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(11) | EP 0 365 348 A2 |
| (12) | EUROPEAN PATENT APPLICATION |
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| (54) | A silver halide color photographic light-sensitive material |
| (57) A silver halide color light-sensitive material and a package thereof in a form of
disposable camera. The light-sensitive material comprises a blue-sensitive, a green-sensitive
and a red-sensitive silver halide emulsion layers provided on a support and at least
one of the color-sensitive emulsion layers has a single-layer structure, wherein at
least one of the silver halide emulsion layers has a single-layer structure and the
emulsion layer having a sigle-layer structure comprises at least two kinds of silver
halide grains deffering in average grain size and contains a development inhibitor
releasing (DIR) compound, and the exposure latitude of the silver halide emulsion
layer with a single-layer structure is 3.0 or more. |
FIELD OF THE INVENTION
[0001] The present invention relates to a silver halide color photographic light-sensitive material, on particularly, relates to a silver halide color photographic light-sensitive in which at least one color-sensitive layer has a single-layer structure.
BACKGROUND OF THE INVENTION
[0002] Today, negative-type light-sensitive materials for color photography are required to be improved in various aspects. Especially, with the recent tendency of making films in small format, the graininess and sharpness of an image, which are factors affecting image qualities, are needed to be improved.
[0003] At present, in the field of color photography, the negative-positive method is widely employed. In this method, a color negative taken by a photographic camera is printed onto a color photographic paper, while being enlarged, thereby obtaining a color photograph. One reason for the spread of this method is that since a color negative film has a very large latitude, the possibility of failure in photographing can be minimized. Therefore, by the use of the negative-positive method, not only professional photographers but also common users having no technical background can enjoy taking a color photograph without fear of failure. This is an important feature which distinguishes the negative-positive method from other methods such as the reversal method. In a color negative film, not only the improved graininess and sharpness of an image, but also the widened latitude of a film is an important factor.
[0004] A negative type photographic light-sensitive materials which are now commercially available generally has a multi-layer structure in which two or more emulsion layers having the same color sensitivity but differing in the size of silver halide grains, i.e., differing in sensitivity, are provided one upon another. Such multi-layer structure of a light-sensitive layer, which leads to an increased latitude and an improved graininess of an image, is described in British Patent No. 923,045 and Japanese Patent Examined Publication No. 15495/1974. The silver halide light-sensitive materials of this type have the following problems, though they are satisfactory to some extent as to latitude and graininess.
(1) Since a color-sensitive layer comprises two or more emulsion layers, the thickness of a light-sensitive material becomes inevitably large, causing the sharpness of an image to be lowered.
(2) In the case of a light-sensitive material of this type, since it has a multi-layer structure in which plural layers are laid one upon another, the development rate varies among layers. That is, layers provided near a support are developed more slowly than layers provided away from a support. This means a photosensitive material of this type hardly remains stable under variable treatment conditions. Unlike a reversal film, negative films for color photography are usually developed in laboratories under variable processing conditions. Therefore, negative films are required to have a high stability to changes in conditions under which processing is carried out.
(3) In the case of a light-sensitive material of multi-layer structure, Since it comprises a lot of layers, coating of emulsion has to be carried out several times. This causes the efficiency of production to be lowered.
(4) The preservability of negative films for color photography has been improved to some extent. However, there is yet room for improvement.
(5) In a light-sensitive material of this type, high-sensitive layers and low-sensitive layers are differently affected by an inhibitor which is diffused from other layers at the time of color development. This leads to a difficulty in obtaining a gradation which allows an image to have an excellent tone-reproducibility to various colors.
SUMMARY OF THE INVENTION
[0005] The object of the present invention is to provide a silver halide light-sensitive material for color photography having a large latitude, which light-sensitive material can produce an image with an excellent graininess and sharpness, and can remain stable under variable processing conditions, and can be produced readily and efficiently.
[0006] The above object has been attained by a silver halide color photographic light-sensitive material comprising blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers are provided on a support and at least one of said color-sensitive layers has a single-layer structure, wherein at least one of said color-sensitive layers with a single-layer structure contains a development inhibitor releasing (DIR) compound, and said color-sensitive. layers with a single-layer structure each comprise at least two kinds of silver halide grains differing in average grain size, and have an exposure latitude of 3.0 or more.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007]
Fig. 1 shows photographic properties of a silver halide light-sensitive material of the present invention (dotted line), in comparison with those of a light-sensitive material which falls outside the scope of the present invention (solid line).
