cc) | 230 | 180 | 260 | 250 |
Compound (1):
[0097]
Just before the chemical sensitization of the emulsion, 50 cc of 1% solution of the sensitizing dye shown below (dissolved in 1/1 mixed solvent of methanol/water) was added to the emulsion.
Sensitizing Dye:
[0098]
After rinsing with water and de-salting with the following Flocculating Agent (a) at pH of 4.1, 22 g of gelatin was added to the emulsion, which was then adjusted to have pH of 6.0 and pAg of 7.9. The emulsion was then subjected to chemical sensitization at 60°C. The compounds used for the chemical sensitization are shown in Table 3 below.
Flocculating Agent (a):
[0099]
The yield of the silver emulsion thus obtained was 630 g. The emulsion was a monodispersed emulsion of cubic grains, having a variation coefficient of 10.3% and a mean silver halide grain size of 0.21 µm.
[0101] Precisely, Solution (I) and Solution (II) each having the composition mentioned in Table 5 below were added to a well stirred aqueous solution having the composition mentioned in Table 4 below, over a period of 18 minutes. Then Solution (III) and Solution (IV) each having the composition mentioned in Table 5 were added thereto over a period of 24 minutes.
TABLE 4
| Components | Amount |
| H₂O | 780 cc |
| Gelatin | 20 g |
| KBr | 0.3 g |
| NaCl | 2.5 g |
| Compound (1) | 0.03 g |
| H₂SO₄ (1 N) | 16 cc |
| Temperature | 45°C |
TABLE 5
| Components | Solutions | |||
| I | II | III | IV | |
| K₂IrCl₆(IV) (g) | - | - | - | 2×10⁻⁵ |
| K₄[Fe(CN)₆].3H₂O (g) | - | - | - | 0.033 |
| AgNO₃ (g) | 30 | - | 70 | - |
| KBr (g) | - | 13.6 | - | 44 |
| NaCl (g) | - | 3.6 | - | 2.4 |
| Water to make (cc) | 230 | 230 | 375 | 365 |
[0103] After rinsing with water and de-salting with the following Flocculating Agent (b) at pH of 3.9, 22 g of gelatin was added to the emulsion, which was then adjusted to have pH of 5.9 and pAg of 7.8. The emulsion was then subjected to chemical sensitization at 70°C. During the course of the chemical sensitization, a methanol solution of a mixture of the following Sensitizing Dyes (c) and (d) (containing 0.2 N p-toluenesulfonic acid) was added to the emulsion. The compounds used for the chemical sensitization are shown in Table 6 below.
Flocculating Agent (b):
Sensitizing Dyes (1/1 mixture of the following (c)and (d):
[0105]
The yield of the silver halide emulsion thus obtained was 645 g. The emulsion was a monodispersed emulsion of cubic grains, having a variation coefficient of 9.7% and a mean silver halide grain size of 0.24 µm.
[0107] Precisely, Solution (I) and Solution (II) each having the composition mentioned in Table 8 below were added to a well stirred aqueous solution having the composition mentioned in Table 7 below, over a period of 18 minutes. Then Solution (III) and Solution (IV) each having the composition mentioned in Table 8 were added thereto over a period of 25 minutes.
TABLE 7
| Components | Amount |
| H₂O | 780 cc |
| Gelatin | 20 g |
| KBr | 0.3 g |
| NaCl | 2.5 g |
| Compound (1) | 0.03 g |
| H₂SO₄ (1 N) | 16 cc |
| Temperature | 50°C |
TABLE 8
| Components | Solutions | |||
| I | II | III | IV | |
| K₂IrCl₆(IV) (g) | - | - | - | 3.9×10⁻⁵ |
| AgNO₃ (g) | 30 | - | 70 | - |
| KBr (g) | - | 13.8 | - | 44.1 |
| NaCl (g) | - | 3.6 | - | 2.4 |
| Water to make (cc) | 225 | 225 | 375 | 365 |
[0109] After rinsing with water and de-salting with the above-mentioned Flocculating Agent (b) at pH of 4.1, 22 g of gelatin was added to the emulsion, which was then adjusted to have pH of 7.4 and pAg of 7.6. The emulsion was then subjected to chemical sensitization at 60°C. During the course of the chemical sensitization, a methanol solution of the following Sensitizing Dye (containing 0.1 N p-toluenesulfonic acid) was added to the emulsion. The compounds used for the chemical sensitization are shown in Table 9 below.
