Silver halide color photographic light-sensitive material and color image formation method using the same

FIELD OF THE INVENTION
The present invention relates to a novel silver halide color photographic light-sensitive material for recording an image and a method for forming a color image using the same.
BACKGROUND OF THE INVENTION
Photographic light-sensitive materials using silver halide are more and more expanding in recent years and at present, a high-quality color image can be easily obtained. For example, in a system usually called a color photograph, photographing is performed using a color negative film and the image information recorded on the color negative film after development is optically printed on a color paper to obtain a color print. Recently, this process has advanced to a higher level so that a color lab as a large-scale centralized base for producing a large quantity of color prints in high efficiency or a so-called mini lab as a compact and simple printer processor installed at a shop is popularized, and as a result, anybody can easily enjoy color photographs.
The color photograph currently popularized has a principle of using color reproduction according to a subtractive color process. A general color negative film comprises a transparent support having provided thereon light-sensitive layers using silver halide emulsions as light-sensitive elements imparted with spectral sensitivity in blue, green and red regions, respectively, each light-sensitive layer containing in combination a so-called color coupler which forms a yellow, magenta or cyan dye as a hue to come to a complementary color. After imagewise exposure by photographing, the color negative film is developed in a color developer containing an aromatic primary amine developing agent. At this time, exposed silver halide grains are developed, namely, reduced by the developing agent and the oxidation product of the developing agent, which is simultaneously produced, causes coupling reaction with the above-described color coupler and thereby each dye is formed. Metal silver (developed silver) generated on development and unreacted silver halide are removed by bleaching and fixing, respectively, to obtain a dye image. Through the thus processed color negative film, a color printing paper as a color light-sensitive material comprising a reflective support having provided thereon light-sensitive layers each having the same combination of sensitive wavelength region with colored hue is optically exposed and then subjected similarly to color development, bleaching and fixing, and thereby a color print comprising a dye image reproducing the scene of an original can be obtained.
The above-described system is widely popularized at present, however, demands for further simplicity are more and more increasing. First, processing baths for performing color development, bleaching and fixing need be precisely controlled on the composition and the temperature and therefore, professional knowledge and skilled operation are required; second, the processing solutions contain materials restricted in the discharge in view of environmental conservation, such as a color developing agent and an iron chelate compound bleaching agent, and therefore, facilities for exclusive use are required in many cases for installing equipments such as a developing machine; and third, although the processing time is reduced by the technical development in recent years, time needs be spent on the above-described development processing and accordingly, the demand for rapid reproduction of a recording image cannot be satisfactorily met.
From these backgrounds, demands are more and more increasing for establishing a system not using the color developing agent or the bleaching agent used in the current color image formation system, to lighten the environmental load and to improve simplicity.
Taking account of these points of view, many improved techniques have been proposed. For example, IS & T's 48th Annual Conference Proceedings, page 180, discloses a system dispensable with the bleach-fixing bath which is indispensable in conventional color photographic processing, where a dye produced on development reaction is moved to a mordanting layer and then, the layer is peeled off to remove developed silver or unreacted silver halide. However, in the technique proposed here, development processing in a processing bath containing a color developing agent is still necessary and the environmental issue can be hardly overcome.
As a system not using a processing solution containing a color developing agent, a Pictrography system has been proposed by Fuji Photo Film Co., Ltd. In this system, a slight amount of water is fed to a light-sensitive material containing a base precursor, laminating it to an image-receiving member, and these are heated to cause development reaction. This system is advantageous in view of environmental issue because the above-described processing bath is not used. However, this system is intended to use in fixing the image formed to a dye fixing layer and viewing it as a dye image, and therefore, a system usable as a recording material for photographing has been demanded.
Under these circumstances, various investigations have been made using the above-described system to obtain a light-sensitive material for photographing reduced in the environmental load and capable of simple image recording, however, it has been found that a problem remains in view of image quality as compared with the current system.
First, when a satisfactory image density is intended to achieve using the above-described system, graininess is conspicuously deteriorated and this deterioration in graininess is accompanied by impairment of the image quality of an image obtained, which is out of keeping with the object of providing a light-sensitive material capable of short-time and simple processing for photographing. Second, using the above-described system, good developing property and wide exposure latitude can be difficultly obtained at the same time and this is also an obstacle to the object of providing a light-sensitive material capable of short-time and simple processing for photographing.
SUMMARY OF THE INVENTION
A first object of the present invention is to provide a light-sensitive material for photographing, capable of rapid image formation reduced in the load on environment.
A second object of the present invention is to provide an excellent color photographic light-sensitive material capable of giving good graininess and wide exposure latitude even in simple and rapid processing.
The above-described objects of the present invention can be effectively attained by the following constructions of the present invention:
1) a silver halide color photographic light-sensitive material capable of forming an image by, after exposure of a light-sensitive material, supplying water corresponding to from 1/10 to 1 times the water necessary for giving maximum swelling of all coated layers of a light-sensitive material and a processing material to the light-sensitive material or the processing material, laminating-these materials to each other and then heating them, the light-sensitive material comprising a support having thereon at least one photographic light-sensitive layer comprising a light-sensitive silver halide, a developing agent, a compound capable of forming a dye upon coupling reaction with an oxidation product of the developing agent and a binder, and the processing material comprising a support having thereon a processing layer containing a base and/or a base precursor, wherein at least two kinds of silver halide emulsions having spectral sensitivity in the same wavelength region and different in the average grain projected area are used in combination such that an emulsion having a larger average grain projected area has a ratio of silver halide grain numbers per unit area of the light-sensitive material larger than the ratio of the values obtained by dividing the coated silver amount of the emulsion by the 3/2nd power of average grain projected area;
2) a silver halide color photographic light-sensitive material as described in item 1), wherein at least one of the silver halide emulsions comprises silver iodobromide grains having in the inside of the silver halide grain a laminate structure composed of a plurality of layers different in the halogen composition and having at least one layer higher in the iodide content than both the layers adjacent thereto in the grain internal side and in the-grain surface side;
3) a silver halide color photographic light-sensitive material as described in item 1) or 2), wherein the developing agent is a compound represented by the following formula I, II, III or IV: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamido group, an arylcarbonamido group, an alkylsulfonamido group, an arylsulfonamido group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylcarbamoyl group, an arylcarbamoyl group, a carbamoyl group, an alkylsulfamoyl group, an arylsulfamoyl group, a sulfamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group or an acyloxy group, R.sub.5 represents an alkyl group, an aryl group or a heterocyclic group, Z represents an atomic group necessary for forming a (hetero)aromatic ring and when Z is a benzene ring, the sum of the Hammett's constants (.sigma.) of the substituents thereof is 1 or more, R.sub.6 represents an alkyl group, X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom, R.sub.7 and R.sub.8 each represents a hydrogen atom or a substituent and R.sub.7 and R.sub.8 may be combined to each other to form a double bond or a ring,
and the compounds represented by formulae I to IV each contains at least one ballast group having 8 or more carbon atoms so as to impart oil solubility to the molecule; and
4) a method for forming a color image comprising imagewise exposing a silver halide light-sensitive material described in item 1), 2) or 3) used as a light-sensitive material, supplying water corresponding to from 1/10 to 1 times the total of the water amount necessary for giving maximum swelling of a light-sensitive material and a processing material to the light-sensitive material or the processing material, laminating these materials to each other and then heating them at a temperature of from 60 to 100.degree. C. for from 5 to 60 seconds.
DETAILED DESCRIPTION OF THE INVENTION
Various silver halides have been proposed as the silver halide preferred in a so-called heat development system of performing development at a high temperature, which is discriminated from usual liquid development photographic system. For example, JP-B-2-48101 (the term "JP-B" as used herein means an "examined Japanese patent publication") discloses a technique to improve heat development process-ability by using tabular silver halide having a grain size of 5 times or more the grain thickness in a heat developable color light-sensitive material.
JP-A-62-78555 (the term "JP-A" as used herein means an "unexamined published Japanese patent application") discloses a technique to improve long-term storage stability of a heat developable light-sensitive material by incorporating tabular light-sensitive silver halide grains having a ratio of the grain size to the grain thickness of 5 or more in an amount of from 0.05 to 1 mol per mol of the organic silver salt.
JP-A-62-79447 discloses a technique to improve the sensitivity and the maximum density upon heat development by incorporating tabular light-sensitive silver halide grains having a ratio of the grain size to the grain thickness of 5 or more and light-sensitive silver halide grains having a silver iodide content of from 4 to 40 mol % and an average grain size of 0.4 .mu.m or less.
However, these techniques all are intended for a print-use photographic light-sensitive material and quite a different technique from the technique of the present invention improving graininess which is an essential matter in constructing a light-sensitive material for photographing using a heat development system. Accordingly, even when these techniques are applied, the objects of the present invention cannot be achieved.
In a color negative film conventionally used in taking a photograph, a technique of, for example, using a so-called DIR coupler which releases a development inhibiting compound upon coupling reaction with an oxidation product of the developing agent, is used. In the light-sensitive material of the present invention, excellent granularity can be obtained even when the DIR coupler is not used, and if the DIR coupler is combined, further excellent granularity is obtained.
In the present invention, a light-sensitive material for use in recording a scene of an original and reproducing it as a color image may be constructed fundamentally using color reproduction by subtractive color process. More specifically, the color information of an original scene can be recorded by providing at least three light-sensitive layers having spectral sensitivity in the blue, green and red regions and incorporating into each light-sensitive layer a color coupler capable of forming a yellow, magenta or cyan dye having a complementary relation to the sensitive wavelength region of the layer itself. Through the thus-obtained dye image, a color printing paper having the same relation between the sensitive wavelength and the colored hue is exposed and thereby, the scene of an original can be reproduced. Further, the information of a dye image obtained by photographing a scene of an original may be read by a scanner or the like to reproduce the information as an image for viewing.
The light-sensitive material of the present invention may be constructed by providing light-sensitive layers having spectral sensitivity in three or more wavelength regions.
Further, the sensitive wavelength region and the colored hue may have a relation therebetween other than the complementary relation. In such a case, after taking in the above-described image information, image processing such as hue conversion may be applied to reproduce the color information of an original.
In the present invention, at least two kinds of silver halide emulsions having spectral sensitivity in the same wavelength region and different in the average grain projected area must be used in combination. The term "having spectral sensitivity in the same wavelength region" as used in the present invention means to have spectral sensitivity in the effectively same wavelength region. Accordingly, when emulsions slightly different in the spectral sensitivity distribution are overlapped in the main light-sensitive region, they are regarded as the emulsions having spectral sensitivity in the same wavelength region.
In the present invention, a plurality of emulsions having spectral sensitivity in the same wavelength region and different in the average grain projected area can be used in different light-sensitive layers separately or the plurality of emulsions may be mixed and incorporated into same light-sensitive layer.
When these emulsions are contained in separate light-sensitive layers, the color coupler to be combined therewith preferably has the same hue, however, couplers of forming color in different hues may be mixed to give different colored hues to respective light-sensitive layers or couplers different in the absorption profile of the colored hue may be used in respective light-sensitive layers.
In the present invention, these emulsions having spectral sensitivity in the same wavelength region must be coated to have a construction such that an emulsion having a larger average grain projected area has a ratio of silver halide grain numbers per unit area of the light-sensitive material larger than the ratio of the values obtained by dividing the coated silver amount of the emulsion by the 3/2nd power of average grain projected area.
That is, the light-sensitive material for use in the present invention comprises at least two kinds of silver halide emulsion having spectral sensitivity in the same wavelength region and different in the average grain projected area, and said at least two kinds of silver halide emulsions satisfying the following relationship: ##EQU1## wherein C.sub.1 and C.sub.2 represents numbers of silver halide grains having a smaller average grain projected area and a larger average grain projected area, respectively, per unit area of the light-sensitive material; D.sub.1 and D.sub.2 represents coated silver halide amounts of silver halide grains having a smaller average grain projected area and a larger average grain projected area, respectively, per unit area of the light-sensitive material; and E.sub.1 and E.sub.2 represents average grain projected areas of silver halide grains having a smaller average grain projected area and a larger average grain projected area, respectively, per unit area of the light-sensitive material.
More specifically, assuming that (i) emulsion a is an emulsion having the smallest average grain projected area, and emulsions b, c, . . . increase their average grain projected areas in this order; (ii) Ka, Kb, Kc . . . are a number of silver halide grains per unit of emulsions a, b, c, . . . , respectively, and Pa, Pb, Pc, . . . are a ratio of Ka, Kb, Kc, to Ka, respectively (Pa=1); and (iii) Ha, Hb, Hc, . . . are a ratio of the value obtained by dividing the coated silver amount of emulsions a, b, c, . . . by the 3/2.sup.nd power of average grain projected area of emulsions a, b, c, . . . , respectively, and Qa, Qb, Qc, . . . are a ratio of Ha, Hb, Hc, . . . , to Ha, respectively (Qa=1), "the larger the average grain projected area of an emulsion is, the larger the ratio of P to Q is" means that the ratio of Pb to Qb (>1) is larger than the ratio of Pa to Qa (=1) and that the ratio of Pc to Qc is larger than the ratio of Pb to Qb. That is, the relationship: . . . >Pc/Qc>Pb/Qb>Pa/Qa is satisfied in the present invention.
In other words, "the larger the average grain projected area of an emulsion, the larger the ratio of P to Q is" means that in emulsion n (n=1 to i; i.gtoreq.2; the larger n is, the larger the average grain projected area of the emulsion n is), any emulsions k and m (1.ltoreq.k.ltoreq.i, 1.ltoreq.m.ltoreq.i, k>m) satisfy the relationship: Pk/Qk>Pm/Qm.
By having such a construction, an image having good graininess can be obtained even under the development condition of heating at a high temperature and also, high developing property and wide exposure latitude can be satisfactorily achieved at the same time.
The emulsion for use in the present invention preferably has a halogen composition of silver iodobromide or silver bromide. The emulsion of the present invention may contain silver chloride, however, the silver chloride content is preferably 8 mol % or less, more preferably 3 mol % or less. The silver halide emulsion more preferably comprises silver iodobromide grains having in the inside of the silver halide grain a laminate structure consisting of a plurality of layers different in the halogen composition and having at least one layer higher in the iodide content than both the layers adjacent thereto in the grain internal side and in the grain surface side.
The silver halide grain for use in the present invention is preferably a so-called tabular grain having a diameter larger than the thickness of the grain. The tabular grain preferably has a shape such that the ratio obtained by dividing the grain diameter by the thickness is 2 or more, more preferably 5 or more. The shape of silver halide grains can be measured by observing the silver halide grain together with a latex ball for reference used as a standard of the size through an electron microscope by a carbon replica method of simultaneously shadowing them with a heavy metal or the like.
The term "diameter of the silver halide grain" as used herein means a diameter of a circle having the same projected area as the grain. The silver halide grain for use in the present invention has a diameter of preferably from 0.1 to 10 .mu.m, more preferably from 0.3 to 5 .mu.m, still more preferably from 0.5 to 4 .mu.m.