Fig. 2 indicates gamma values at various points on the characteristic curve of a light-sensitive material of the present invention and a comparative light-sensitive material
DETAILED DESCRIPTION OF THE INVENTION
[0008] In the present invention, the expression "a single-layer structure of a silver halide emulsion layer" should be construed to include a structure in which a plurality of emulsion layers which are same in color sensitivity, kind of a coupler contained, grain size of silver halide granules, composition and crystal habit of a halide, and proportion of a coupler to a silver halide, are laid one upon another to form a continuous layer.
[0009] In the expression "same in color sensitivity", color sensitivity means sensitivity to blue, green or red colors. In the present invention, emulsion layers constituting one color-sensitive layer are not required to be completely same in spectral sensitivity.
[0010] In the present invention, it is preferred that at least blue-sensitive silver halide emulsion layer has a single-layer structure. It is more preferred that blue-sensitive and green-sensitive emulsion layers each have a single-layer structure. It is most preferred that blue-sensitive, green-sensitive and red-sensitive layers each have a single-layer structure.
[0011] Unlike conventional light-sensitive materials with multi-layer configuration, in the case of a light-sensitive material in which at least one color-sensitive emulsion layer has a single-layer structure, there is no need to provide a lot of layers on a support, enabling the light-sensitive material to have a reduced thickness. A light-sensitive material with a reduced thickness can be produced readily and efficiently, and an image obtained in this material is excellent in graininess and sharpness. In the present invention, a silver halide light-sensitive material may preferably have a total layer thickness (thickness in a dried state) of 20 to 3 sm, more preferably 15 to 5 §m.
[0012] In the present invention, a DIR compound means a compound which splits off, upon a reaction with an oxidized product of a color developing agent, a development inhibitor or a compound which is capable of releasing a development inhibitor.
[0013] In the above-mentioned compound being capable of splitting off a development inhibitor, the development inhibitor may be split-off either imagewise or non-imagewise.
[0014] Examples of a compound which can split-off imagewise a development inhibitor include compounds which split-off a development inhibitor by a reaction with an oxidized product of a color developing agent. As the compound which can split-off a development inhibitor non-imagewise, there may be mentioned compounds containing a TIME group, which will be explained later.
[0015] The representative structural formula of such compound is given below.
Formula D-1 A-(Y)m wherein A is a coupler residue; m is 1 or 2; and Y is a development inhibitor or a group capable of releasing a development inhibitor which is bounded to a coupling position of A and is split-off therefrom upon a reaction with an oxidized product of a color developing agent.
[0017] In the Formulae D-2 to D-7, Rd1 is a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group, an alkoxycarbonyl group, a thiazolidinonylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group, an N,N-dialkylcarbamoyl group, a nitro group, an amino group, an N-arylcarbamoyloxy group, a sulfamoyl group, an N-alkylcarbamoyloxy group, a hydroxy group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a hetero cyclic group, a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group.
[0018] n represents 0, 1 or 2. When n is 2, Rd1 may either be identical or different. The total number of carbon atoms contained in (Rd1)n is 0 to 10.
[0022] In Formula D-9, Rd3 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a hetero cyclic group; Rd4 is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkanesulfonamido group, a cyano group, a heterocyclic group, an alkylthio group or an amino group.
[0023] When Rd1, Rd2, Rd3 or Rd4 is an alkyl group, this alkyl group may have a substituent. This alkyl group may either be straight chain or branched chain.
[0025] When Rd,, Rd2, Rd3 or Rd4 is a heterocyclic group, this heterocyclic group may have a substituent. This heterocyclic group may preferably be a 5-or 6-membered single or condensed ring which contains, as a hetero atom, at least one member selected from a nitrogen atom, an oxygen atom and a sulfur atom. Examples of such heterocyclic group include a pyridyl group, a quinolyl group, a furyl group, a ben- zothiozolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imido group, and an oxazine group.