Sensitizing Dye:
[0110]
The yield of the silver halide emulsion thus obtained was 650 g. The emulsion was a monodispersed emulsion of cubic grains, having a variation coefficient of 12.6% and a mean silver halide grain size of 0.25 µmm.
[0112] Precisely, 12.55 g of zinc oxide having a mean grain size of 0.25 µmm was added to 100 cc of 4% aqueous gelatin solution along with a dispersing agent comprising 1 g of carboxymethyl cellulose and 0.1 g of sodium polyacrylate. The mixture was milled in a mill having therein glass beads having a mean grain size of 0.75 mm for 30 minutes. The glass beads were separated and a gelatin dispersion containing zinc hydroxide was obtained.
[0114] Precisely, the oily phase components mentioned in Table 10 below were dissolved in 250 cc of ethyl acetate to form a uniform solution of 60°C. To this were added the aqueous phase components also mentioned in the same table, which had been heated up to 60°C. The resulting mixture was dispersed in a dissolver having a 8 cm-diameter disperser, for 30 minutes at 5000 rpm. To this was added additional water in the amount mentioned in the same table, and the whole was stirred to give a uniform dispersion. The dispersion is called a gelatin dispersion of hydrophobic additives.
TABLE 10
| Components | Cyan | Magenta | Yellow | |
| Oily Phase | Dye Donor Compound (1) | - | - | 172.5 |
| Dye Donor Compound (2) | - | 146.5 | - | |
| Dye Donor Compound (3) | 72.5 | - | - | |
| Dye Donor Compound (4) | 106.3 | - | - | |
| Filter Dye (5) | 4.7 | - | 15.2 | |
| Auxiliary Developing Agent (6) | 10.0 | 2.0 | 12.0 | |
| Antifoggant (7) | 2.5 | 2.1 | 1.5 | |
| High-Boiling Point Organic Solvent (8) | 36.9 | - | 86.3 | |
| High-Boiling Point Organic Solvent (9) | 49.2 | 73.2 | - | |
| High-Boiling Point Organic Solvent (10) | 12.3 | - | - | |
| Aqueous Phase | Lime-processed Gelatin | 100.0 | 100.0 | 140.0 |
| Water-Soluble Polymer (11) | 2.5 | - | - | |
| Surfactant (12) | 7.5 | 3.8 | 15.0 | |
| Water | 890.0 | 896.2 | 965.0 | |
| Additional Water | 2830 | 2610 | 1560 |
[0115] Using the materials prepared above and the materials shown below, a heat-developing color photographic material Sample No. 101 having the layer constitution of Table 11 below and a Dye-Fixing Material Sample (R-1) having the layer constitution of Table 12 below were prepared.
Yellow Dye Donor Compound (1):
Magenta Dye Donor Compound (2):
Cyan Dye Donor Compound (3):
Cyan Dye Donor Compound (4):
Filter Dye (5):
Auxiliary Developing Agent (6):
Antifoggant (7):
High-Boiling Point Organic Solvent (8):
High-Boiling Point Organic Solvent (9):
High-Boiling Point Organic Solvent (10):
Water-Soluble Polymer (11):
Surfactant (12):
Reducing Agent (13):
Surfactant (14):
Surfactant 15:
Water-Soluble Polymer (16):
Antifoggant (17):
Surfactant (18):
Antifoggant (19):
Hardening Agent (20):
Surfactant (21):
Water-Soluble Polymer (22):
Water-Soluble Polymer (23):
Hardening Agent (24):
Water-Soluble Polymer (25):
Mordant Agent (26):
High-boiling Point Organic Solvent (27):
Brightening Agent (28):
Reducing Agent (29):
Surfactant (30):
[0147] Samples Nos. 102 to 110 were prepared in the same manner as in preparation of Sample No. 101, except that the mean grain sizes of the emulsions in the constituent layers were varied to those as indicated in Table 13 below by varying the condition of dispersing the emulsion grains.