The silver halide emulsion for use in the present invention may be selected from the silver halide emulsions prepared by the methods described, specifically, in U.S. Pat. Nos. 4,500,626 (column 50) and 4,628,021, Research Disclosure (hereinafter simply referred to as RD) No. 17029 (1978), ibid., No. 17643 (December 1978), pages 22 to 23, ibid., No. 18716 (November 1979), page 648, ibid., No. 307105 (November 1989), pages 863 to 865, JP-A-62-253159, JP-A-64-13546, JP-A-2-236546, JP-A-3-110555, P. Glafkides, Chimie et Phisique Photographique, Paul Montel (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966) and V. L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press (1964).
In the process of preparing the light-sensitive silver halide emulsion of the present invention, so-called desilvering for removing excessive salts is preferably performed. As a means therefor, a noodle washing method of performing desilvering by gelling gelatin or a precipitation method using an inorganic salt comprising a polyvalent anion (e.g., sodium sulfate), an anionic surface active agent, an anionic polymer (e.g., sodium polystyrenesulfonate) or a gelatin derivative (e.g., aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin) may be used. A precipitation method is preferably used.
The light-sensitive silver halide emulsion for use in the present invention may contain for various purposes a heavy metal such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron and osmium. These compounds may be used individually or in combination of two or more thereof. The addition amount varies depending on the use purpose, however, it is generally on the order of from 10.sup.-9 to 10.sup.-3 mol per mol of silver halide. The heavy metal may be incorporated uniformly into the grain or may be localized in the inside or on the surface of the grain. Specifically, emulsions described in JP-A-2-236542, JP-A-1-11637 and Japanese Patent Application No. 4-126629 (corresponding to JP-A-5-181246) are preferably used.
At the stage of forming grains of the light-sensitive silver halide emulsion of the present invention, a rhodanate, an ammonia, a tetra-substituted thiourea compound, an organic thioether derivative described in JP-B-47-11386 or a sulfur-containing compound described in JP-A-53-144319 may be used as a silver halide solvent.
With respect to other conditions, description in P. Glafkides, Chimie et Phisique Photographique, Paul Montel (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966) and V. L. Zelikman et al. Making and Coating Photographic Emulsion, The Focal Press (1964) may be referred to. More specifically, any of an acid process, a neutral process and an ammonia process may be used, and as a method of reacting a soluble silver salt with a soluble halogen salt, any of a single jet method, a double jet method and a combination thereof may be used. In order to obtain a monodisperse emulsion, a double jet method is preferably used.
A reverse mixing method of forming grains in excessive silver ions may be used. A so-called controlled double jet method, which is one form of the double jet method, of keeping constant the pAg of the liquid phase where the silver halide is formed may also be used.
Further, in order to accelerate growth of grains, the concentration, the amount or the addition rate of silver salt and halogen salt added may be increased (see, JP-A-55-142329, JP-A-55-158124, U.S. Pat. No. 3,650,757).
The reaction solution may be stirred by any known stirring method. The temperature and the pH of the reaction solution during formation of silver halide grains may be freely selected depending on the purpose. The pH is preferably from 2.2 to 7.0, more preferably from 2.5 to 6.0.
The light-sensitive silver halide emulsion is usually a silver halide emulsion subjected to chemical sensitization. In the chemical sensitization of the light-sensitive silver halide emulsion for use in the present invention, chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization, noble metal sensitization using gold, platinum or palladium, and reduction sensitization, which are all known to the emulsion for normal type light-sensitive materials, may be used individually or in combination (see, for example, JP-A-3-110555 and Japanese Patent Application No. 4-75798 (corresponding to JP-A-5-241267)). The chemical sensitization may also be performed in the presence of a nitrogen-containing heterocyclic compound (see, JP-A-62-253159). Further, an antifoggant which will be described later, may be added after completion of the chemical sensitization. Specifically, the methods described in JP-A-5-45833 and JP-A-62-40446 may be used.
At the time of chemical sensitization, the pH is preferably from 5.3 to 10.5, more preferably from 5.5 to 8.5, and the pAg is preferably from 6.0 to 10.5, more preferably from 6.8 to 9.0.
The light-sensitive silver halide for use in the present invention is coated in an amount of, in terms of silver, from 1 mg/m.sup.2 to 10 g/m.sup.2.
The light-sensitive silver halide emulsion for use in the present invention may be spectrally sensitized by a methine dye or the like so that the light-sensitive silver halide emulsion can have spectral sensitivity such as green sensitivity and red sensitivity. Further, spectral sensitization in the blue region may be applied to the blue-sensitive emulsion, if desired.
Examples of the dye used therefor include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxonol dye.
Specific examples thereof include the sensitizing dyes described in U.S. Pat. No. 4,615,257, JP-A-59-180550, JP-A-64-13546, JP-A-5-45828 and JP-A-5-45834.
These sensitizing dyes may be used individually or in combination and the combination of sensitizing dyes is often used for the purpose of supersensitization or for controlling the wavelength of spectral sensitization.
In combination with a sensitizing dye, a dye which itself has no spectral sensitization effect or a material which absorbs substantially no visible light, but which exhibits supersensitization, may be contained in the emulsion (those described, for example, in U.S. Pat. No. 3,615,641 and JP-A-63-23145).
The spectral sensitizing dye may be added to the emulsion before, during or after chemical sensitization or according to U.S. Pat. Nos. 4,183,756 and 4,225,666, may be added before or after nucleation of silver halide grains. The sensitizing dye or the supersensitizing dye may be added as a solution in an organic solvent such as methanol, a dispersion, for example, in gelatin, or a one-part solution with a surface active agent. The addition amount is generally on the order of from 10.sup.-8 to 10.sup.-2 mol per mol of silver halide.
The additives for use in these processes and known photographic additives which can be used in the present invention are described in RD, No. 17643, ibid., No. 18716 and ibid., No. 307105, and the pertinent portions are summarized in the table below.
______________________________________Kinds of Additives RD17643 RD18716 RD307105______________________________________1. Chemical sensitizer p. 23 p. 648, right p. 866 col.2. Sensitivity increasing p. 648, right agent col3. Spectral sensitizer, pp. 23-24 p. 648, right pp. 866-868 supersensitizer col.-p. 649, right col.4. Whitening agent p. 24 p. 648, right p. 868 col.5. Antifoggant, pp. 24-25 p. 649, right pp. 868-870 stabilizer col.6. Light absorbent, pp. 25-26 p. 649, right p. 873 filter dye, UV col.-p. 650, absorbent left col.7. Dye image stabilizer p. 25 p. 650, left p. 872 col.8. Hardening agent p. 26 p. 651, left pp. 874-875 col.9. Binder p. 26 p. 651, left pp. 873-874 col.10. Plasticizer, p. 27 p. 650, right p. 876 lubricant col.11. Coating aid, surface pp. 26-27 p. 650, right pp. 875-876 active agent col.12. Antistatic agent p. 27 p. 650, right pp. 876-877 col.13. Matting agent pp. 878-879______________________________________
In the present invention, together with the light-sensitive silver halide, an organic metal salt may be used as an oxidizing agent. Among the organic metal salts, an organic silver salt is particularly preferred.
Examples of the organic compound which can be used in forming the above-described organic silver salt oxidizing agent, include benzotriazoles described in U.S. Pat. No. 4,500,626, columns 52 to 53, aliphatic acids and other compounds. Further, silver acetylide described in U.S. Pat. No. 4,775,613 is useful. The organic silver salts may be used in combination of two or more thereof.
The organic silver salt may be used in an amount of from 0.01 to 10 mol, preferably from 0.01 to 1 mol, per mol of the light-sensitive silver halide. The total coated amount of the light-sensitive silver halide and the organic silver salt is suitably, in terms of silver, from 0.05 to 10 g/m.sup.2, preferably from 0.1 to 4 g/m.sup.2.
As the binder in the constituent layers of the light-sensitive material, a hydrophilic binder is preferably used. Examples thereof include those described in Research Disclosure and JP-A-64-13546, pages (71) to (75). More specifically, a transparent or translucent hydrophilic binder is preferred and examples thereof include natural compounds such as proteins (e.g., gelatin and gelatin derivative) and polysaccharides (cellulose derivatives, starch, gum arabi, dextran, plurane); and synthetic polymer compounds such as polyvinyl alcohol, polyvinyl pyrrolidone and acrylamide polymer. Further, highly absorptive polymers described in U.S. Pat. No. 4,960,681 and JP-A-62-245260, more specifically, homopolymers of a vinyl monomer having --COOM or --SO.sub.3 M (wherein M represents a hydrogen atom or an alkali metal) and copolymers of the vinyl monomers or of the vinyl monomer with other vinyl monomer (e.g., sodium methacrylate, ammonium methacrylate, Sumikagel L-5H produced by Sumitomo Chemical Co., Ltd.) may also be used. These binders may be used in combination of two or more thereof. In particular, a combination of gelatin with the above-described binder is preferred. The gelatin may be selected from lime-processed gelatin, acid-processed gelatin and so-called delimed gelatin reduced in the content of calcium or the like, and these may be preferably used in combination.
In the present invention, the amount of binder coated is preferably 20 g/m.sup.2 or less, more preferably 10 g/m.sup.2 or less.
The coupler for use in the present invention may be either a 4-equivalent coupler or a 2-equivalent coupler. Further, a non-diffusible group may form a polymer chain. Specific examples of the coupler are described in detail in T. H. James, The Theory of the Photographic Process, 4th Ed. pp. 291-334 and pp. 354-361, JP-A-58-123533, JP-A-58-148046, 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, JP-A-60-66249, and Japanese Patent Application Nos. 6-270700, 6-307049 and 6-312380.
Further, the following couplers are preferably used.
Yellow Coupler:
Couplers represented by formulae (I) and (II) of EP 502424A; couplers represented by formulae (1) and (2) of EP 513496A; couplers represented by formula (I) in claim 1 of Japanese Patent Application No. 4-134523 (corresponding to JP-A-5-307248); couplers represented by formula D in column 1, lines 45 to 55 of U.S. Pat. No. 5,066,576; couplers represented by formula D in paragraph 0008 of JP-A-4-274425; couplers described in claim 1 at page 40 of EP 498381A1; couplers represented by formula (Y) at page 4 of EP 447969A1; couplers represented by formulae (I) to (IV) in column 7, lines 36 to 58 of U.S. Pat. No. 4,476,219.
Magenta Coupler:
Couplers described in JP-A-3-39737, JP-A-6-43611, JP-A-5-204106 and JP-A-4-3626.
Cyan Coupler:
Couplers described in JP-A-204843, JP-A-4-43345 and Japanese Patent Application No. 4-236333.
Polymer Coupler:
Couplers described in JP-A-2-44345.
As the coupler which provides a colored dye having an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, EP 96570 and German Patent 3,234,533 are preferred.
Further, the light-sensitive material of the present invention may contain the following functional couplers. Examples of the coupler for correcting unnecessary absorption of a colored dye include yellow colored cyan couplers described in EP 456257A1, yellow colored magenta couplers described in EP 456257A1, magenta colored cyan couplers described in U.S. Pat. No. 4,833,069, and colorless masking couplers represented by formula (2) of U.S. Pat. No. 4,837,136 and formula (A) claim 1 of WO92/11575 (particularly, compounds described in pages 36 to 45).
Examples of the compound (including coupler) which releases a photographically useful compound upon reaction with an oxidation product of a developing agent include the following compounds.
Development Inhibitor-Releasing Compound:
Compounds represented by formulae (I), (II), (III) and (IV) described at page 11 of EP 78236A1; compounds represented by formula (I) described at page 7 of EP 436938A2; compounds represented by formula (1) of JP-A-5-307248; compounds represented by formulae (I), (II) and (III) described at pages 5 and 6 of EP 440195A2; compound-ligand releasing compound represented by formula (I) of claim 1 of JP-A-6-59411; and Compounds represented by LIG-X described in claim 1 of U.S. Pat. No. 4,555,478.
The light-sensitive material of the present invention must contain a color developing agent of which oxidation product produced by silver development can couple with the above-described coupler to form a dye.
In this case, a combination of a p-phenylenediamine developing agent with a phenol or active methylene coupler described in U.S. Pat. No. 3,531,256, or a combination of a p-aminophenol developing agent with an active methylene coupler described in U.S. Pat. No. 3,761,270 may be used.
The sulfonamidophenol as described in U.S. Pat. No. 4,021,240 and JP-A-60-128438 is preferred because when they are contained in the light-sensitive material, excellent stock storability is provided.
In incorporating a color developing agent, a precursor of the color developing agent may also be used. Examples thereof include indoaniline compounds described in U.S. Pat. No. 3,342,597, Schiff base type compounds described in U.S. Pat. No. 3,342,599, Research Disclosure, No. 14850 and ibid., No. 15159, aldol compounds described in ibid., No. 13924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-base compounds described in JP-A-53-135628.
Also, a combination of a sulfonamidophenol developing agent described in Japanese Patent Application No. 7-180568 or a hydrazine-base developing agent described in Japanese Patent Application Nos. 7-49287 (corresponding to EP 727708 A) and 7-63572 (JP-A-8-234388) with a coupler is preferably used in the light-sensitive material of the present invention.
In the present invention, the compound represented by formula I, II, III or IV is preferably used as the developing agent. Among these, the compounds represented by formulae I and II are preferred.
These developing agents are described in detail below.
The compound represented by formula I is a compound generically called as sulfonamidophenol and known in the art. When used in the present invention, at least one of the substituents R.sub.1 to R.sub.5 preferably has a ballast group having 8 or more carbon atoms.
In formula I, R.sub.1 to R.sub.4 each represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine), an alkyl group (e.g., methyl, ethyl, isopropyl, n-butyl, t-butyl), an aryl group (e.g., phenyl, tolyl, xylyl), an alkylcarbonamido group (e.g., acetylamino, propionylamino, butyroylamino), anarylcarbonamido group (e.g., benzoylamino), an alkylsulfonamido group (e.g., methanesulfonylamino, ethanesulfonylamino), an arylsulfonamido group (e.g., benzenesulfonylamino, toluenesulfonylamino), an alkoxy group (e.g., methoxy, ethoxy, butoxy), an aryloxy group (e.g., phenoxy), an alkylthio group (e.g., methylthio, ethylthio, butylthio), an arylthio group (e.g., phenylthio, tolylthio), an alkylcarbamoyl group (e.g., methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidylcarbamoyl, morpholylcarbamoyl), an arylcarbamoyl group (e.g., phenylcarbamoyl, methylphenylcarbamoyl, ethylphenylcarbamoyl, benzylphenylcarbamoyl), a carbamoyl group, an alkylsulfamoyl group (e.g., methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoyl, morpholylsulfamoyl), an arylsulfamoyl group (e.g., phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), a sulfamoyl group, a cyano group, an alkylsulfonyl group (e.g., methanesulfonyl, ethanesulfonyl), an arylsulfonyl group (e.g., phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an alkylcarbonyl group (e.g., acetyl, propionyl, butyroyl), an arylcarbonyl group (e.g., benzoyl, alkylbenzoyl) or an acyloxy group (e.g., acetyloxy, propionyloxy, butyroyloxy). Out of R.sub.1 to R.sub.4, R.sub.2 and R.sub.4 each is preferably a hydrogen atom. The sum of the Hammett's constants .sigma..sub.p of R.sub.1 to R.sub.4 is preferably 0 or more. R.sub.5 represents an alkyl group (e.g., methyl, ethyl, butyl, octyl, lauryl, cetyl, stearyl), an aryl group (e.g., phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-(methoxycarbonyl)) or a heterocyclic group (e.g., pyridyl).