[0027] The total number of carbon atoms contained in Rd3 and Rd4 in Formula D-9 is 0 to 15. Formula D-10 -(TIME)n-INHIBIT wherein a TIME group is a group which is bound to a coupling position of A, and can be split-off by a reaction with an oxidized product of a color development agent; said TIME groups are split-off in sequence after being split-off from a coupler, and finally release an INHIBIT group while controlling it appropriately; n represents 1 to 3; and when n is 2 or 3, said TIME groups may either be identical or different.
[0028] An INHIBIT group is a group which becomes an development inhibitor when split-off from a TIME group. Examples of such group include groups represented by the above-mentioned Formulae D-2 to D-9.
[0030] In Formulae D-11 to D-15 and D-18, Rds is a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, an ureido group, a cyano group, a nitro group, a sulfonamido group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group, or an alkanesulfonyl group. In Formulae D-11 to 0-13, D-15 and D-18, Rd5 may combine with each other to form a condensed ring. In Formulae D-11, D-14, D-15 and D-19, Rd6 is an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, a heterocyclic group, or an aryl group. In Formulae D-16 and D-17, Rd7 is a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group, a heterocyclic group or an aryl group. In Formula D-19, Rd8 and Rds each are a hydrogen atom or an alkyl group, preferably having a carbon atoms of 1 to 4. In Formulae D-11, and D-15 to D-18, k is an integer of 0, 1 or 2. In Formulae D-11 to D-13, D-15 and D-18, t is an integer of 1 to 4. In Formula D-16, m is an integer of 1 or 2. When I and m are 2 or more, Rds and Rd7 each may either be identical or different. In Formula D-19, n is an integer of 2 to 4, and Rd8 and Rds each may either be same or different. In Formulae D-16 to D-18, B is an oxygen atom or
in which Rd6 is as defined above. In Formula D-16 means that the bond may either be a single bond or a double bond. When the bond is a single bond, m is 2, and when the bond is a double bond, m is 1. Formula D-20 (̵T1
S R(̵T2
. INH--BIT wherein T1 is a component which splits-off SR (̵T2
, INHIBIT; SR is a component which produces, after the formation of SR(̵T2
INHIBIT, (T2
, I N H |B| T by a reaction with an oxidized product of a color developing agent; T2 is a component which splits off INHIBIT after the formation of (T2 INHIBIT ; INHIBIT is a development inhibitor; and I and m each are 0 or 1.
[0031] As the component represented by SR, any component may be employed as long as it can produce (T2 )̵m'-INHIBIT by the reaction with an oxidized product of a color developing agent. For example, use can be made of a coupler component which undergoes a coupling raction with an oxidized product of a developing agent, or a redox component which undergoes a redox reaction with an oxidized product of a developing agent.
[0032] As the coupler component, there may be mentioned acylacetoanilides, 5-pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetoanilides, 2(5H)-imidazolones, 5-isoox- azolones, uracils, homophthalimides, oxazolones, 2,5-thiazoline-1,1-dioxides, triazolothiadiazines, indoles. Such coupler components include yellow couplers, magenta couplers, and cyan couplers, other dye-forming components and components which do not form a dye are also usable.
[0034] When SR is a coupler component, SR is bound to (T and (T 2)̵m, INHIBIT so that SR cannot serve as a coupler until it is split-off from ( T )̵ .
[0035] For example, when the coupler component is phenols or naphthols, an oxygen atom of a hydroxyl group; when the coupler component is 5-pyrazolones, an oxygen atom of a 5-position hydroxyl group of a tautomer or a nitrogen atom at the 2-position; and when the coupler component is acetophenones or indanones, an oxygen atom of a hydroxyl group of a traumer may preferably be bounded to (̵T )̵ and (T 2)̵m, INHIBIT may preferably be bound to an active point of a coupler.
[0036] When SR is a redox component, examples of such redox component include hydroquinones, catechols, pyrogallols, aminophenols such as p-aminophenols, o-aminophenols, naphthalene diols such as 1,2-naphthalene diols, 1,4-naphthalene diols, 2,6-naphthalene diols, or aminonaphthols such as 1,2-aminonaphthols, 1,4-aminonaphthols, 2,6-aminonaphthols. When SR is a redox component, SR is bounded to (̵T1)̵ and (T 2 )̵m INHIBIT so that SR cannot serve as a redox component until it is split-off from (̵T 3)̵.