TABLE 13
| Sample No. | Mean Grain Size of Emulsion (µm) | ||
| C | M | Y | |
| 101 (comparative sample) | 0.36 | 0.39 | 0.37 |
| 102 (comparative sample) | 0.45 | 0.39 | 0.37 |
| 103 (comparative sample) | 0.36 | 0.55 | 0.37 |
| 104 (comparative sample) | 0.45 | 0.47 | 0.52 |
| 105 (comparative sample) | 0.55 | 0.55 | 0.47 |
| 106 (sample of the invention) | 0.22 | 0.39 | 0.37 |
| 107 (sample of the invention) | 0.36 | 0.25 | 0.26 |
| 108 (sample of the invention) | 0.20 | 0.20 | 0.19 |
| 109 (sample of the invention) | 0.15 | 0.17 | 0.16 |
| 110 (sample of the invention) | 0.12 | 0.13 | 0.12 |
| The grain size was measured with TEM (transmission electronic microscope). | |||
[0148] The multi-layer color photographic materials of Sample Nos. 101 to 110 were exposed with a semiconductor laser exposing machine under the conditions mentioned in Table 14 below.
TABLE 14
| Condition for Laser Exposure | |
| Beam Strength on Sample | 1 mV |
| Scanning Line Density | 800 dpi (32 resters/mm) |
| Beam Diameter | 100 ± 10 µm in the main scanning direction |
| 100 ± 10 µm in the sub-scanning direction | |
| Exposure Time | 0.9 msec/rester |
| Laser Ray Wavelength for Exposure | 670 nm (laser ray) |
| 750 nm (laser ray) | |
| 810 nm (laser ray) | |
| Exposure Amount | 1 log E variation (for each track) per 2.5 cm in the sub-scanning direction |
| Method of Varying Exposure Amount | Emission Time Modulation |
[0149] Fifteen ml/m² of water was applied onto the emulsion layer of each of the thus exposed samples, while the samples were moved at a line speed of 20 mm/sec. Immediately after the application of water, the samples were attached to image-receiving material samples with the coated layers of the both samples facing each other. The attached samples were heated for 30 seconds, using a heat roller which was conditioned so that the temperature of the water-absorbed layers of the attached samples was 83°C.
[0150] The photographic material samples were then peeled off from the image-receiving material samples, whereby a sharp transfer image was formed on the latter. The transfer image was subjected to sensitometry to give the results shown in Table 15 below.
[0151] From the results of Table 15 above, it is understood that the samples of the present invention give an image of good discrimination.
EXAMPLE 2
[0152] Light-sensitive Silver Halide Emulsions (IV) to (IX) were prepared in the manner as mentioned below.
Preparation of Light-sensitive Silver Halide Emulsion (IV) (for red-sensitive emulsion layer):
[0153] Solution (I) and Solution (II) each having the composition mentioned in Table 16 below were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin, 0.5 g of potassium bromide, 3 g of sodium chloride and 30 mg of Chemical (A) shown below in 480 cc of water and kept at 45°C), at the same flow rate over a period of 20 minutes. After 5 minutes, Solution (III) and Solution (IV) mentioned in Table 16 were simultaneously added thereto at the same flow rate over a period of 25 minutes. Ten minutes after the start of the addition of Solutions (III) and (IV), an aqueous solution of a gelatin dispersion of dyes (containing 1 g of gelatin, 67 mg of Dye (a), 133 mg of Dye (b) and 4 mg of Dye (c), all of which are shown below, in 105 ml of water and kept at 45°C) was added thereto over a period of 20 minutes.
[0154] The emulsion thus formed was rinsed with water and desalted by an ordinary method, and 22 g of lime-processed ossein gelatin was added to the emulsion, which was then adjusted to have pH of 6.2 and pAg of 7.7. The emulsion was subjected to optimum chemical sensitization with sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and chloroauric acid at 60°C. Thus, 635 g of a monodispersed emulsion of cubic silver chlorobromide grains having a mean grain size of 0.30 µmm was obtained.