The compound represented by formula II is a compound generically called as carbamoylhydrazine and known in the art. In the compound when used in the present invention, R.sub.5 or a substituent of the ring preferably has a ballast group having 8 or more carbon atoms.
In formula II, Z represents an atomic group necessary for forming an aromatic ring. The aromatic ring formed by Z must be sufficiently electron attractive (withdrawing property) so as to impart silver development activity to the compound. Accordingly, a nitrogen-containing aromatic ring or an aromatic group resulting from introducing an electron attractive (withdrawing) group into the benzene ring is preferably formed. Preferred examples of the aromatic ring include a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring and a quinoxaline ring. In the case of a benzene ring, examples of the substituent thereof include an alkylsulfonyl group (e.g., methanesulfonyl, ethanesulfonyl), a halogen atom (e.g., chlorine, bromine), an alkylcarbamoyl group (e.g., methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl, diethylcarbamoyl, dibutylcarbamoyl, piperidinecarbamoyl, morpholinocarbamoyl), an arylcarbamoyl group (e.g., phenylcarbamoyl, methylphenylcarbamoyl), a carbamoyl group, an alkylsulfamoyl group (e.g., methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoyl, morpholylsulfamoyl), an arylsulfamoyl group (e.g., phenylsulfamoyl, methylphenylsulfamoyl, ethylphenylsulfamoyl, benzylphenylsulfamoyl), a sulfamoyl group, a cyano group, an alkylsulfonyl group (e.g., methanesulfonyl, ethanesulfonyl), an arylsulfonyl group (e.g., phenylsulfonyl, 4-chlorophenylsulfonyl, p-toluenesulfonyl), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl), an aryloxycarbonyl group (e.g., phenoxycarbonyl), an alkylcarbonyl group (e.g., acetyl, propionyl, butyroyl) and an arylcarbonyl group (e.g., benzoyl, alkylbenzoyl). The sum of the Hammett's constant a values of the substituents is preferably 1 or more.
The compound represented by formula III is a compound generically called as carbamoylhydrazine. The compound represented by formula IV is a compound generally called as sulfonylhydrazine. These compounds both are known in the art. In the compounds when used in the present invention, at least one of R.sub.5 to R.sub.8 preferably has a ballast group having 8 or more carbon atoms.
In formulae III and IV, R.sub.6 represents an alkyl group (e.g., methyl, ethyl), X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom, with the alkyl-substituted tertiary nitrogen atom being preferred, R.sub.7 and R.sub.8 each represents a hydrogen atom or a substituent (examples thereof include those described above as the substituent of the benzene ring formed by Z), and R.sub.7 and R.sub.8 may be combined with each other to form a double bond or a ring.
Among the compounds represented by formulae I to IV, the compounds represented by formulae I and II are preferred in the present invention in view of stock storability.
The groups represented by R.sub.1 to R.sub.8 each may have a substituent, if possible, and examples of the substituent include those described above as the substituent of the benzene ring formed by Z.
Specific examples of the compounds represented by formulae I to IV are set forth below, however, the compounds of the present invention are by no means limited thereto. ##STR2##
The above-described compounds can be synthesized by a generally known method. Examples of simple synthesis routes are described below.
Synthesis of Developing Agent D-2: ##STR3## Synthesis of Developing Agent D-27: ##STR4## Synthesis of D-42: ##STR5##
In the case when a non-diffusible developing agent is used, an electron transferring agent and/or an electron transferring agent precursor may be used in combination, if desired, so as to accelerate transfer of electrons between the non-diffusible developing agent and developable silver halide. In particular, those described in U.S. Pat. No. 5,139,919 and European Unexamined Patent Publication 418743 are preferred. Further, a method of stably introducing it into a layer as described in JP-A-2-230143 and JP-A-2-235044 is preferably used.
The electron transferring agent or a precursor thereof may be selected from the above-described developing agents and precursors thereof. The electron transferring agent or a precursor thereof preferably has mobility larger than that of the non-diffusible developing agent (electron donor). Particularly useful electron transferring agents are 1-phenyl-3-pyrazolidones and aminophenols.
The electron donor precursors described in JP-A-3-160443 are also preferably used.
The interlayer or the protective layer may use a reducing agent for various purposes such as prevention of color mixing or improvement of color reproduction. Specific preferred examples thereof include reducing agents described in European Unexamined Patent Publications 524649 and 357040, JP-A-4-249245, JP-A-2-46450 and JP-A-63-186240. The development inhibitor-releasing reducing agent compounds described in JP-B-3-63733, JP-A-1-150135, JP-A-2-46450, JP-A-2-64634, JP-A-3-43735 and European Unexamined Patent Publication 451833 may also be used.
A developing agent precursor which itself has no reducing property but exerts reducing property by the action of a nucleophilic reagent or heat, may be used.
In addition, a reducing agent as described below may also be incorporated into the light-sensitive material.
Examples of the reducing agent for use in the present invention include reducing agents and reducing agent precursors described in U.S. Pat. Nos. 4,500,626 (columns 49 and 50), 4,839,272, 4,330,617, 4,590,152, 5,017,454 and 5,139,919, 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-60-128439, JP-A-60-198540, JP-A-60-181742, JP-A-61-259253, JP-A-62-244044, JP-A-62-131253, JP-A-62-131256, JP-A-64-13546 (pates (40) to (57)), JP-A-1-120553 and European Unexamined Patent Publication 220746A2 (pages 78 to 96).
Further, various reducing agents may be used in combination as disclosed in U.S. Pat. No. 3,039,869.
The developing agent or the reducing agent may be incorporated into the processing sheet which will be described layer, or may be incorporated into the light-sensitive material.
In the present invention, the total addition amount of the developing agent and the reducing agent is from 0.1 to 20 mol, preferably from 0.1 to 10 mol per mol of silver.
As the coupler for use in the present invention, a 4-equivalent coupler or a 2-equivalent coupler may be properly used depending upon the kind of the developing agent. Specific examples of the coupler, both the 4-equivalent coupler and the 2-equivalent coupler, are described in detail in T. H. James (compiler), Theory of the Photographic Process, 4th ed., pages 291 to 334 and pages 354 to 361, Macmillan (1977), JP-A-58-12353, JP-A-58-149046, JP-A-58-149047, JP-A-59-11114, JP-A-59-124399, JP-A-59-174835, JP-A-59-231539, JP-A-59-231540, JP-A-60-2951, JP-A-60-14242, JP-A-60-23474, JP-A-60-66249 and patents and publications cited therein.
The hydrophobic additive such as coupler, developing agent and non-diffusible reducing agent can be introduced into a layer of the light-sensitive material by a known method such as the method described in U.S. Pat. No. 2,322,027. In this case, a high boiling point as described in U.S. Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476 and 4,599,296 and JP-B-3-62256 may be used, if desired, in combination with a low boiling point organic solvent having a boiling point of from 50 to 160.degree. C. The dye donating compounds, the non-diffusible reducing agents or the high-boiling point organic solvents may be used in combination of two or more thereof.
The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, more preferably from 0.1 to 1 g, per g of the hydrophobic additive used. Further, it is suitably 1 ml or less, preferably 0.5 ml or less, more preferably 0.3 ml or less, per g of the binder.
The dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943 or the method of forming a fine particle dispersion and adding it described in JP-A-62-30242 may also be used.
In the case of a compound substantially insoluble in water, other than the above-described methods, the compound may be dispersed and contained in the binder after forming it into fine particle.
In dispersing a hydrophobic compound in hydrophilic colloid, various surface active agents may be used. Examples thereof include those described as the surface active agent in JP-A-59-157636, pages (37) and (38), and the above-described Research Disclosure. Further, phosphoric ester type surface active agents described in Japanese Patent Application Nos. 5-204325 (JP-A-5-204325) and 6-19247 (JP-A-7-228589) and West German Patent Publication (OLS) No. 1,932,299A may also be used.
In the present invention, the light-sensitive material may contain a compound capable of achieving activation of development and at the same time, stabilization of the image. Specific preferred examples of the compound include those described in U.S. Pat. No. 4,500,626, columns 51 and 52.
The light-sensitive material may have various light-insensitive layers such as a protective layer, an undercoat layer, an interlayer, a yellow filter layer and an antihalation layer, between the above-described silver halide emulsion layers or as the uppermost layer or the lowermost layer. On the opposite side of the support, various auxiliary layers such as a back layer may be provided. More specifically, the layer structure as described in U.S. Pat. No. 4,500,626 may be used, or an undercoat layer as described in U.S. Pat. No. 5,051,335, an interlayer having a solid pigment as described in JP-A-1-167838 and JP-A-61-20943, an interlayer having a reducing agent or a DIR compound as described in JP-A-1-120553, JP-A-5-34884 and JP-A-2-64634, an interlayer having an electron transferring agent as described in U.S. Pat. Nos. 5,017,454 and 5,139,919 and JP-A-2-235044, a protective layer having a reducing agent as described in JP-A-4-249245 or a layer comprising a combination of these layers, may be provided.
The dyestuff which can be used in the yellow filter layer or the antihalation layer is preferably a dyestuff capable of decoloring or dissolving out at the time of development and having no contribution to the density after processing.
The term "a dyestuff in the yellow filter layer or the antihalation layer decolors or is removed at the time of development" means that the amount of the dyestuff remaining after processing is reduced to 1/3 or less, preferably 1/10 or less of the amount immediately before coating. The dyestuff component may dissolve out from the light-sensitive material or transfer into the processing material during development or may react upon development to turn into a colorless compound.
The dyestuff which can be used in the light-sensitive material of the present invention may be a known dyestuff. Examples thereof include a dyestuff which dissolves in alkali of the developer and a dyestuff which reacts with the component in the developer, with the sulfite ion or developing agent, or with the alkali to decolor.
Specific examples thereof include dyestuffs described in EP 549489A and Dyestuffs ExF2 to ExF6 described in JP-A-7-152129. A solid disperse dyestuff as described in Japanese Patent Application No. 6-259805 (JP-A-8-101487) may also be used. This dyestuff may be used in the case where the light-sensitive material is developed with a processing solution, however, it is preferably used in the case where the light-sensitive material is heat developed using a processing sheet which will be described later.
The dyestuff may be mordanted to a mordanting agent and a binder. In this case, the mordanting agent and the dyestuff each may be one known in the photographic field, and examples of the mordanting agent include mordanting agents described in U.S. Pat. No. 4,500,626 (columns 58 and 59), JP-A-61-88256 (pages 32 to 41), JP-A-62-244043 and JP-A-62-244036.
Further, a compound which releases a diffusible dye upon reaction with a reducing agent may be used together with a reducing agent, whereby a movable dye is released in alkali during development and removed by dissolving out into a processing solution or transferring to the processing sheet. Specific examples of the compound include those described in U.S. Pat. Nos. 4,559,290 and 4,783,369, EP 220746A2, JIII Journal of Technical Disclosure No. 87-6119 and Japanese Patent Application No. 6-259805 (paragraph Nos. 0080 and 0081; corresponding to JP-A-8-101487).
A leuco dye which decolors may also be used and JP-A-1-150132 specifically discloses a silver halide light-sensitive material containing a leuco dye previously colored by an organic acid metal salt developer. The leuco dye and the developer complex decolor upon heating or reaction with an alkali agent and accordingly, in the case where the light-sensitive material is heat developed in the present invention, the combination of a leuco dye and a developer is preferred.
The leuco dye used may be a known one and it is described in Moriga and Yoshida , Senryo to Yakuhin (Dyestuff and Chemicals), 9, page 84, Kaseihin Kogyo Kyokai, Shin-pan Senryo Binran (New Version of Dyestuff Handbook), page 242, Maruzen (1970), R. Garner, Reports on the Process of Appl. Chem., 56, page 199 (1971), Senryo to Yakuhin (Dyestuff and Chemicals), 19, page 230, Kaseihin Kogyo Kyokai (1974), Shikizai (Coloring Materials), 62, page 288 (1989), and Senryo Kogyo (Dyestuff Engineering), 32, 208.
The developer is preferably an acid clay-base developer, a phenolformaldehyde resin or an organic acid metal salt. The organic acid metal salt is preferably a metal salt of salicylic acids, a metal salt of phenol-salicylic acid-formaldehyde resin, a rhodanate or a metal salt of xanthate, and the metal is preferably zinc. Out of the above-described developer, with respect to the oil-soluble zinc salicylate, those described in U.S. Pat. Nos. 3,864,146 and 4,046,941 and JP-B-52-1327 may be used.
The light-sensitive material of the present invention is preferably hardened by a hardening agent.
Examples of the hardening agent include hardening agents described in U.S. Pat. Nos. 4,678,739 (column 41) and 4,791,042, JP-A-59-116655, JP-A-62-245261, JP-A-61-18942 and JP-A-4-218044. Specific examples thereof include an aldehyde-base hardening agent (e.g., aldehyde), an aziridine-base hardening agent, an epoxy-base hardening agent, a vinylsulfone-base hardening agent (e.g., N,N'-ethylenebis(vinylsulfonyl-acetamido)ethane), an N-methylol-base hardening agent (e.g., dimethylolurea), a boric acid, a metaboric acid and a high molecular hardening agent (e.g., compounds described in JP-A-62-234157, etc.).
The hardening agent is used in an amount of from 0.001 to 1 g, preferably from 0.005 to 0.5 g, per g of the hydrophilic binder.
The light-sensitive material may contain an antifoggant, a photographic stabilizer or a precursor thereof. Specific examples thereof include the compounds described in the above-described Research Disclosure, U.S. Pat. Nos. 5,089,378, 4,500,627 and 4,614,702, JP-A-64-13564 (pages (7) to (9), pages (57) to (71) and pages (81) to (97)), U.S. Pat. Nos. 4,775,610, 4,626,500 and 4,983,494, JP-A-62-174747, JP-A-62-239148, JP-A-1-150135, JP-A-2-110557, JP-A-2-178650 and RD No. 17643 (1978), pages (24) to (25).
The compound is preferably used in an amount of from 5.times.10.sup.-6 to 1.times.10.sup.-1 mol, more preferably from 1.times.10.sup.-5 to 1.times.10.sup.-2 mol, per mol of silver.