[0037] As the group represented by T1 and T2, there may be mentioned groups represented by Formulae D-11 to D-19.
[0038] AS the development inhibitor represented by INHIBIT, there may be mentioned groups represented by Formulae D-2 to D-9.
[0039] The preferred examples of the DIR compound include those in which Y is represented by Formula D-2, D-3, D-8, D-10 or D-20. When Y is represented by Formula D-10 or D-20, it is preferred that INHIBIT is a group represented by Formula D-2, D-3, D-6, especially when X shown in Formula D-6 is an oxygen atom, or D-8.
[0040] As the coupler component represented by A in Formula D-1, there may be mentioned a yellow dye image-forming coupler residue, a magenta dye image-forming coupler residue, a cyan dye image-forming coupler residue, and non-color-forming coupler residue.
[0041] The preferred examples of the DIR compound to be used in the present invention will be given below. The DIR compound to be used in the present invention is not limited to those given below.
Exemplified Compound
[0043] Examples of the DIR compound to be used in the present invention, including those mentioned above, are described in U.S. Patent Nos. 4,234,678, 3,227,554, 3,617,291, 3,958,993, 4,149,886, 3,933,500, 2,072,363, 2,070,266, Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese O.P.I. Publication) Nos. 56837/1982, 13239/1976, and Research Disclosure (hereinafter referred to as RD), No. 21228 (December 1981).
[0044] According to the present invention, the DIR compound may be employed preferably in an amount of 0.0001 to 0.1 mol, more preferably 0.001 to 0.05 mol, per mol of a silver halide.
[0045] In the present invention, by using two or more kinds of silver halides differing in average grain size in mixture, the latitude of a silver halide emulsion layer of single-layer configuration can be as large as 3.0 or more.
[0046] The term "latitude" means a region from a highlight part to a deep shadow part of a characteristic curve. The latitude can be determined by a method described in Shashin no Kagaku, p393 (Shashin Kogyo Shuppan, 1982).
[0047] More specifically, the latitude means a difference in logH between a point at the toe portion and a point at the shoulder portion of a characteristic curve, the axis of abcissas: iogH, the axis of ordinates: transmission density, at each of which the gradient of the tangent line becomes 0.2. H stands for the amount of light to which a light-sensitive material is exposed, and can be defined as the product of the intensity of light to which a light-sensitive material is exposed and the time of exposure.
[0048] The negative-type silver halide light-sensitive material for color photography of the present invention has a latitude of 3.0 or more, preferably 3.0 to 8.0.
[0049] In the present invention, a light-sensitive emulsion layer of single-layer structure preferably contains, in combination, a silver halide emulsion of the largest average grain size having an average grain size of 0.2 to 2.0 /.Lm and a silver halide emulsion of the smallest average grain size having an average grain size of 0.05 to 1.0 u.m. It is possible that a light-sensitive emulsion of single-layer structure further contains one or more kinds of silver halide emulsion with a medium average grain size.
[0050] According to the present invention, the average grain size of silver halide emulsion having the largest average size is preferably 1.5 to 40 times larger than the average grain size of silver halide emulsion having the smallest average grain size.
[0051] As the silver halide emulsion to be used in the present invention, use can be made of silver halide emulsions normally employed. However, as the silver halide grains to be contained in an emulsion layer of single-layer configuration, it is preferable to employ a silver halide grain being composed of two or more phases differing in silver iodide content, in which the average silver iodide content of interior phases is larger than that of exterior phases. The use of such silver halide grains leads to an improvement in the sharpness of an image, and in the preservability and stability of a light-sensitive material.
[0052] Now, an explanation, will be given as to the above-mentioned silver halide grain being composed of two or more phases differing in silver iodide content, in which the average silver iodide content of interior phases is larger than that of exterior phases.
[0053] The following method can be used to confirm the fact that the average silver halide content of interior phases is higher than that of exterior phases.
[0054] When a silver halide emulsion contains silver halide grains in which a ratio of the grain size to the grain thickness is smaller than 5, the average content of silver iodide satisfies the following relationship: J1 > J2 wherein J1 stands for the average silver iodide content obtained by X-ray fluorometry and J2 stands for the silver iodide content of the surface portion of a grain which is obtained by X-ray photoelectronic spectrophotometry.