TABLE 16
| Components | Solution (I) | Solution (II) | Solution (III) | Solution (IV) |
| AgNO₃ | 50.0 g | - | 50.0 g | - |
| NH₄NO₃ | 0.19 g | - | 0.19 g | - |
| KBr | - | 28.0 g | - | 35.0 g |
| NaCl | - | 3.45 g | - | - |
| Water to make 250 ml | Water to make 250 ml | Water to make 200 ml | Water to make 200 ml |
Chemical (A):
Dye (a):
Dye (b):
Dye (c):
Preparation of Light-sensitive Silver Halide Emulsion (V) (for red-sensitive emulsion layer):
[0159] Solution (I) and Solution (II) each having the composition mentioned in Table 17 below were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin, 0.5 g of potassium bromide, 6 g of sodium chloride and 30 mg of Chemical (A) shown above in 783 cc of water and kept at 65°C), at the same flow rate over a period of 30 minutes. After 5 minutes, Solution (III) and Solution (IV) mentioned in Table 17 were simultaneously added thereto at the same flow rate over a period of 15 minutes. Two minutes after the start of the addition of Solutions (III) and (IV), an aqueous solution of a gelatin dispersion of dyes (containing 0.9 g of gelatin, 67 mg of Dye (a), 121 mg of Dye (b) and 4 mg of Dye (c) all of which are shown above, and kept at 50°C) was added thereto over a period of 18 minutes.
[0160] The emulsion thus formed was rinsed with water and desalted by an ordinary method, and 22 g of lime-processed ossein gelatin was added to the emulsion, which was then adjusted to have pH of 6.2 and pAg of 7.7. The emulsion was subjected to optimum chemical sensitization with sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and chloroauric acid at 60°C. Thus, 635 g of a monodispersed emulsion of cubic silver chlorobromide grains having a mean grain size of 0.50 µmm was obtained.
TABLE 17
| Components | Solution (I) | Solution (II) | Solution (III) | Solution (IV) |
| AgNO₃ | 50.0 g | - | 50.0 g | - |
| NH₄NO₃ | 0.19 g | - | 0.19 g | - |
| KBr | - | 28.0 g | - | 35.0 g |
| NaCl | - | 3.45 g | - | - |
| Water to make 200 ml | Water to make 140 ml | Water to make 145 ml | Water to make 155 ml |
Preparation of Light-sensitive Silver Halide Emulsion (VI) (for green-sensitive emulsion layer):
[0161] Solution (I) and Solution (II) each having the composition mentioned in Table 18 below were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride and 15 mg of Chemical (A) shown above in 675 cc of water and kept at 48°C), at the same flow rate over a period of 30 minutes. After 10 minutes, Solution (III) and Solution (IV) mentioned in Table 18 were simultaneously added thereto at the same flow rate over a period of 20 minutes. One minute after the finish of the addition of Solutions (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (containing 3.0 g of gelatin and 300 mg of Dye (d), which is shown below, in 120 ml of water and kept at 45°C) was added thereto all at a time.
[0162] The emulsion thus formed was rinsed with water and desalted by an ordinary method, and 22 g of lime-processed ossein gelatin was added to the emulsion, which was then adjusted to have pH of 6.0 and pAg of 7.6. The emulsion was subjected to optimum chemical sensitization with sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and chloroauric acid at 68°C. Thus, 635 g of a monodispersed emulsion of cubic silver chlorobromide grains having a mean grain size of 0.27 µmm was obtained.
TABLE 18
| Components | Solution (I) | Solution (II) | Solution (III) | Solution (IV) |
| AgNO₃ | 50.0 g | - | 50.0 g | - |
| NH₄NO₃ | 0.25 g | - | 0.25 g | - |
| KBr | - | 21.0 g | - | 28.0 g |
| NaCl | - | 6.90 g | - | 3.45 g |
| Water to make 200 ml | Water to make 150 ml | Water to make 200 ml | Water to make 150 ml |
Dye (d):
Preparation of Light-sensitive Silver Halide Emulsion (VII) (for green-sensitive emulsion layer):
[0164] Solution (I) and Solution (II) each having the composition mentioned in Table 19 below were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin, 0.3 g of potassium bromide, 6 g of sodium chloride and 15 mg of Chemical (A) shown above in 675 cc of water and kept at 55°C), at the same flow rate over a period of 20 minutes. After 10 minutes, Solution (III) and Solution (IV) mentioned in Table 19 were simultaneously added thereto at the same flow rate over a period of 20 minutes. One minute after the finish of the addition of Solutions (III) and (IV), an aqueous solution of a gelatin dispersion of a dye (containing 2.5 g of gelatin and 250 mg of Dye (d), which is shown above, in 95 ml of water and kept at 45°C) was added thereto all at a time.