The light-sensitive material of the present invention is, after exposure, developed by supplying water corresponding to from 1/10 to 1 times the water necessary for giving maximum swelling of all coated layers constituting the light-sensitive material and the processing material, laminating the light-sensitive material on the processing material containing a base and/or a base precursor, and heating the materials.
The present invention has an object of achieving good graininess and wide exposure latitude in the above-described heat development and is intended to lighten the load on environment to be imposed in liquid development. However, the light-sensitive material of the present invention may be developed by an activator method using an alkali processing solution or with a processing solution containing a developing agent and a base to form an image.
Heat treatment of a light-sensitive material is known in this technical field, and the heat-developable light-sensitive material and the process therefor are described, for example, in Shashin Kogaku no Kiso (Primary Study of Photographic Industry), pages 553 to 555, Corona Sha (1970), Eizo Joho (Image Information), page 40 (April 1978), Nabletts Handbook of Photography and Reprography, 7th ed., pages 32 to 33, Vna Nostrand and Reinhold Company, U.S. Pat. Nos. 3,152,904, 3,301,678, 3,392,020 and 3,457,075, British Patents 1,131,108 and 1,167,777, and Research Disclosure (RD-17029), pages 9 to 15 (June 1978).
The activator processing is a processing method of developing a light-sensitive material self-containing a color developing agent with a processing solution containing no color developing agent. In this case, the processing solution is characterized by containing no color developing agent which is contained in usual development processing solution components, and may contain other components (for example, alkali or auxiliary developing agent). Examples of the activator processing are described in known publications such as EP 545491A1 and EP 565165A1.
The method of developing a light-sensitive material with a processing solution containing a developing agent and a base is described in RD No. 17643, pages 28 and 29, ibid. No. 18716, page 651, left to right columns, and ibid., No. 307105, pages 880 and 881.
The processing raw materials and the processing method for use in the present invention in the case of heat development processing are described in detail below.
In the light-sensitive material of the present invention, a base or a base precursor is preferably used for the purpose of accelerating silver development and dye formation reaction. Examples of the base precursor include a salt of a base with an organic acid capable of decarboxylation by heat and a compound which releases an amine by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. Specific examples thereof are described in U.S. Pat. Nos. 4,514,493 and 4,657,848 and Kochi Gijutu (Known Techniques), No. 5, Aztec Limited (Mar. 22, 1991). Also, a method of generating a base by the combination of a sparingly water-soluble basic metal compound with a compound capable of complex formation reaction with the metal ion constituting the basic metal compound using water as a medium, may also be used.
The amount of the base or the base precursor used is from 0.1 to 20 g/m.sup.2, preferably from 1 to 10 g/m.sup.2.
The light-sensitive material of the present invention may contain a heat solvent for the purpose of accelerating heat development. Examples thereof include organic compounds having polarity as described in U.S. Pat. Nos. 3,347,675 and 3,667,959. Specific examples thereof include amide derivatives (e.g., benzamide), urea derivatives (e.g., methylurea, ethyleneurea), sulfonamide derivatives (e.g., compounds described in JP-B-1-40974 and JP-B-4-13701), polyol compounds, sorbitols and polyethylene glycols.
When the heat solvent is water insoluble, it is preferably used as a solid dispersion. The layer to which the heat solvent is added may be either a light-sensitive layer or a light-insensitive layer depending on the purpose.
The addition amount of the heat solvent is from 10 to 500 wt %, preferably from 20 to 300 wt %, of the binder in the layer to which the heat solvent is added.
The heating temperature in the heat development process may be from about 50 to 250.degree. C., preferably from 60 to 100.degree. C. The developing time may be 3 to 100 seconds, and the heating time is preferably 5 to 60 seconds.
In order to feed the base necessary in the heat development process, a processing material having a processing layer containing a base or a base precursor is used. The processing material may have additional functions of shielding air at the heat development, preventing volatilization of raw materials from the light-sensitive material, feeding materials for the processing other than the base to the light-sensitive material, or removing materials (e.g., YF dyestuff, AH dyestuff) in the light-sensitive material which become unnecessary after the development or unnecessary components generated during the development. The support and the binder of the processing material may be the same as those used in the light-sensitive material.
The processing material may contain a mordanting agent for the purpose of removing the dyestuff as described above.
The mordanting agent used may be a mordanting agent known in the photographic field and examples thereof include the mordanting agents described in U.S. Pat. No. 4,500,626, columns 58 and 59, JP-A-61-88256, pages 32 to 41, JP-A-62-244043 and JP-A-62-244036. A dye acceptable high molecular compound described in U.S. Pat. No. 4,463,079 may also be used. Further, the processing material may contain the above-described heat solvent.
The processing material contains a base or a base precursor in the processing layer. The base may be either an organic base or an inorganic base. Examples of the base precursor which can be used include those described above. The amount of the base or the base precursor used is from 0.1 to 20 g/m.sup.2, preferably from 1 to 10 g/m.sup.2.
In performing heat development using a processing material, a slight amount of water is used for the purpose of accelerating development, accelerating transfer of the material for processing or accelerating diffusion of unnecessary matters. This is specifically described in U.S. Pat. Nos. 4,704,245 and 4,470,445, and JP-A-61-238056. The water may contain an inorganic alkali metal salt, an organic base, a low boiling point solvent, a surface active agent, an antifoggant, a complex forming compound with a sparingly soluble metal salt, a fungicide or a bactericide.
The water may be any water commonly used. More specifically, distilled water, tap water, well water or mineral water may be used. In the heat development apparatus using the light-sensitive material and the processing material of the present invention, the water may be used up or may be circulated and repeatedly used. In the latter case, water used contains components dissolved out from the light-sensitive material. Apparatuses and water described in JP-A-63-144354, JP-A-63-144355, JP-A-62-38460 and JP-A-3-210555 may also be used.
The water may be fed to the light-sensitive material, the processing material or both of them. The water is used in an amount corresponding to from 1/10 to 1 times the amount necessary for giving maximum swelling of all coated layers (excluding the back layer) of the light-sensitive material and the processing material.
The timing for providing water may be anytime after exposing the light-sensitive material and before the heat-development, preferably just before the heat-development.
The above water amount defined in the present invention defines the water amount necessiated at the heat-development after attaching the light-sensitive material to the processing material. Accordingly, for example, after supplying water more than the water amount defined above to the light-sensitive material or the processing material, an excess amount of water may be removed by e.g., squeegeeing until the light-sensitive material and the processing material are attached to each other, and then the heat development may be conducted. This method may be also within the scope of the present invention.
Normally, the light-sensitive material and the processing material are attached to each other after supplying the necessiated water to one of the light-sensitive material and the processing material or both of them, or after controlling the necessiated water with the means described above, and then the heat development is conducted; however, after attaching the light-sensitive material to the processing material, water may be supplied to the gap between the light-sensitive material and the processing material, whereby the necessiated water exists.
A variety of methods for providing water content may be used in the present invention. An example of the method for providing water includes a method comprising immersing the light-sensitive material or the processing material to water and removing an excess amount of water with a squeegee roller. In this case, the constant amount of water is preferably provided to the light-sensitive material or the procssing material in the disposable form. A particularly preferred method for jetting water is a method using a water coat apparatus similar to an ink-jet type recoring head comprising a nozzle wherein a plurality of nozzle holes for jetting water are arranged in a straight line or in a plurality of lines at definite intervals along a direction to intersect a conveying direction of the light-sensitive material or the processing material, and an actuator for displacing said nozzle toward the light-sensitive material or the processing material on the conveying path. A method for coating water with e.g., sponge is preferably used because of the simplicity of apparatus.
In feeding the water, the methods described, for example, in JP-A-62-253159, page (5), and JP-A-63-85544 are preferably used. Also, a solvent may be enclosed in a microcapsule or previously incorporated in the form of a hydrate into the light-sensitive material, the processing material or both of them.
The temperature of water fed may be from 30 to 60.degree. C. as described in JP-A-63-85544.
In performing heat development in the presence of a slight amount of water, use of a method of generating a base by a combination of a sparingly water-soluble basic metal compound with a compound capable of complex formation reaction with the metal ion constituting the basic metal compound using water as a medium is effective as described in European Unexamined Patent Publication 210660 and U.S. Pat. No. 4,740,445. In this case, in view of stock storability, the sparingly water-soluble basic metal compound is preferably added to the light-sensitive material and the complex forming compound is preferably added to the processing material.
The heating method in the development process includes a method of contacting with a heated block or plate, a method of contacting with a hot plate, a hot presser, a heat roller, a heat drum, a halogen lamp heater or an infrared or far infrared lamp heater, and a method of passing through a high temperature atmosphere.
For attaching the light-sensitive material and the processing material so that the light-sensitive layer and the processing layer face to each other, the methods described in JP-A-62-253159 and JP-A-61-147244, page (27) may be used. The heating time is preferably from 3 to 100 seconds, most preferably 5 to 60 seconds.
In processing the photographic elements of the present invention, any of various heat development apparatuses may be used. For example, apparatuses described in JP-A-59-75247, JP-A-59-177547, JP-A-59-181353, JP-A-60-18951, JP-U-A-62-25944 (the term "JP-U-A" as used herein means an "unexamined published Japanese utility model application"), Japanese Patent Application Nos. 4-277517 (JP-A-6-130509), 4-243072 (JP-A-6-95338), 4-244693 (JP-A-6-95267), 6-164421 (JP-A-8-29955) and 6-164422 (JP-A-8-29954) are preferably used.
Examples of commercially available apparatuses which can be used in the present invention include Pictrostat 100, Pictrostat 200, Pictrostat 300, Pictrostat 330, Pictrostat 50, Pictrography 3000 and Pictrography 2000, all manufactured by Fuji Photo Film Co., Ltd.
The light-sensitive material or the processing sheet of the present invention may be in the form having an electrically conductive heating element layer as a heating means for heat development. As the heating element, those described in JP-A-61-145544 may be used.
In the present invention, image information may be taken in without removing developed silver generated by the development or undeveloped silver halide, however, an image may be taken in after removing them. In the latter case, a means for removing them simultaneously with or after the development may be used.
In order to remove developed silver in the light-sensitive material simultaneously with development, to convert silver halide into a complex or to solubilize silver halide, the processing material may contain an oxidizing agent for silver or a rehalogenating agent, which acts as a bleaching agent, or a silver halide solvent which acts as a fixing agent, so that it can cause reaction on heat development.
Further, a second material containing an oxidizing agent for silver, a rehalogenating agent or a silver halide solvent may be laminated on the light-sensitive material after completion of development in the image formation, to remove developed silver, to convert silver halide into a complex or to solubilize silver halide.
In the present invention, the above-described treatment is preferably applied to such a degree that no obstacle arises to the reading of image information after photographing and development in the subsequent image formation. In particular, undeveloped silver halide generates high haze in the gelatin layer to increase the background density of an image and therefore, the above-described complex forming agent is preferably used to reduce haze or solubilize and then remove wholly or partly the undeveloped silver halide from the layer. Further, in order to reduce haze of the silver halide itself, tabular grains having a high aspect ratio or having a high silver chloride content may also be preferably used.
The bleaching agent which can be used in the processing material of the present invention may be any silver bleaching agent commonly used. Such a bleaching agent is described in U.S. Pat. Nos. 1,315,464 and 1,946,640, and Photographic Chemistry, Vol. 2, Chapter 30, Foundation Press, London, England. The bleaching agent effectively oxidizes and then solubilizes the photographic silver image. Useful examples of the silver bleaching agent include an alkali metal bichromate and an alkali metal ferricyanide.
The bleaching agent is preferably soluble in water and examples thereof include ninhydrine, indanedione, hexaketo-cyclohexane, 2,4-dinitrobenzoic acid, benzoquinone, benzene-sulfonic acid and 2,5-dinirobenzoic acid. A metal organic complex such as a ferric salt of cyclohexyldialkylamino-tetraacetic acid, a ferric salt of ethylenediaminetetraacetic acid and a ferric salt of citric acid may also be used. As the fixing agent, the above-described silver halide solvent which can be incorporated into the processing material (first processing material) for developing the light-sensitive material, may be used. The binder, the support and other additives which can be used in the second processing material may be the same as used in the first processing material.
The amount of the bleaching agent coated should be varied depending on the amount of silver contained in the light-sensitive material to be processed, however, it is, based on the coated silver amount per unit area of the light-sensitive material, from 0.01 to 10 mol/mol-coated silver of light-sensitive material, preferably from 0.1 to 3 mol/mol-coated silver of light-sensitive material, more preferably from 0.1 to 2 mol/mol-coated silver of light-sensitive material.
The silver halide solvent used may be a known silver halide solvent. Examples thereof include thiosulfate such as sodium thiosulfate and ammonium thiosulfate, sulfites such as sodium sulfite and sodium hydrogensulfite, thiocyanates such as potassium thiocyanate and ammonium thiocyanate, thioether compounds such as 1,8-di-3,6-dithiaoctane, 2,2'-thiodiethanol and 6,9-dioxa-3,12-dithiatetradecan-1,14-diol described in JP-B-47-11386, compounds having a 5- or 6-membered ring such as uracil and hydantoin described in Japanese Patent Application No. 6-325350, and the compound represented by the following formula (I) described in JP-A-53-144319. Mesoionthiolate compounds such as trimethyltriazolium thiolate described in Analytica Chemica Acta, Vol. 248, pages 604 to 614 (1991) are also preferred. The compound capable of fixing and stabilizing silver halide described in Japanese Patent Application No. 6-206331 (JP-A-8-69097) can also be used as the silver halide solvent.
N(R.sup.1)(R.sup.2)--C(.dbd.S)--X--R.sup.3 (I)
wherein X represents a sulfur atom or an oxygen atom, R.sup.1 and R.sup.2, which may be the same or different, each represents an aliphatic group, an aryl group, a heterocyclic residue or an amino group, R.sup.3 represents an aliphatic group or an aryl group, and R.sup.1 and R.sup.2 or R.sup.2 and R.sup.3 may be combined to each other to form a 5- or 6-membered heterocyclic ring. The above-described silver halide solvent may be used in combination.
Among the compounds described above, sulfites and compounds having a 6-membered imide ring such as uracil and hydantoin are preferred. In particular, uracil or hydantoin is preferably added in the form of a potassium salt because reduction in the gloss during storage of the processing material can be improved.
The amount of all silver halide solvents contained in the processing layer is from 0.01 to 100 mmol/m.sup.2, preferably from 0.1 to 50 mmol/m.sup.2, more preferably from 10 to 50 mmol/m.sup.2, and in terms of molar ratio to the coated silver amount of the light-sensitive material, from 1/20 to 20 times, preferably from 1/10 to 10 times, more preferably from 1/3 to 3 times. The silver halide solvent may be added to a solvent such as water, methanol, ethanol, acetone, dimethylformamide or methylpropyl glycol or an alkaline or acidic aqueous solution. Or, it may be formed into a solid fine particle dispersion and added to the coating solution.