[0055] The term "grain size" as referred to herein means the diameter of a circumcircle of a plane of a grain having the largest projection area.
[0057] Prior to measurement, an emulsion is pretreated according to the following method. A pronase solution is added to an emulsion, and the resultant is stirred at 40 C for one hour to decompose gelatin. The resultant is then centrifuged to make emulsion grains sedimented. After removing a supernatant, a pronase solution is added to decompose gelatin in the same manner as mentioned above. The resultant is again centrifused. After removing a supernatant, a distilled water is added to make emulsion grains dispersed in the distilled water. The resultant is centrifuged and a supernatant is removed. This procedure of washing is repeated three times. Subsequently, emulsion grains are dispersed in ethanol. The resultant is coated on a mirror-ground silcon wafer to form a thin coating layer. The resulting product is used as a test piece.
[0058] For X-ray photoelectronic spectrophotometry, for example, ESCA/SAM560 (manufactured by PHI Company) is used. An Mg-Ka ray is used as the X-ray for excitation. Voltage and electric current for generating the X-ray are 15 KV and 40 mA, respectively. Path energy is 50 eV.
[0059] In order to know the composition of halides on the surface of a test piece, Ag3d, Br3d, and 13d3/2 electrons are detected. The composition ratio is calculated in accordance with the relative sensitivity coefficient method, by using the integrated intensity of each peak. As the relative sensitivity coefficient, 5.10, 0.81, and4.592 are respectively employed for Ag3d, Br3d, and 13d3/2. As a result of this, the composition ratio is given in terms of atomic percent.
[0060] In the case of an emulsion containing silver halide grains in which the ratio of the grain size to the grain thickness is smaller than 5, it is preferred that the grain size distribution of this emulsion is monodispersed. A monodispersed silver halide emulsion means an emulsion in which the weight of silver halide grains with grain sizes falling in the range of ±20% of the average grain size (d) accounts for 60% or more, preferably 70% or more, more preferably 80% or more, of the total weight of silver halide grains.
[0061] The term "average grain size" (d) as referred to herein means a diameter (di) which makes the value of ni x di3 reaches the maximum, wherein ni represents the frequency of a silver halide grain having a diameter of di (figures of three desimal places are regarded as significant figures, and the smallest cipher is rounded).
[0062] The term "grain size" as referred to herein means a diameter of a grain when the grain is spherical. As to grains in other shapes than sphere, the grain size is obtained by converting its projected image into a circular image having the same area.
[0063] The grain size can be obtained by measuring the diameter of an electron-microphotographed image (x 10,000 to 50,000) of a grain. Alternatively, the grain size can be obtained by measuring the area of the projected image of a grain. (measurement is done with respect to more than 1,000 granules selected arbitrarily.)
[0064] In the present invention, the size distribution of a monodispersed emulsion may preferably 20% or less, more preferably 15% or less. The size distribution is defined by the following formula:
[0065] In the above formula, the average grain size and the standard deviation of grain size can be obtained from the value or di, which is defined above.
[0066] When a silver halide emulsion contains flat-type silver halide grains in which the ratio of the grain size to the grain thickness is 5 or more on average, the silver iodide content satisfies the following relationship: Fi > Js wherein J, is as defined above. J3 means the average content of silver iodide obtained by X-ray micro-analysis method. J3 is obtained at a portion which is 80% way in the direction of diameter from the central portion of a grain.
[0068] Silver halide grains are dispersed on a grid for electron microscopic examination, which is prepared by attaching an energy diffusion-type X-ray analyzer to an electron microscope. The magnification is set by chilling with liquid nitrogen in such a way that one granule comes within the analysing field. For a predetermined period of time, the intensities of an AgL« ray and an ILa ray are added up. The silver iodide content is calculated by using a calibration curve, from the intensity ratio of lLa/AgLa which is obtained in advance.
[0069] In a silver halide emulsion containing flat-type silver halide granules in which the average ratio of the grain size to the grain thickness is 5 or more, said ratio may preferably be in the range of 6 to 100, more preferably 7 to 50.
[0070] The average silver iodide content may preferably be in the range of 2 to 20 mol%, more preferably 5 to 15 mol%, most preferably 6 to 12 mol%.