[0165] The emulsion thus formed was rinsed with water and desalted by an ordinary method, and 20 g of lime-processed ossein gelatin was added to the emulsion, which was then adjusted to have pH of 6.0 and pAg of 7.6. The emulsion was subjected to optimum chemical sensitization with sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and chloroauric acid at 68°C. Thus, 635 g of a monodispersed emulsion of cubic silver chlorobromide grains having a mean grain size of 0.42 µmm was obtained.
TABLE 19
| Components | Solution (I) | Solution (II) | Solution (III) | Solution (IV) |
| AgNO₃ | 50.0 g | - | 50.0 g | - |
| NH₄NO₃ | 0.25 g | - | 0.25 g | - |
| KBr | - | 28.0 g | - | 35.0 g |
| NaCl | - | 3.45 g | - | - |
| Water to make 200 ml | Water to make 200 ml | Water to make 150 ml | Water to make 150 ml |
Preparation of Light-sensitive Silver Halide Emulsion (VIII) (for blue-sensitive emulsion layer):
[0166] Solution (I) and Solution (II) each having the composition mentioned in Table 20 below were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin, 0.5 g of potassium bromide, 4 g of sodium chloride and 15 mg of Chemical (A) shown above in 675 cc of water and kept at 50°C), at the same flow rate over a period of 8 minutes. After 10 minutes, Solution (III) and Solution (IV) shown in Table 20 were simultaneously added thereto at the same flow rate over a period of 32 minutes. One minute after the finish of the addition of Solutions (III) and (IV), an aqueous solution of dyes (containing 220 mg of Dye (e) and 110 mg of Dye (f), all of which are shown below, dissolved in 95 ml of water and 5 ml of methanol and kept at 45°C) was added thereto all at a time.
[0167] The emulsion thus formed was rinsed with water and desalted by an ordinary method, and 22 g of lime-processed ossein gelatin was added to the emulsion, which was then adjusted to have pH of 6.0 and pAg of 7.8. The emulsion was subjected to optimum chemical sensitization with sodium thiosulfate and 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene at 68°C. Thus, 635 g of a monodispersed emulsion of cubic silver chlorobromide grains having a mean grain size of 0.30 µmm was obtained.
TABLE 20
| Components | Solution (I) | Solution (II) | Solution (III) | Solution (IV) |
| AgNO₃ | 20.0 g | - | 80.0 g | - |
| NH₄NO₃ | 0.10 g | - | 0.40 g | - |
| KBr | - | 9.8 g | - | 44.8 g |
| NaCl | - | 2.60 g | - | 5.52 g |
| Water to make 80 ml | Water to make 80 ml | Water to make 240 ml | Water to make 240 ml |
Dye (e):
Dye (f):
Preparation of Light-sensitive Silver Halide Emulsion (IX) (for blue-sensitive emulsion layer):
[0170] Solution (I) and Solution (II) each having the composition mentioned in Table 21 below were simultaneously added to a well stirred aqueous gelatin solution (containing 20 g of gelatin, 0.3 g of potassium bromide, 9 g of sodium chloride and 15 mg of Chemical (A) shown above in 675 cc of water and kept at 65°C), at the same flow rate over a period of 10 minutes. After 10 minutes, Solution (III) and Solution (IV) shown in Table 21 were simultaneously added thereto at the same flow rate over a period of 30 minutes. One minute after the finish of the addition of Solutions (III) and (IV), an aqueous solution of dyes (containing 150 mg of Dye (e) and 75 mg of Dye (f), all of which are shown above, dissolved in 66 ml of water and 4 ml of methanol and kept at 60°C) was added thereto all at a time.