Further, physical developing nuclei and a silver halide solvent may be contained in the processing material so that the silver halide in the light-sensitive material can be solubilized at the same time with development and fixed to the processing layer.
The physical developing nuclei are to reduce a soluble silver salt diffused out from the light-sensitive material to convert into a physical developed silver and fix it to the processing layer. As the physical developing nuclei, any known physical developing nuclei may be used and examples thereof include a heavy metal such as zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper and ruthenium, a noble metal such as palladium, platinum, silver and gold, and colloid particles thereof of a chalcogen compound such as sulfuric acid, selenium or tellurium. The physical developing nuclei substance can be obtained by reducing a corresponding metal ion with a reducing agent such as ascorbic acid, sodium boron hydride or hydroquinone to form a metal colloid dispersion or by mixing a corresponding metal ion with a soluble sulfide, selenide or telluride solution to form a colloid dispersion of water-insoluble metal sulfide, metal selenide or metal telluride. The dispersion is preferably formed in a hydrophilic binder such as gelatin. The preparation method of colloidal silver particles is described in U.S. Pat. No. 2,688,601. If desired, desalting known to the preparation method of a silver halide emulsion may be performed for removing excessive salts.
The physical developing nuclei preferably have a particle size of from 2 to 200 nm.
The physical developing nuclei are contained in the processing layer in an amount of usually from 10.sup.-3 to 100 mg/m.sup.2, preferably from 10.sup.-2 to 10 mg/m.sup.2.
The physical developing nuclei may be separately prepared and added to the coating solution, however, it may also be formed by reacting, for example, silver nitrate with sodium sulfide, or gold chloride with a reducing agent or the like, in a coating solution containing a hydrophilic binder.
The physical developing nuclei are preferably silver, silver sulfide or palladium. In the case where the physical developed silver transferred to the complex forming agent sheet is used as an image, palladium sulfide and silver sulfide are preferred because Dmin is reduced and Dmax is high.
The first processing material and the second processing material each may have at least one polymerizable timing layer.
The polymerizable timing layer can temporarily delay the bleaching/fixing reaction until reaction of the desired silver halide with a dye donative compound or a developing agent substantially completes. The timing layer may comprise gelatin, polyvinyl alcohol or polyvinyl alcohol-polyvinyl acetate. This layer may also be a barrier timing layer as described, for example, in U.S. Pat. Nos. 4,056,394, 4,061,496 and 4,229,516.
In the case of coating the timing layer, it may be coated to have a thickness of from 5 to 50 .mu.m, preferably from 10 to 30 .mu.m.
In the present invention, for bleaching/fixing a developed light-sensitive material using the second processing material, water in an amount corresponding to from 0.1 to 1 times the amount necessary for achieving maximum swelling of all coated layers excluding the back layer, of both the light-sensitive material and the second processing material is supplied to the light-sensitive material or the second processing material, the light-sensitive material and the second processing material are superposed so that the light-sensitive layer and the processing layer can face to each other, and these materials are preferably heated at a temperature of from 60 to 100.degree. C. for from 5 to 60 seconds.
The amount and the kind of water, the method of supplying water and the method of superposing the light-sensitive material on the processing material may be the same as those described with respect to the first processing material.
More specifically, the bleaching/fixing sheet described in JP-A-59-136733, U.S. Pat. No. 4,124,398 and JP-A-55-28098 may be used.
The light-sensitive material may use various surface active agents as a coating aid or for the purpose of improving releasability, improving slipperiness, preventing electrification or accelerating development. Specific examples of the surface active agent are described in Kochi Gijutu (Known Techniques), No. 5, pages 136 to 138, Aztec Limited (Mar. 22, 1991), JP-A-62-173463 and JP-A-62-183457.
The light-sensitive material may contain an organic fluoro compound for the purpose of preventing slipperiness, inhibiting electrification or improving releasability. Representative examples of the organic fluoro compound include fluorine-base surface active agents described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20944 and JP-A-62-135826, and hydrophobic fluorine compounds such as an oily fluorine-base compound (e.g., fluorine oil) and a solid fluorine compound resin (e.g., tetraethylene fluoride resin).
The light-sensitive material preferably has slipperiness. A slipping agent-containing layer is preferably provided on both the light-sensitive layer surface and the back surface. The slipperiness is preferably, in terms of coefficient of dynamic friction, from 0.01 to 0.25. This value is determined by transporting the light-sensitive material at a speed of 60 cm/min (25.degree. C., 60% RH) against a stainless steel ball having a diameter of 5 mm. In this evaluation, even when the other party is changed to the light-sensitive layer surface, the value almost on the same level is obtained.
Examples of the slipping agent which can be used include polyorganosiloxane, a higher fatty acid amide, a higher fatty acid metal salt and an ester of a higher fatty acid with a higher alcohol. Examples of the polyorganosiloxane include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane and polymethylphenylsiloxane. The layer to which the slipping agent is added is preferably an outermost layer of the emulsion layer or a back layer. In particular, polydimethylsiloxane and an ester having a long chain alkyl group are preferred.
In the present invention, an antistatic agent is preferably used. Examples of the antistatic agent include a carboxylic acid, a carboxylate, a polymer containing sulfonate, a cationic polymer and ionic surface active agent compound.
Most preferred antistatic agents are a fine particle of at least one crystalline metal oxide having a volume resistivity of 10.sup.7 .OMEGA..multidot.cm or less, more preferably 10.sup.5 .OMEGA..multidot.cm or less, and a particle size of from 0.001 to 1.0 .mu.m, selected from ZnO, TiO.sub.2, SnO.sub.2, Al.sub.2 O.sub.3, In.sub.2 O.sub.3, SiO.sub.2, MgO, BaO, MoO.sub.3 and V.sub.2 O.sub.5 or of a composite oxide thereof (e.g., Sb, P, B, In, S, Si, C) and a fine particle of a sol-like metal oxide or of a composite oxide thereof. The content of the antistatic agent in the light-sensitive material is preferably from 5 to 500 mg/m.sup.2, more preferably from 10 to 350 mg/m.sup.2. The weight ratio of the electrically conductive crystalline oxide or a composite oxide thereof to the binder is preferably from 1/300 to 100/1, more preferably from 1/100 to 100/5.
In the construction (including a back layer) of the light-sensitive material or the processing sheet, various polymer latexes may be contained for the purpose of improving physical properties of the layer, such as dimensional stabilization or prevention of curling, adhesion, cracking of layers or reduction/increase in sensitivity due to pressure. Specific examples of the polymer latex include those described in JP-A-62-245258, JP-A-62-136648 and JP-A-62-110066. In particular, when a polymer latex having a low glass transition point (40.degree. C. or lower) is used in a mordant layer, cracking of the mordant layer can be prevented, whereas when a polymer latex having a high glass transition point is used in a back layer, a curl-preventing effect can be provided.
The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be used either on the emulsion surface or the back surface, but it is particularly preferably added to the outermost layer on the emulsion layer side. The matting agent may be either soluble in the processing solution or insoluble in the processing solution, and both are preferably used in combination. Preferred examples thereof include polymethyl methacrylate, poly(methyl methacrylate/methacrylic acid=9/1 or 5/5 (by mol)) and polystyrene particles. The particle size is preferably from 0.8 to 10 .mu.m, the particle size distribution is preferably narrower, and 90% by number or more of all particles have a size between 0.9 and 1.1 times the average particle size. In order to increase the matting property, fine particles of 0.8 .mu.m or less are preferably added at the same time and examples thereof include polymethyl methacrylate (0.2 .mu.m), poly(methyl methacrylate/methacrylic acid=9/1 (by mol), 0.3 .mu.m)., polystyrene particles (0.25 .mu.m) and colloidal silica (0.03 .mu.m).
Specific examples of the matting agent include the compounds described in JP-A-61-88256 (page (29)), 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, and the compounds described in the above-described Research Disclosure.
In the present invention, the light-sensitive material and the processing sheet each uses a support capable of withstanding the processing temperature. In general, a photographic support such as paper and synthetic polymer (film) described in Nippon Shashin Gakkai (compiler), Shashin Kogaku no Kiso --Gin'en Sashin Hen-- (Primary Study of Photographic Engineering --Silver Salt Photograph--), pages (223) to (240), Corona Sha (1979) is used. Specific examples thereof includes polyethylene terephthalate, polyethylene naphthalate, polycarbonates, polyvinyl chloride, polystyrene, polypropylene, polyimide and celluloses (e.g., triacetyl cellulose).
These each may be used alone or may be used as a support laminated on one surface or both surfaces thereof by a synthetic polymer such as polyethylene.
In addition, supports described in JP-A-62-253159 (pages (29) to (31)), JP-A-1-161236 (pages (14) to (17)), JP-A-63-316848, JP-A-2-22651, JP-A-3-56955 and U.S. Pat. No. 5,001,033 may also be used.
In the case where requirement for heat durability or curling property is severe, the supports described in JP-A-6-41281, JP-A-6-43581, JP-A-6-51426, JP-A-6-51437, JP-A-6-51442 and Japanese Patent Application Nos. 4-251845 (corresponding to JP-A-6-82961), 4-231825 (corresponding to JP-A-6-82960), 4-253545 (corresponding to JP-A-6-123937), 4-258828 (corresponding to JP-A-6-82959), 4-240122 (corresponding to JP-A-6-67346), 4-221538 (corresponding to U.S. Pat. No. 5,326,689), 5-21625 (JP-A-6-266050), 5-15926 (corresponding to JP-A-6-202277), 4-331928 (corresponding to JP-A-6-175282), 5-199704 (corresponding to U.S. Pat. No. 5,326,689), 6-13455 (corresponding to JP-A-7-219129) and 6-14666 (corresponding to JP-A-7-219144) may be preferably used as the support for the light-sensitive material.
A support of a styrene-base polymer mainly having a syndiotactic structure may also be preferably used.
Surface treatment is preferably performed so that the support can be bonded to the light-sensitive constituent layer. Examples thereof include surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet light treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these surface treatments, preferred are ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment.
The undercoating method is described below. The undercoat layer may comprise a single layer or two or more layers. The binder for the undercoat layer includes a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid and maleic anhydride, and in addition, polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose and gelatin. The compound which swells the support include resorcinol and p-chlorophenol. The undercoat layer may contain a gelatin hardening agent and examples thereof include chromium salts (e.g., chromium alum), aldehydes (e.g., formaldehyde, glutaraldehyde), isocyanates, active halogen compounds (e.g., 2,4-dichloro-6-hydroxy-s-triazine), epichlorohydrin resins and active vinyl sulfone compounds. Further, the undercoat layer may contain SiO.sub.2, TiO.sub.2, an inorganic fine particle or a polymethyl methacrylate copolymer fine particle (0.01 to 10 .mu.m) as a matting agent.
A support having a magnetic recording layer described, for example, in JP-A-4-124645, JP-A-5-40321, JP-A-6-35092 and Japanese Patent Application No. 5-106979 (JP-A-6-317875) is preferably used to record photographing information or the like.
The magnetic recording layer is provided by coating an aqueous or organic solvent-base coating solution containing a binder having dispersed therein magnetic particles, on a support.
The magnetic particle which can be used includes ferromagnetic iron oxide (e.g., .gamma.Fe.sub.2 O.sub.3), Co-doped .gamma.Fe.sub.2 O.sub.3, Co-doped magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite and Ca ferrite. Among these, Co-doped ferromagnetic iron oxide such as Co-doped .gamma.Fe.sub.2 O.sub.3 is preferred. The shape of the magnetic particle may be any of acicular, rice grain-like, spherical, cubic and platy forms. The specific surface area as S.sub.BET is preferably 20 m.sup.2 /g or more, more preferably 30 m.sup.2 /g or more. The saturation magnetization (as) of the ferromagnetic material is preferably from 3.0.times.10.sup.4 to 3.0.times.10.sup.5 A/m, more preferably from 4.0.times.10.sup.4 to 2.5.times.10.sup.5 A/m. The ferromagnetic particle may be subjected to surface treatment with silica and/or alumina or with an organic material. Further, the magnetic particle may be subjected to surface treatment with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also, a magnetic particle having coated on the surface thereof an inorganic or organic material described in JP-A-4-259911 and JP-A-5-81652 may be used.
The binder for use in the magnetic particle includes a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, alkali or biodegradable polymer, a natural polymer (e.g., cellulose derivative, saccharide derivative) and a mixture thereof described in JP-A-4-219569. The above-described resin has a Tg of from -40.degree. C. to 300.degree. C. and a weight average molecular weight of from 2,000 to 1,000,000. Examples of the resin include a vinyl-base copolymer, a cellulose derivative such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate and cellulose tripropionate, an acrylic resin and a polyvinyl acetal resin, and gelatin is also preferably used. Among these, cellulose di(tri)acetate is preferred. The binder may be cured by adding thereto an epoxy-base, aziridine-base or isocyanate-base crosslinking agent. Examples of the isocyanate-base crosslinking agent include isocyanates such as tolylenediisocyanate, 4,4'-diphenylmethanediisocyanate, hexamethylenediisocyanate and xylylenediisocyanate, a reaction product of the isocyanate described above with polyalcohol (e.g., a reaction product of 3 mol of tolylenediisocyanate with 1 mol of trimethylolpropane) and a polyisocyanate produced by condensation of these isocyanates, which are described, for example, in JP-A-6-59357.
The magnetic material is dispersed in the above-described binder by the method preferably using a kneader, a pin-type mill or an annular-type mill as described in JP-A-6-35092 and these may also be preferably used in combination. The dispersant described in JP-A-5-088283 and other known dipersants may be used. The thickness of the magnetic recording layer is from 0.1 to 10 .mu.m, preferably from 0.2 to 5 .mu.m, more preferably from 0.3 to 3 .mu.m. The weight ratio of the magnetic particle to the binder is preferably from 0.5:100 to 60:100, more preferably from 1:100 to 30:100. The coating amount of magnetic particles is from 0.005 to 3 g/m.sup.2, preferably from 0.01 to 2 g/m.sup.2, more preferably from 0.02 to 0.5 g/m.sup.2. The magnetic recording layer preferably has a transmission yellow density of from 0.01 to 0.50, more preferably from 0.03 to 0.20, still more preferably from 0.04 to 0.15. The magnetic recording layer may be provided throughout the surface of or stripedly on the back surface of the photographic support by coating or printing. The magnetic recording layer can be coated by using air doctor, blade, air knife, squeeze, impregnation, reverse roller, transfer roller, gravure, kiss, cast, spray, dip, bar or extrusion, and the coating solution described in JP-A-5-341436 is preferred.