[0071] In a silver halide emulsion containing silver halide grains in which the ratio of the grain size to the grain thickness is smaller than 5, the silver iodide content at the surface portion of a grain (J2) obtained by X-ray photoelectronic spectrophotometry may preferably be in the range of 0 to 6 mol%, more preferably 0 to 5 mol%, most preferably 0.01 to 4 mol%.
[0072] In a silver halide emulsion containing flat-type silver halide grains in which the ratio of the grain size to the grain thickness is 5 or more on average, the average silver iodide content obtained by the X-ray micro-analysis at a portion which is 80% or more away in the direction of diameter from the central portion of a grain (J3) may preferably be in the range of 0 to 6 mol%, more preferably 0 to 5 mol%, most preferably 0.01 to 4 mol%. The thickness of a flat-type silver halide grain may preferably be in the range of 0.5 to 0.01 u.m, more preferably 0.3 to 0.05 nm. The average grain size of flat-type silver halide grains may preferably be 0.5 to 30 u.m.
[0073] In a silver halide emulsion comprising flat-type grains having a core/shell structure and a grain size/grain thickness ratio of 5 or more, it is preferred that silver iodide grains are localized in the central portion of a grain.
[0074] In the case of a silver halide emulsion comprising silver halide grains with a core/shell structure and having a grain size/grain thickness ratio of smaller than 5, a grain has a structure consisting of two or more phases differing in silver iodide content. In this structure, a phase having the largest silver iodide content (hereinafter referred to as "core") is located other portions than the outermost surface (hereinafter referred to as "shell").
[0075] In the present invention, the silver iodide content of the interior phases (core) of a grain may preferably be in the range of 6 to 40 mol%, more preferably 8 to 40 mol%, most preferably 10 to 40 mol%. The silver iodide content of the outermost surface (shell) of a grain may preferably be smaller than 6 mol%, more preferably 0 to 4.0 mol%.
[0076] In a core/shell type silver halide grain, the volume occupied by the shell portion may preferably 10 to 80%, more preferably 15 to 70%, most preferably 20 to 60%, of the total volume of the grain.
[0077] The volume occupied by the core portion may preferably be 10 to 80%, more preferably 20 to 50% of the total volume of the grain.
[0078] Differences in silver iodide content between the core portion and the shell portion may have a sharp boundary. It is also possible that the differences constitutes a continuous line which does not have any clear boundary. It is also preferred to employ a silver halide grain having a medium phase between the core and the shell. The silver iodide content of the medium phase is intermediate between the silver iodide content of the core and that of the shell.
[0079] In the case of a silver halide emulsion 'comprising silver halide grains with the above-mentioned medium phase, the volume of such medium phase may preferably be 5 to 60%, more preferably 20 to 55% of the total volume of the grain. It is preferred that a difference in silver iodide content between the shell and the medium phase and that between the medium phase and the core each may preferably be 3 mol% or more. A difference in silver iodide content between the shell and the core may preferably be 6 mol% or more. It is preferred that a silver halide emulsion comprising silver halide grains of core/shell structure is an emulsion of silver iodo-bromide.
[0080] In this case, the average content of silver iodide may preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Silver chloride may be contained in a silver iodo-bromide emulsion in such an amount as will not adversely affect the effects of the present invention.
[0081] A silver halide emulsion comprising silver halide grains of core/shell structure can be prepared by known methods disclosed in Japanese Patent O.P.I. Publication No. 177535/1984, 138538/1985, 52238/1984, 14331/1985, 35726/1985 and 25836/1985.
[0082] When a core/shell type silver halide grain is grown from a seed grain, as described in Examples of Japanese Patent O.P.I. Publication No. 138538/1985, there is a possibility that the central portion of the grain has a region' with a halogen composition different from that of the core.
[0083] In this case, there is no restriction as to the halogen composition of a seed grain. For example, as the seed grain, use can be made of silver bromide, silver iodo-bromide, silver chloro-iodo-bromide, silver chloro-bromide, silver chloride. Of them, silver bromide or silver iodo-bromide having a silver iodide content of 12 mol% or less is preferable.
[0084] In the production of silver iodo-bromide or silver bromide, soluble silver salts and soluble halides are generally employed. As is apparent from Examples which will be given later, in order to obtain a light-sensitive material being excellent in preservability and stability, it is preferred that iodine salts are employed in the form of a crystallite of silver iodide.