[0171] The emulsion thus formed was rinsed with water and desalted by an ordinary method, and 22 g of lime-processed ossein gelatin was added to the emulsion, which was then adjusted to have pH of 6.0 and pAg of 7.8. The emulsion was subjected to optimum chemical sensitization with sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene and chloroauric acid at 68°C. Thus, 635 g of a monodispersed emulsion of cubic silver chlorobromide grains having a mean grain size of 0.55 µmm was obtained.
TABLE 21
| Components | Solution (I) | Solution (II) | Solution (III) | Solution (IV) |
| AgNO₃ | 25.0 g | - | 75.0 g | - |
| NH₄NO₃ | 0.13 g | - | 0.37 g | - |
| KBr | - | 12.3 g | - | 42.0 g |
| NaCl | - | 2.58 g | - | 5.18 g |
| Water to make 100 ml | Water to make 100 ml | Water to make 225 ml | Water to make 225 ml |
[0173] Precisely, the oily phase components mentioned in Table 22 below were dissolved to form a uniform solution of 60°C. To this were added the aqueous phase components also mentioned in the same table, which had been heated up to 60°C. The resulting mixture was dispersed in a dissolver having a 8 cm-diameter disperser, for 30 minutes at 5000 rpm. To this was added additional water in the amount mentioned in the same table, and the whole was stirred to give a uniform dispersion. The dispersion is called a gelatin dispersion of hydrophobic additives.
TABLE 22
| Components | Cyan | Magenta | Yellow | Reducing Agent | |
| Oily Phase | Dye Donor Compound (31) | - | - | 1300 | - |
| Dye Donor Compound (32) | - | 1550 | - | - | |
| Dye Donor Compound (33) | 619 | - | - | - | |
| Dye Donor Compound (34) | 905 | - | - | - | |
| Reducing Agent (13) | 484 | 561 | 453 | - | |
| Reducing Agent (35) | - | - | - | 1390 | |
| Reducing Agent (36) | - | - | - | 260 | |
| Electron Transmitting Agent Precursor (37) | 142 | 142 | 142 | - | |
| Nucleophilic Agent (38) | - | 48 | - | 82 | |
| High-Boiling Point Organic Solvent (9) | 191 | 194 | 520 | - | |
| High-Boiling Point Solvent (39) | 571 | 581 | - | 590 | |
| High-Boiling Point Solvent (40) | - | - | 390 | - | |
| Antifoggant (41) | 40 | 44 | 41 | - | |
| UV Absorbent (42) | 305 | 388 | - | - | |
| Ethyl Acetate | 3800 | 3800 | 2775 | 2750 | |
| Methyl Ethyl Ketone | 5900 | 5900 | - | - | |
| Aqueous Phase | Lime-processed Gelatin | 1000 | 1000 | 1000 | 1000 |
| Water-Soluble Polymer (11) | 150 | 100 | - | - | |
| Surfactant (12) | 150 | 50 | 150 | 45 | |
| Water | 8850 | 8850 | 8850 | 8934 | |
| Sodium Hydrogensulfite | - | - | - | 15 | |
| Citric Acid | - | - | - | 6 | |
| Additional Water | 15000 | 15000 | 15000 | 5000 |
[0174] A dispersion of the following Electron Transmitting Agent (43) was prepared in the manner as mentioned below.
[0175] Precisely, 10 g of Electron Transmitting Agent (43), 0.5 g of a dispersing agent of Polyethylene Glycol Nonylphenyl Ether (g) and 0.5 g of Anionic Surfactant (h), all of which are shown below, were added to an aqueous 5% solution of lime-processed gelatin and milled in a mill having therein glass beads having a mean grain size of 0.75 mm for 60 minutes. The glass beads were separated, and a gelatin dispersion containing Electron Transmitting Agent (43) was obtained, having a mean grain size of 0.3 µmm.
Electron Transmitting Agent (43):
Polyethylene Glycol Nonylphenyl Ether (g):
Anionic Surfactant (h):
[0178]
A dispersion of the following Dye Trapping Agent was prepared in the manner as mentioned below.