The magnetic recording layer may be designed to have functions such as improvement of lubricity, control of curl, prevention of electrification, inhibition of adhesion or head abrasion, or other functional layers may be provided to undertake these functions. At least one or more of particles is preferably an abrasive of an aspheric inorganic particle having a Mhos' hardness of 5 or more. The composition of the aspheric inorganic particle is preferably an oxide such as aluminum oxide, chromium oxide, silicon dioxide or titanium dioxide, a carbide such as silicon carbide or titanium carbide, or a fine particle of diamond. The abrasive may be subjected to surface treatment with a silane coupling agent or a titanium coupling agent. The particle may be added to a magnetic recording layer or may be overcoated on the magnetic recording layer (for example, as a protective layer or a lubricant layer). The binder used here may be one selected from those described above and it is preferably the same as the binder in the magnetic recording layer. The light-sensitive material having a magnetic recording layer is described in U.S. Pat. Nos. 5,336,589, 5,250,404, 5,229,259 and 5,215,874 and European Patent 466130.
The polyester support which is preferably used in a light-sensitive material having the above-described magnetic recording layer is described below, however, details including the light-sensitive material, the processing, the cartridge and the experimental examples are described in JIII Journal of Technical Disclosure No. 94-6023, Japan Institute of Invention and Innovation (Mar. 15, 1994). The polyester is formed using a diol and an aromatic dicarboxylic acid as essential components. Examples of the aromatic dicarboxylic acid include 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, terephthalic acid, isophthalic acid and phthalic acid, and examples of the diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A and bisphenol. The polymer includes a homopolymer such as polyethylene terephthalate, polyethylene naphthalate and polycyclohexanedimethanol terephthalate. Among these, preferred is a polyester containing from 50 to 100 mol % of 2,6-naphthalenedicarboxylic acid. Particularly preferred is polyethylene 2,6-naphthalate. The average molecular weight is approximately from 5,000 to 200,000. The polyester preferably has a Tg of 50.degree. C. or higher, more preferably 90.degree. C. or higher.
The polyester support is subjected to heat treatment to become difficult of having curling habit, at a heat treatment temperature of from 40.degree. C. to less than the Tg, more preferably from (Tg-20.degree. C.) to less than the Tg. The heat treatment may be performed either at a constant temperature within the above-described range or while cooling. The heat treatment time is from 0.1 to 1,500 hours, more preferably from 0.5 to 200 hours. The support may be subjected to heat treatment either in the roll state or as a web on the way of conveyance. The surface may be made uneven (for example, by coating electrically conductive inorganic fine particles such as SnO.sub.2 or Sb.sub.2 O.sub.5) to improve the surface state. Also, it is preferred to make some designs such that the edge is knurled to slightly increase the height only of the edge, thereby preventing the cut copy at the core portion. The heat treatment may be performed at any stage, such as after formation of support film, after surface treatment, after coating of a back layer (e.g., antistatic agent, slipping agent), or after undercoating. The preferred stage is after coating of an antistatic agent.
Into the polyester, an ultraviolet absorbent may be kneaded in. Or, for preventing light piping, a commercially available dye or pigment for polyester, such as Diaresin produced by Mitsubishi Chemicals Industries, Ltd. or Kayaset produced by Nippon Kayaku K. K., may be mixed so as to attain the object.
The film patrone into which the light-sensitive material can be loaded is described below. The patrone for use in the present invention may be mainly made of a metal or a synthetic plastic.
Preferred plastic materials are polystyrene, polyethylene, polypropylene and polyphenyl ether. The patrone may further contain various antistatic agents and preferred examples thereof include carbon black, a metal oxide particle, a nonionic, anionic, cationic or betaine surface active agent and a polymer. The patrone imparted with the antistatic property is described in JP-A-1-312537 and JP-A-1-312538. In particular, the resistance at 25.degree. C. and 25% RH is preferably 10.sup.12 .OMEGA. or less. Usually, the plastic patrone is produced using a plastic having kneaded therein carbon black or a pigment so as to give light-shielding property. The patrone may have a 135 size currently used but it is also effective for achieving miniaturization of a camera to reduce the cartridge size from 25 mm in the current 135 size to 22 mm or less. The volume of the patrone case is preferably 30 cm.sup.3 or less, more preferably 25 cm.sup.3 or less. The weight of plastics used in the patrone and the patrone case is preferably from 5 to 15 g.
A patrone which delivers the film by rotation of a spool may also be used. Further, the patrone may have such a structure that a film leading end is housed in the patrone body and the film leading end is delivered from the port part of the patrone towards the outside by rotating the spool shaft in the film delivery direction. These are disclosed in U.S. Pat. Nos. 4,834,306 and 5,226,613.
For producing a print on a color paper or a heat-developable light-sensitive material using the above-described color photographing material, the methods described in JP-A-5-241251, JP-A-5-19364 and JP-A-5-19363 may be used.
The present invention will be described in greater detail below with reference to Examples but the present invention should not be construed as being limited to these Examples.

EXAMPLE 1
Into a reaction vessel, 950 ml of distilled water containing 12.5 g of gelatin having an average molecular weight of 15,000, 4.35 g of potassium bromide and 0.32 g of potassium iodide was charged, and the temperature was raised to 45.degree. C. To the resulting solution, 50 ml of an aqueous solution containing 8.3 g of silver nitrate and 50 ml of an aqueous solution containing 2.67 g of potassium bromide were added while vigorously stirring over 45 seconds. After completion of the addition, 0.38 mg of potassium iridate hexachloride was added. After keeping the mixture at 45.degree. C. for 4 minutes, the temperature of the reaction solution was raised to 63.degree. C. To the solution, 17.0 g of gelatin was added together with 130 ml of distilled water and thereafter, 150 ml of an aqueous solution containing 51.2 g of silver nitrate and a 24.8% aqueous solution of potassium bromide were added over 13 minutes while accelerating the addition flow rate and at the same time, keeping the silver potential in the reaction solution at 0 mV to the saturation calomel electrode. After completion of the addition, the reaction solution was kept at 63.degree. C. for 2 minutes and then the temperature was lowered to 45.degree. C. Subsequently, 50 ml of an aqueous solution containing 5.9 g of silver nitrate and 320 ml of an aqueous solution containing 5.82 g of potassium iodide were added over 5 minutes. Further, 350 ml of an aqueous solution containing 104.3 g of silver nitrate and a 25% aqueous solution of potassium bromide were added over 45 minutes while keeping the silver potential in the reaction solution at 90 mV to the saturation calomel electrode. After completion of the addition, 1.4 g of potassium bromide and 4 mg of sodium ethylthiosulfonate were added and after keeping the mixture at 45.degree. C. for 5 minutes, the temperature of the solution was lowered and the solution was desalted according to a usual method.
The thus-obtained emulsion was an emulsion comprising hexagonal tabular grains having an average grain size, in terms of a sphere-corresponding diameter (i.e., equivalent-sphere diameter), of 0.37 .mu.m and a ratio obtained by dividing the average grain diameter by the average grain thickness of 2.2. This emulsion was designated as Emulsion A-1. Grains having a grain diameter/thickness ratio of 3.8 or 5.4 were prepared by changing the silver potential during grain formation in Emulsion A-1 and designated as Emulsion A-2 and Emulsion A-3.
Into a reaction vessel, 930 ml of distilled water containing 0.74 g of gelatin having an average molecular weight of 15,000 and 0.7 g of potassium bromide was charged, and the temperature was raised to 40.degree. C. To the resulting solution, 30 ml of an aqueous solution containing 1.2 g of silver nitrate and 30 ml of an aqueous solution containing 0.82 g of potassium bromide were added while vigorously stirring over 30 seconds. After completion of the addition, the mixture was kept at 40.degree. C. for 1 minute and then the temperature of the reaction solution was raised to 75.degree. C. To the solution, 27.0 g of gelatin was added together with 200 ml of distilled water and thereafter, 100 ml of an aqueous solution containing 22.5 g of silver nitrate and 80 ml of an aqueous solution containing 15.43 g of potassium bromide were added over 11 minutes while accelerating the addition flow rate. Subsequently, 250 ml of an aqueous solution containing 75.1 g of silver nitrate and an aqueous solution (concentration of potassium bromide: 26%) containing potassium iodide and potassium nitrate at a molar ratio of 3:97 were added over 20 minutes while accelerating the addition flow rate and at the same time, keeping the silver potential in the reaction solution at 2 mV to the saturation calomel electrode. Further, 75 ml of an aqueous solution containing 18.7 g of silver nitrate and a 21.9% aqueous solution of potassium bromide was added over 3 minutes while keeping the silver potential in the reaction solution at 0 mV to the saturation calomel electrode. After completion of the addition, the mixture was kept at 75.degree. C. for 1 minute and then, the temperature of the reaction solution was lowered to 55.degree. C. Thereafter, 120 ml of an aqueous solution containing 8.1 g of silver nitrate and 320 ml of an aqueous solution containing 7.26 g of potassium iodide were added over 5 minutes. After completion of the addition, 5.5 g of potassium bromide and 0.04 mg of potassium iridate hexachloride were added, the mixture was kept at 55.degree. C. for 1 minute, and then, 180 ml of an aqueous solution containing 44.3 g of silver nitrate and 160 ml of an aqueous solution containing 34.0 g of potassium bromide were further added over 8 minutes. The temperature of the solution was lowered and then, the solution was desalted according to a usual method.
The thus-obtained emulsion was an emulsion comprising hexagonal tabular grains having an average grain size, in terms of a sphere-corresponding diameter, of 0.66 .mu.m and a ratio obtained by dividing the average grain diameter by the average grain thickness of 3.8. This emulsion was designated as Emulsion B-1. Grains having a grain diameter/thickness ratio of 5.4 or 7.1 were prepared by changing the silver potential during grain formation in Emulsion B-1 and designated as Emulsion B-2 and Emulsion B-3.
An aqueous solution (1;600 ml) containing 7.9 g of gelatin having an average molecular weight of 15,000 and 4.5 g of potassium bromide was heated at 40.degree. C. To the resulting solution, an aqueous solution containing 8.9 g of silver nitrate and an aqueous solution containing 6.2 g of potassium bromide and 0.39 g of potassium iodide were added over 40 seconds. Thereto, 38 g of gelatin was added and the solution was heated to 58.degree. C. Subsequently, an aqueous solution containing 5.6 g of silver nitrate was added, 0.1 mol of ammonia was added, and after ripening for 15 minutes, the solution was neutralized with an acetic acid to a pH of 5.0. Further, an aqueous solution containing 219.0 g of silver nitrate and a 20% aqueous solution of potassium bromide were added while accelerating the addition flow rate and at the same time, keeping the silver potential in the reaction solution at -10 mV to the saturation calomel electrode. The temperature of the solution was lowered and then, the solution was desalted according to a usual method and adjusted to have a pH of 5.8 and a pAg of 8.8 at 40.degree. C. by adding 50 g of gelatin. The resulting emulsion contained 1.0 mol/kg of silver and 80.0 g/kg of gelatin. The silver halide grains contained therein had an average grain size, in terms of a sphere-corresponding diameter, of 0.25 .mu.m, a ratio obtained by dividing the average grain diameter by the average grain thickness of 6.0, and a hexagonal tabular shape.
An aqueous solution (850 ml) containing the emulsion obtained above as a seed emulsion in an amount necessary for giving a silver amount of 2.76 mol %, 0.92 g of potassium bromide and 25.3 g of gelatin was heated at 75.degree. C. To this solution, 10 ml of a 0.05% methanol solution of sodium benzene-thiosulfonate was added and then, 430 ml of an aqueous solution containing 90.5 g of silver nitrate and an aqueous solution (concentration of potassium bromide: 15%) containing potassium iodide and potassium bromide at a molar ratio of 3:97 were added over 38 minutes while accelerating the addition flow rate and at the same time, keeping the silver potential in the reaction solution at 0 mV to the saturation calomel electrode. The mixture was kept at 75.degree. C. for 2 minutes, and then 125 ml of an aqueous solution containing 18.5 g of silver nitrate and a 26.5% aqueous solution of potassium bromide were added over 5 minutes while keeping the silver potential in the reaction solution at 0 mV to the saturation calomel electrode. The mixture was kept at 75.degree. C. for 2 minutes and then, the temperature of the solution was raised to 55.degree. C. Subsequently, 100 ml of an aqueous solution containing 9.0 g of silver nitrate and 320 ml of an aqueous solution containing 7.81 g of potassium iodide were added over 5 minutes. Thereto, 4.69 g of potassium bromide was added and further, 180 ml of an aqueous solution containing 47.1 g of silver nitrate and 130 ml of an aqueous solution containing 33,11 g of potassium bromide were added over 14 minutes. Thereafter, the temperature of the solution was lowered and the solution was desalted according to a usual method.
The resulting emulsion was an emulsion comprising hexagonal tabular grains having an average grain size, in terms of a sphere-corresponding diameter, of 0.86 .mu.m and a ratio obtained by dividing the average grain diameter by the average grain thickness of 3.8. This emulsion was designated as Emulsion C-1. Grains having a grain diameter/thickness ratio of 5.4 or 7.1 were prepared by changing the silver potential during grain formation in Emulsion C-1 and designated as Emulsion C-2 and Emulsion C-3.
Each of these emulsions was subjected to spectral sensitization and chemical sensitization by adding spectral sensitizing dyes shown below, Compound I shown below, potassium thiocyanate, chloroauric acid and sodium thiosulfate. At this time, the spectral sensitizing dye was changed in proportion to the grain surface area of each emulsion and the amount of the chemical sensitizer was adjusted to give an optimal chemical sensitization degree.
The thus prepared green-sensitive emulsions each was expressed with a suffix of g, for example, A-2g.
Sensitizing Dye I for Green-Sensitive Emulsion: ##STR6## Sensitizing Dye II for Green-Sensitive Emulsion: ##STR7## Sensitizing Dye III for Green-Sensitive Emulsion: ##STR8##
Then, a dispersion of zinc hydroxide to be used as a base precursor was prepared.
Zinc hydroxide powder (31 g) having a primary grain size of 0.2 .mu.m, 1.6 g of carboxymethyl cellulose and 0.4 g of sodium polyacrylate as dispersants, 8.5 g of lime-processed ossein gelatin and 158.5 ml of water were mixed and the mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, glass beads were separated by filtration and 188 g of a zinc hydroxide dispersion was obtained.
An emulsion dispersion of a magenta coupler was prepared.
Magenta Coupler (a) (7.80 g), 5.45 g of Developing Agent (b), 2 mg of Antifoggant (c), 8.21 g of High Boiling Point Organic Solvent (d) and 24.0 ml of ethyl acetate were dissolved at 60.degree. C. The resulting solution was mixed into 150 g of an aqueous solution having dissolved therein 12.0 g of lime-processed gelatin and 0.6 g of sodium dodecylbenzenesulfonate and the mixture was emulsion dispersed using a dissolver at a revolution of 10,000 for 20 minutes. After the emulsion dispersion, distilled water was added to make the total amount of 300 g and mixed at a revolution of 2,000 for 10 minutes.
By combining these dispersions and the silver halide emulsions prepared above, 14 kinds of heat-developable color photographic light-sensitive material Samples 101 to 114 were prepared as shown in Table 1 and Table 2.
TABLE 1__________________________________________________________________________ Sample (mg/m.sup.2) 101 102 103 104 105 106 107__________________________________________________________________________Protective LayerLime-processed gelatin 1,000 1,000 1,000 1,000 1,000 1,000 1,000Matting agent (silica) 50 50 50 50 50 50 50Surface Active Agent (f) 100 100 100 100 100 100 100Surface Active Agent (g) 300 300 300 300 300 300 300Water-Soluble Polymer (h) 15 15 15 15 15 15 15Hardening Agent (i) 35 35 35 35 35 35 35InterlayerLime-processed gelatin 375 375 375 375 375 375 375Surface Active Agent (g) 15 15 15 15 15 15 15Zinc hydroxide 1,100 1,100 1,100 1,100 1,100 1,100 1,100Water Soluble Polymer (h) 15 15 15 15 15 15 15MagentaColoring LayerLime-processed gelatin 2,000 2,000 2,000 2,000 2,000 2,000 2,000Emulsion (in terms of A-2 g A-2 g A-2 g B-2 g B-2 g B-2 g B-2 gcoated silver amount) 863 1,726 4,315 863 1,726 4,315 1,079 A-1 g 647Magenta Coupler (a) 637 637 637 637 637 637 637Developing Agent (b) 444 444 444 444 444 444 444Antifoggant (c) 0.20 0.20 0.20 0.20 0.20 0.20 0.20High Boiling Point 670 670 670 670 670 670 670Organic Solvent (d)Surface Active Agent (e) 33 33 33 33 33 33 33Water-Soluble Polymer (h) 14 14 14 14 14 14 14Lime-processed gelatin -- -- -- -- -- -- --Emulsion -- -- -- -- -- -- --Magenta Coupler (a) -- -- -- -- -- -- --Developing Agent (b) -- -- -- -- -- -- --Antifoggant (c) -- -- -- -- -- -- --High Boiling Point -- -- -- -- -- -- --Solvent (d)Surface Active Agent (e) -- -- -- -- -- -- --Water Soluble Polymer (h) -- -- -- -- -- -- --Lime-processed gelatin -- -- -- -- -- -- --Emulsion (in terms of -- -- -- -- -- -- --coated silver amount)Magenta Coupler (a) -- -- -- -- -- -- --Developing Agent (b) -- -- -- -- -- -- --Antifoggant (c) -- -- -- -- -- -- --High Boiling Point -- -- -- -- -- -- --Organic Solvent (d)Surface Active Agent (e) -- -- -- -- -- -- --Water-Soluble Polymer (h) -- -- -- -- -- -- --Transparent PET base (120 .mu.m)__________________________________________________________________________
TABLE 2__________________________________________________________________________(continuation of Table 1) Sample 108 109 110 111 112 113 114__________________________________________________________________________Protective LayerLime-processed gelatin 1,000 1,000 1,000 1,000 1,000 1,000 1,000Matting agent (silica) 50 50 50 50 50 50 50Surface Active Agent (f) 100 100 100 100 100 100 100Surface Active Agent (g) 300 300 300 300 300 300 300Water-Soluble Polymer (h) 15 15 15 15 15 15 15Hardening Agent (i) 35 35 35 35 35 35 33InterlayerLime-processed gelatin 375 375 375 375 375 375 375Surface Active Agent (g) 15 15 15 15 15 15 15Zinc hydroxide 1,100 1,100 1,100 1,100 1,100 1,100 1,100Water Soluble Polymer (h) 15 15 15 15 15 15 15MagentaColoring LayerLime-processed gelatin 2,000 2,000 2,000 500 500 500 150Emulsion (in terms of B-2 g B-2 g B-3 g B-2 g B-2 g B-3 g C-3 gcoated silver amount) 1,079 1,079 1,079 1,079 1,079 1,079 647 A-2 g A-3 g A-3 g 647 647 647Magenta Coupler (a) 637 637 637 159 159 159 48Developing Agent (b) 444 444 444 111 111 111 33Antifoggant (c) 0.20 0.20 0.20 0.05 0.05 0.05 0.02High Boiling Point 670 670 670 168 168 168 50Organic Solvent (d)Surface Active Agent (e) 33 33 33 8 8 8 3Water-Soluble Polymer (h) 14 14 14 4 4 4 1Lime-processed gelatin -- -- -- 1,500 1,500 1,500 220Emulsion -- -- -- A-2 g A-3 g A-3 g B-2 g 647 647 647 475Magenta Coupler (a) -- -- -- 377 477 471 70Developing Agent (b) -- -- -- 333 333 333 49Antifoggant (c) -- -- -- 0.15 0.15 0.15 0.02High Boiling Point -- -- -- 504 504 504 74Solvent (d)Surface Active Agent (e) -- -- -- 24 24 24 4Water Soluble Polymer (h) -- -- -- 12 12 12 2Lime-processed gelatin -- -- -- -- -- -- 1,400Emulsion (in terms of -- -- -- -- -- -- A-2 gcoated silver amount) 604Magenta Coupler (a) -- -- -- -- -- -- 446Developing Agent (b) -- -- -- -- -- -- 311Antifoggant (c) -- -- -- -- -- -- 0.14High Boiling Point -- -- -- -- -- -- 469Organic Solvent (d)Surface Active Agent (e) -- -- -- -- -- -- 23Water-Soluble Polymer (h) -- -- -- -- -- -- 10Transparent PET base (120 .mu.m)__________________________________________________________________________ ##STR9##
Further, Processing Materials P-1 and P-2 as shown in Tables 3-1, 3-2 and 4 was prepared.
TABLE 3-1______________________________________Construction of Processing Material P-1 Addition AmountLayer Structure Materials (mg/m.sup.2)______________________________________Fourth Layer Acid-processed gelatin 220(Protective Layer) Water Soluble Polymer (j) 60 Water Soluble Polymer (k) 200 Additive (1) 80 Palladium sulfide 3 Potassium nitrate 12 Matting Agent (m) 10 Surface Active Agent (g) 7 Surface Active Agent (n) 7 Surface Active Agent (o) 10Third Layer Lime-processed gelatin 240(Interlayer) Water-Soluble Polymer (k) 24 Hardening Agent (p) 180 Surface Active Agent (e) 9Second Layer Lime-processed gelatin 2,400(Base generating Water-Soluble Polymer (k) 360Layer) Water-Soluble Polymer (q) 700 Water-Soluble Polymer (r) 600 High Boiling Point Solvent (s) 2,000 Additive (t) 20 Potassium hydantoin 260 Guanidine picolinate 2,910 Potassium quinolinate 225 Sodium quinolinate 180 Surface Active Agent (e) 24First Layer Lime-processed gelatin 280(Undercoat Layer) Water-Soluble Polymer (j) 12 Surface Active Agent (g) 14 Hardening Agent (p) 185Transparent Support A (63 .mu.m)______________________________________
TABLE 3-2______________________________________Construction of Processing Material P-2 Addition AmountLayer Structure Materials (mg/m.sup.2)______________________________________Fourth Layer Acid-processed gelatin 180 Water Soluble Polymer (j) 60 Water Soluble Polymer (k) 200 Potassium nitrate 12 Matting Agent (m) 10 Surface Active Agent (g) 7 Surface Active Agent (n) 7 Surface Active Agent (o) 10Third Layer Lime-processed gelatin 240 Water-Soluble Polymer (k) 24 Hardening Agent (p) 180 Surface Active Agent (e) 9Second Layer Lime-processed gelatin 2,400 Water-Soluble Polymer (k) 120 Water-Soluble Polymer (q) 700 Water-Soluble Polymer (r) 600 High Boiling Point Solvent (s) 2,000 Additive A 1,270 Additive B 683 Surface Active Agent (e) 20First Layer Gelatin 190 Water-Soluble Polymer (j) 12 Surface Active Agent (g) 14 Hardening Agent (p) 185Transparent Support A (63 .mu.m)______________________________________
TABLE 4______________________________________Construction of Support A WeightName of Layer Composition (mg/m.sup.2)______________________________________Surface Undercoat Gelatin 100LayerPolymer Layer Polyethylene terephthalate 62,500Back Surf ace Methyl methacrylate-styrene- 1,000Undercoat Layer 2-ethylhexyl acrylate- 120 methacrylic acid copolymer PMMA latex (average particle size: 12 .mu.m) 63,720______________________________________Water-Soluble Polymer (j).kappa.-carrageenanWater-Soluble Polymer (k)Sumikagel L-5H (produced by Sumitomo Chemical Company,Limited)Additive (1)1 #STR10##Matting Agent (m)SYLOID79 (produced byFuji Davison)Surface Active Agent (n)2 #STR11##Surface Active Agent (O)3 #STR12##Hardening Agent (p)7 #STR13##Water-Soluble Polymer (q)Dextran (molecularweight: 70,000)Water-Soluble Polymer (r)MP polymer MP102 (produced by Kuraray KK)High Boiling Point Solvent (s)En-para 40 (produced by Ajinomoto KK)Additive (t)4 #STR14##Additive A5 #STR15##Additive B6 #STR16## Each of these light-sensitive materials was exposed through an optical
After the exposure, 15 ml/m.sup.2 of warm water at 40.degree. C. was applied to the surface of each light-sensitive material, the light-sensitive material was-laminated on the processing material such that the layer surfaces faced to each other, and the laminate was heat developed at 83.degree. C. for 30 seconds using a heat drum. After the processing, the light-sensitive material was peeled off and a magenta colored wedgewise image was obtained. Each sample was subjected to the second stage processing using a second processing sheet described below. In the second stage processing, 10 ml/m.sup.2 of water was coated on a second processing sheet, the sheet was laminated on the light-sensitive material after the first processing, and the laminate was heated at 60.degree. C. for 30 seconds. These colored samples each was measured on the transmission density and a so-called characteristic curve was obtained. A reciprocal of the exposure amount necessary for giving a density 0.15 higher than the fog density was used as a relative sensitivity and the sensitivity was shown by a value relative to the value of Sample 101 taken as 100. The maximum coloring density was used as an index for developability.
Further, a logarithm of the difference between the exposure amount necessary for giving a density 0.1 higher than the fog density and the exposure amount corresponding to the density 0.2 lower than the maximum density was used as a latitude.
Then, each sample was examined on the granularity. Each sample was exposed to give a magenta coloring density of 1.0 and heat-developed in the same manner as above to prepare a colored specimen, and the RMS granularity was measured through an aperture having a diameter of 48 .mu.m using a diffuse light source.
For comparison with conventional liquid development, the same exposed samples each was processed using Processing CN-16 for a color negative film under the development conditions of 38.degree. C. and 185 seconds, and these were measured on the RMS granularity in the same manner.
The relation of the coated grain numbers of silver halide in these light-sensitive materials is shown in Table 5 and Table 6, and the results obtained are shown in Table 7.
TABLE 5__________________________________________________________________________ Sample 101 102 103 104 105 106 107__________________________________________________________________________Used emulsion-1 A-2 g A-2 g A-2 g B-2 g B-2 g B-2 g A-1 gAverage projected area 0.1963 0.1963 0.1963 0.7088 0.7088 0.7088 0.1385(.mu.m.sup.2)Coated silver amount 0.8630 1.7260 4.3150 0.8630 1.7260 4.3150 0.6470(g/m.sup.2)Grain number (.times.10.sup.12 /m.sup.2) 8.8724 17.7448 44.3620 1.5749 3.1498 7.8745 6.6517Used emulsion-2 -- -- -- -- -- -- B-2 gAverage projected area 0.7088(.mu.m.sup.2)Coated silver amount 1.0790(g/m.sup.2)Grain number (.times.10.sup.12 /m.sup.2) 1.9696Used emulsion-3 -- -- -- -- -- -- --Average projected area(.mu.m.sup.2)Coated silver amount(g/m.sup.2)Grain number (.times.10.sup.12 /m.sup.2)Ratio* specified in the -- -- -- -- -- -- 1/0.1441present inventionRatio of grain numbers -- -- -- -- -- -- 1/0.2960Remarks Comparison Comparison Comparison Comparison Comparison Comparison Invention__________________________________________________________________________ *Ratio of the values obtained by dividing the coated silver amount by the 3/2nd power of average grain projected area (hereinafter the same).
TABLE 6__________________________________________________________________________ Sample 108 109 110 111 112 113 114__________________________________________________________________________Emulsion-1 A-2 g A-3 g A-3 g A-2 g A-3 g A-3 g A-2 gAverage projected area 0.1963 0.2552 0.2552 0.1963 0.2552 0.2552 0.1963(.mu.m.sup.2)Coated silver amount 0.6470 0.6470 0.6470 0.6470 0.6470 0.6470 0.6040(g/m.sup.2)Grain number (.times.10.sup.12 /m.sup.2) 6.6517 6.6517 6.6517 6.6517 6.6517 6.6517 6.2097Emulsion-2 B-2 g B-2 g B-3 g B-2 g B-2 g B-3 g B-2 gAverage projected area 0.7088 0.7088 0.8495 0.7088 0.7088 0.8495 0.7088(.mu.m.sup.2)Coated silver amount 1.0790 1.0790 1.0790 1.0790 1.0790 1.0790 0.4750(g/m.sup.2)Grain number (.times.10.sup.12 /m.sup.2) 1.9691 1.9691 1.9691 1.9691 1.9691 1.9691 0.8668Emulsion-3 -- -- -- -- -- -- C-3 gAverage projected area 1.6286(g/m.sup.2)Coated silver amount 0.6470(g/m.sup.2)Grain number (.times.10.sup.12 /m.sup.2) 0.5349Ratio* specified in the 1/0.2431 1/0.3603 1/0.2746 1/0.2431 1/0.3603 1/0.2746 1/0.1146/0.0448present inventionRatio of grain numbers 1/0.2960 1/0.2966 1/0.2960 1/0.2960 1/0.2960 1/0.2960 1/0.1396/0.0861Remarks Invention Comparison Invention Invention Comparison Invention Invention__________________________________________________________________________
TABLE 7__________________________________________________________________________ Sample 101 102 103 104 105 106 107 108 109 110 111 112 113 114__________________________________________________________________________Sensitivity 100 108 91 361 534 509 521 523 525 610 499 501 583 998Maximum 2.91 3.09 3.25 1.75 2.34 2.85 2.90 2.82 2.70 2.79 2.79 2.68 2.76 2.78densityLatitude 1.42 1.36 1.31 1.61 1.45 1.42 2.25 2.10 1.69 2.14 2.49 1.82 2.53 3.47RMSgranularityHeat 0.011 0.012 0.011 0.018 0.014 0.012 0.013 0.013 0.016 0.013 0.011 0.015 0.011 0.011developmentCN-16 0.021 0.020 0.021 0.033 0.032 0.028 0.024 0.025 0.028 0.026 0.024 0.027 0.023 0.023ProcessingRemarks Comp. Comp. Comp. Comp. Comp. Comp. Inv. Inv. Comp. Inv. Inv. Comp. Inv. Inv.__________________________________________________________________________
It is seen from these results that Samples 101 to 106 using one kind of emulsion cannot achieve sensitivity, latitude and granularity at the same time. More specifically, Samples 101 to 103 using a small-size emulsion have good granularity, however, are insufficient in sensitivity. Samples 104 to 106 using a large size emulsion have high sensitivity, however, the granularity is large and if the granularity is improved by increasing the coated amount of emulsion, the latitude becomes insufficient.