[0179] Precisely, 600 cc of an aqueous 5% solution of the following Anionic Surfactant (j) was added to a mixture comprising 108 cc of the following polymer latex (solid content: 13.3%), 20 g of the following Nonionic Surfactant (i) and 1232 cc of water, with stirring, over a period of 10 minutes. The suspension thus formed was concentrated to 500 cc, using an ultrafiltration module (fractionating molecular weight: 10,000) and desalted . Fifteen hundred cc of water was added thereto, and the same operation was repeated once more. Thus, a dispersion of Dye Trapping Agent was obtained.
Polymer Latex:
Nonionic Surfactant (i):
Anionic Surfactant (j):
[0182]
Using the materials prepared above and the materials mentioned below, a heat-developing multi-layer color photographic material Sample No. 201 having the layer constitution of Table 23 below was prepared.
Yellow Dye Donor Compound (31):
Magenta Dye Donor Compound (32):
Cyan Dye Donor Compound (33):
Cyan Dye Donor Compound (34):
Reducing Agent (35):
Reducing Agent (36):
Electron Transmitting Agent Precursor (37):
Nucleophilic Agent (38):
High-boiling Point Solvent (39):
High-boiling Point Solvent (40):
Antifoggant (41):
UV Absorbent (42):
Antifoggant (45):
Antifoggant (46):
[0197]
Samples Nos. 202 to 206 were prepared in the same manner as in preparation of Sample No. 201, except that the mean grain (oil droplet) sizes of the emulsions in the constituent layers were varied to those indicated in Table 24 below by varying the dispersing condition.
TABLE 24
| Sample No. | Mean Grain Size of Emulsion (µm) | ||
| C | M | Y | |
| 201 (comparative sample) | 0.39 | 0.35 | 0.38 |
| 202 (comparative sample) | 0.45 | 0.47 | 0.46 |
| 203 (comparative sample) | 0.55 | 0.55 | 0.56 |
| 204 (sample of the invention) | 0.24 | 0.25 | 0.27 |
| 205 (sample of the invention) | 0.17 | 0.18 | 0.18 |
| 206 (sample of the invention) | 0.12 | 0.14 | 0.13 |
[0198] The above-mentioned multi-layer color photographic material Sample Nos. 201 to 206 were each exposed through a blue-green-red-gray wedge having a continuously varying color density. The exposed samples were dipped in water kept at 45°C, squeezed with rollers, and then immediately attached to the above-mentioned image-receiving material Sample (R-1) in such a way that the coated top surfaces of the two faced each other. The combined samples were heated with a heat drum for 15 seconds so that the water-applied surfaces were heated up to 80°C. Then, the photographic material sample was peeled off from the image-receiving material sample, whereupon a sharp positive color image was formed on the image-receiving material sample.
[0199] The gray area of the image thus formed was subjected to sensitometry to give the results shown in Table 25 below.
1. A heat-developing diffusion transfer color photographic material having on a support
at least one layer containing therein a light-sensitive silver halide, a binder and
a non-diffusive dye donor compound capable of releasing or forming a diffusive dye
in correspondence or reverse correspondence to a reduction reaction of the silver
halide to silver, in which the non-diffusive dye donor compound has been added to
the material as an emulsified dispersion thereof having a mean grain size of 0.3 µmm
or less.
2. The heat-developing diffusion transfer color photographic material as claimed in claim
1, in which the the non-diffusive dye donor compound has been added to the material
as an emulsified dispersion thereof having a mean grain size of 0.2 µmm or less.
3. The heat-developing diffusion transfer color photographic material as claimed in claim
1, in which the the non-diffusive dye donor compound has been added to the material
as an emulsified dispersion thereof having a mean grain size of 0.15 µmm or less.
4. The heat-developing diffusion transfer color photographic material as claimed in claim
1, wherein the light-sensitive silver halide, the binder, and the dye donor compound
are in the same layer.
5. The heat-developing diffusion transfer color photographic material as claimed in claim
1, wherein the dye donor compound is located in a layer which is adjacent an emulsion
layer and between said emulsion layer and said support.