On reviewing the data of Samples 107 to 110 using two kinds of emulsions different in the average grain size, samples where as the emulsion having a larger average grain projected area, the ratio of silver halide grain numbers per unit area of the present invention is larger than the ratio of the values obtained by dividing the coated silver amount of emulsion by the 3/2nd power of average grain projected area, as specified in the present invention, provide good results. In other words, Samples 107, 108 and 110 achieve high sensitivity, wide latitude and excellent granularity. Sample 109 failed in satisfying the specific ratio of the present invention is worsened in the granularity and can have only narrow latitude.
Further, on comparison between Sample 108 and Sample 111, between Sample 109 and Sample 112, and between Sample 110 and Sample 113, it is clearly seen that when the emulsions different in the average grain projected area are provided as separate layers, the above-described effects of the present invention are more outstanding.
Furthermore, when the development step CN-16 for a conventional negative film is used, the effects of the present invention cannot be obtained, and they can first be provided when the heat development specified in the present invention is performed. These effects cannot be expected at all from known techniques and are very surprising discovery.
EXAMPLE 2
A blue-sensitive emulsion and a red-sensitive emulsion were prepared by changing the spectral sensitizing dyes used in spectral sensitization of the silver halide emulsion prepared in Example 1.
Sensitizing Dye IV for Blue-Sensitive Emulsion: ##STR17## Sensitizing Dye V for Red-Sensitive Emulsion: ##STR18## Sensitizing Dye VI for Red-Sensitive Emulsion: ##STR19## Sensitizing Dye VII for Red-Sensitive Emulsion: ##STR20##
Further, a cyan coupler dispersion and a yellow coupler dispersion were prepared according to the preparation method of a coupler dispersion in Example 1.
Furthermore, coloring agent dispersions were also prepared by combining a leuco dye shown below for yellow magenta or cyan with a zinc complex for the purpose of forming a colored layer capable of decoloration at the time of heat development processing.
Using the thus-obtained silver halide emulsions, coupler dispersions and coloring agent dispersions, heat-developable color light-sensitive materials having a multi-layer structure shown in Table 8 were prepared.
TABLE 8__________________________________________________________________________ Sample 201 202 203 204__________________________________________________________________________Protective Lime-processed 1,000 1,000 1,000 1,000Layer gelatin Matting agent 50 50 50 50 (silica) Surface Active 100 100 100 100 Agent (f) Surface Active 300 300 300 300 Agent (g) Water-Soluble 15 15 15 15 Polymer (h) Hardening Agent 98 98 98 91 (i)Interlayer Lime-processed 375 375 375 375 gelatin Surface Active 15 15 15 15 Agent (g) Zinc hydroxide 1,100 1,100 1,100 1,100 Water Soluble 15 15 15 15 Polymer (h)Yellow Lime-processed 2,000 500 500 150Coloring gelatinLayer Emulsion (in B-2b B-2b B-2b C-3b terms of coated 1,726 1,079 1,079 647 silver amount) Yellow Coupler 760 190 190 57 (u) Developing 546 137 137 41 Agent (v) Antifoggant (w) 57 14 14 4 High Boiling 670 168 168 50 Point Organic Solvent (d) Surface Active 33 8 8 3 Agent (e) Water-Soluble 14 4 4 1 Polymer (h)Yellow Lime-processed -- 1,500 1,500 220Coloring gelatinLayer Emulsion (in -- A-3b A-2b B-2b terms of coated 647 647 475 silver amount) Yellow Coupler -- 570 570 84 (u) Developing -- 410 410 60 Agent (v) Antifoggant (w) -- 43 43 6 High Boiling -- 503 503 74 Point Solvent (d) Surface Active -- 24 24 4 Agent (e) Water Soluble -- 12 12 2 Polymer (h)Yellow Lime-processed -- -- -- 1,400Coloring gelatinLayer Emulsion (in -- -- -- A-2b terms of coated 604 silver amount) Yellow Coupler -- -- -- 532 (u) Developing -- -- -- 382 Agent (v) Antifoggant (w) -- -- -- 40 High Boiling -- -- -- 469 Point Organic Solvent (d) Surface Active -- -- -- 23 Agent (e) Water-Soluble -- -- -- 10 Polymer (h)Interlayer Lime-processed 750 750 750 750 gelatin Surface Active 15 15 15 15 Agent (e) Leuco Dye (x) 303 303 303 303 Developer (y) 433 433 433 433 Water-Soluble 15 15 15 15 Polymer (h)Magenta Lime-processed 2,000 500 500 150Coloring gelatinLayer Emulsion (in B-2g B-2g B-2g C-3g terms of coated 1,726 1,079 1,079 647 silver amount) Magenta Coupler 637 159 159 48 (a) Developing 444 111 111 33 Agent (b) Antifoggant (c) 0.20 0.05 0.05 0.02 High Boiling 670 168 168 50 Point Organic Solvent (d) Surface Active 33 8 8 3 Agent (e) Water-Soluble 14 4 4 1 Polymer (h)Magenta Lime-processed -- 1,500 1,500 220Coloring gelatinLayer Emulsion -- A-3g A-2g B-2g 647 647 475 Magenta Coupler -- 477 477 70 (a) Developing -- 333 333 49 Agent (b) Antifoggant (c) -- 0.15 0.15 0.02 High Boiling -- 504 504 74 Point Solvent (d) Surface Active -- 24 24 4 Agent (e) Water-Soluble -- 12 12 2 Polymer (h)Magenta Lime-processed -- -- -- 1,400Coloring gelatinLayer Emulsion -- -- -- A-2g 604 Magenta Coupler -- -- -- 446 (a) Developing -- -- -- 311 Agent (b) Antifoggant (c) -- -- -- 0.14 High Boiling -- -- -- 469 Point Organic Solvent (d) Surface Active -- -- -- 23 Agent (e) Water-Soluble -- -- -- 10 Polymer (h)Interlayer Lime-processed 900 900 900 900 gelatin Surface Active 15 15 15 15 Agent (e) Leuco Dye (z) 345 345 345 345 Developer (y) 636 636 636 636 Zinc hydroxide 1,100 1,100 1,100 1,100 Water-Soluble 15 15 15 15 Polymer (h)Cyan Lime-processed 2,000 500 500 150Coloring gelatinLayer Emulsion B-2r B-2r B-2r C-3r 1,726 1,079 1,079 647 Cyan Coupler 872 218 218 65 (aa) Developing 444 111 111 33 Agent (b) Antifoggant (c) 0.45 0.11 0.11 0.03 High Boiling 670 168 168 50 Point Organic Solvent (d) Surface Active 33 8 8 3 Agent (e) Water-Soluble 14 4 4 1 Polymer (h)Cyan Lime-processed -- 1,500 1,500 220Coloring gelatinLayer Emulsion -- A-3r A-2r B-2r 647 647 475 Cyan Coupler -- 654 654 96 (aa) Developing -- 333 333 49 Agent (b) Antifoggant (c) -- 0.34 0.34 0.05 High Boiling -- 504 504 74 Point Solvent (d) Surface Active -- 24 24 4 Agent (e) Water-Soluble -- 12 12 2 Polymer (h)Cyan Lime-processed -- -- -- 1,400Coloring gelatinLayer Emulsion -- -- -- A-2r 604 Cyan Coupler -- -- -- 610 (aa) Developing -- -- -- 311 Agent (b) Antifoggant (c) -- -- -- 0.32 High Boiling -- -- -- 469 Point Organic Solvent (d) Surface Active -- -- -- 23 Agent (e) Water-Soluble -- -- -- 10 Polymer (h)Anti- Lime-processed 750 750 750 750halation gelatinLayer Surface Active 15 15 15 15 Agent (e) Leuco Dye (ab) 243 243 243 243 Developer (y) 425 425 425 425 Water-Soluble 15 15 15 15 Polymer (h)__________________________________________________________________________Transparent PET base (120 .mu.m)Yellow Coupler (u)8 #STR21##Developing Agent (v)9 #STR22##Antifoggant (w)0 #STR23##Cyan Coupler (aa)1 #STR24##Leuco Dye (ab)2 #STR25##Yellow Colored Leuco Dye (X)3 #STR26##Developer (y)4 #STR27##Magenta Colored Leuco Dye (Z)5 #STR28## Each of these light-sensitive materials was tested on the photographicproperty in the same manner as in Example 1. First, each light-sensitivematerial was exposed through an optical wedge and a blue, green or red
After the exposure, 15 ml/m.sup.2 of warm water at 40.degree. C. was applied to the surface of each light-sensitive material, the light-sensitive material was laminated on the processing material used in Example 1 such that the layer surfaces faced to each other, and the laminate was heat developed at 83.degree. C. for 30 seconds using a heat drum. After the processing, the light-sensitive material was peeled off and then, a yellow colored wedgewise image was obtained on the sample exposed through a blue filter, a magenta colore wedgewise image on the sample exposed through a green filter, and a cyan colored wedgewise image on the sample exposed through a red filter. These colored samples each was measured on the transmission density and characteristic values were obtained in the same manner as in Example 1. The sensitivity was shown by a relative value to the sensitivity of Sample 201 to blue, green or red, taken as 100.
Then, each sample was examined on the granularity. Each sample was exposed to give a yellow, magenta or cyan coloring density of 1.0 and heat-developed in the same manner as above to prepare a colored specimen, and the RMS granularity was measured through an aperture having a diameter of 48 .mu.m using a diffuse light source.
For comparison with conventional liquid development, the same exposed samples each was processed using Processing CN-16 for a color negative film under the development conditions of 38.degree. C. and 185 seconds, dipped in an alkali buffer solution having a pH of 10 and then dried. These were measured on the RMS granularity in the same manner.
The relation of the coated grain numbers of silver halide in these light-sensitive materials is shown in Table 10 and the results obtained are shown in Table 11.
TABLE 10______________________________________ Sample 201 202 203 204______________________________________Blue-SensitiveLayer:Used emulsion-1 B-2b A-3b A-2b A-2bAverage 0.7088 0.2552 0.1963 0.1963projected area(.mu.m.sup.2)Coated silver 1.7260 0.6470 0.6470 0.6040amount (g/m.sup.2)Grain number 3.1498 6.6517 6.6517 6.2097(.times.10.sup.12 /m.sup.2)Used emulsion-2 -- B-2b B-2b B-2bAverage 0.7088 0.7088 0.7088projected area(.mu.m.sup.2)Coated silver 1.0790 1.0790 0.4750amount (g/m.sup.2)Grain number 1.9691 1.9691 0.8668(.times.10.sup.12 /m.sup.2)Used emulsion-3 -- -- -- C-3bAverage 1.6286projected area(.mu.m.sup.2)Coated silver 0.6470amount (g/m.sup.2)Grain number 0.5349(.times.10.sup.12 /m.sup.2)Ratio specified -- 1/0.3600 1/0.2431 1/0.1146/in the present 0.0448inventionRatio of grain -- 1/0.2960 1/0.2960 1/0.1396/numbers 0.0861Green-SensitiveLayer:Used emulsion-1 B-2b A-3b A-2b A-2bAverage 0.7088 0.2552 0.1963 0.1963projected area(.mu.m.sup.2)Coated silver 1.7260 0.6470 0.6470 0.6040amount (g/m.sup.2)Grain number 3.1498 6.6517 6.6517 6.2097(.times.10.sup.12 /m.sup.2)Used emulsion-2 -- B-2b B-2b B-2bAverage 0.7088 0.7088 0.7088projected area(.mu.m.sup.2)Coated silver 1.0790 1.0790 0.4750amount (g/m.sup.2)Grain number 1.9691 1.9691 0.8668(.times.10.sup.12 /m.sup.2)Used emulsion-3 -- -- -- C-3bAverage 1.6286projected area(.mu.m.sup.2)Coated silver 0.6470amount (g/m.sup.2)Grain number 0.5349(.times.10.sup.12 /m.sup.2)Ratio specified -- 1/0.3603 1/0.2431 1/0.1146/in the present 0.0448inventionRatio of grain -- 1/0.2960 1/0.2960 1/0.1396/numbers 0.0861Red-SensitiveLayer:Used emulsion-1 B-2b A-3b A-2b A-2bAverage 0.7088 0.2552 0.1963 0.1963projected area(.mu.m.sup.2)Coated silver 1.7260 0.6470 0.6470 0.6040amount (g/m.sup.2)Grain number 3.1498 6.6517 6.6517 6.2097(.times.10.sup.12 /m.sup.2)Used emulsion-2 -- B-2b B-2b B-2bAverage 0.7088 0.7088 0.7088projected area(.mu.m.sup.2)Coated silver 1.0790 1.0790 0.4750amount (g/m.sup.2)Grain number 1.9691 1.9691 0.8668(.times.10.sup.12 /m.sup.2)Used emulsion-3 -- -- -- C-3bAverage 1.6286projected area(.mu.m.sup.2)Coated silver 0.6470amount (g/m.sup.2)Grain number 0.5349(.times.10.sup.12 /m.sup.2)Ratio specified -- 1/0.3603 1/0.2431 1/0.1146/in the present 0.0448inventionRatio of grain -- 1/0.2960 1/0.2960 1/0.1396/numbers 0.0861Remarks Comparison Comparison Invention Invention______________________________________
TABLE 11__________________________________________________________________________ Sample 201 Sample 202 Sample 203 Sample 204 B G R B G R B G R B G R__________________________________________________________________________Sensitivity 100 100 100 92 93 90 91 91 89 187 190 185Maximum density 2.18 2.25 2.21 2.61 2.49 2.43 2.48 2.39 2.35 2.41 2.35 2.32Latitude 1.51 1.46 1.45 1.89 1.86 1.79 2.91 2.83 2.81 3.56 3.50 3.48RMS granularityHeat 0.013 0.014 0.016 0.014 0.015 0.016 0.010 0.011 0.012 0.011 0.011 0.011developmentCN-16 0.030 0.033 0.034 0.027 0.028 0.030 0.025 0.024 0.027 0.022 0.023 0.025ProcessingRemarks Comparison Comparison Invention Invention__________________________________________________________________________
The effects of the present invention can be clearly seen from the results above. That is, Samples 203 and 204 constructed to satisfy the ratio of silver halide grain numbers specified in the present invention can achieve excellent graininess and wide exposure latitude even in heat development within a short time. Further, similarly to Example 1, the effects of the present invention cannot be obtained when the processing solution for a normal color negative film is used, and the effects are outstanding in the heat development method of the present invention.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Silver halide color photographic light-sensitive material and color image formation method using the same

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