[0085] As the crystallite of silver iodide, a crystallite of silver iodo-bromide with a high Agl content may also preferably be employed.
[0086] The distribution condition of silver iodide in a core/shell type grain can be examined by various physical measurement methods. For instance, it can be examined by measuring luminescence at lower temperatures or by the X-ray diffraction method, as described in Summaries of Lectures at 1981 annual convention of the Japanese Society of Photography.
[0087] A core/shell type silver halide grain may comprise a normal crystal, such as cubic, quadridecahedral, and octahedral crystal. A silver halide grain may also comprise a twin crystal. It is also possible to employ a mixture of normal crystals and twin crystals. In the present invention, however, a silver halide grain comprising a normal crystal is preferable.
[0088] In a silver halide emulsion comprising flat-type silver halide grains with a ratio of the grain size to the grain thickness of 5 or more, in which silver iodide is localized in the central portion of the grain, the volume of the central portion may preferably be 80% or less, more preferably 10 to 60% of the total volume. The silver iodide content of the central portion may preferably be 5 to 40 mol%, more preferably 10 to 30 mol%.
[0089] The surface portion with a lower silver iodide content may preferably comprises silver iodo-bromide containing 0 to 10 mol%, preferably 0.1 to 6.0 mol%, of silver iodide.
[0090] A silver halide emulsion comprising flat-type silver halide grains in which silver iodide is localized in the central portion can be prepared by a known method disclosed, for example, in Japanese Patent O.P.I. Publication No. 99433/1984.
[0091] A silver halide emulsion to be used in the present invention can be chemically sensitized by known technique. A silver halide emulsion can be spectrally sensitized by using a sensitization dye so that it can be sensitive to a desired wavelength region.
[0092] According to the present invention, in order to improve the preservability of a light-sensitive material and the preservability of an latent image, it is preferred that a silver halide light-sensitive material contains a nitrogen-containing heterocyclic mercapto compound. The term "preservability of a light-sensitive material" means the preservability of a light-sensitive material before photographing, against various external conditions including temperature and humidity. The term "preservability of an latent image" means the preservability of a light-sensitive material after photographing. Addition of the nitrogen-containing heterocyclic mercapto compound is more preferable when two or more of blue-, green- and red-sensitive layers of the light-sensitive material are each constructured with single layer.
[0093] In the present invention, as the nitrogen-heterocyclic mercapto compound, it is preferable to employ compounds represented by the following Formula I.
wherein Z is a group of atoms necessary for forming a 5- or 6-membered heterocyclic ring comprising atoms selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, and a selenium atom and said heterocycle may be condensed with another ring; and M is a hydrogen atom, an alkali metal atom or an ammonium group.
[0094] As the heterocyclic group to be formed by Z, there may be mentioned, for example, pyridine, pyrimidine, imidazole, benzoimidazole, naphthoimidazole, oxazole, benzoxazole, naththoxazole, thiazolinethiazole, benzothiazole, naphthothiazole, selenazole, benzoselenazole, naphthoselenazole, triazole, oxadiazole, thiadiazole, triazine, tetrazole, purine, azaindene. These heterocycles may have a substituent. As such substituent, there may be mentioned for example, an aromatic group, an aliphatic group, a hydroxy group, an alkoxy group, an aryloxy group, an amino group, a nitro group, a halogen atom, a carboxyl group and a salt thereof, a sulfo group and a salt thereof, a mercapto group and a salt thereof, an alkylmercapto group, an acrylamino group, a sulfamoyl group, a sulfoamino group, a carbomoyl group.
[0095] Of the compounds represented by Formula I, compounds represented by the following Formulae II, III and IV are especially preferable.
wherein Ar is a phenylene group, a naphthylene group, or a cyclohexylene group; R, is a hydrogen atom or a substituent of Ar; and M has the same meaning as mentioned above.
wherein Z1 is a sulfur atom, an oxygen atom, a selenium atom, or a
R2 is a substituent or a hydrogen atom; m is an integer of 1 to 4, and when m is 2 to 4, R2 may either be identical or different, or they may be combined with each other to form a condensed ring; and M has the same meaning as mentioned above.
wherein Z2 is a sulfur atom, an oxygen atom, or a selenium atom or a
group; R3 is a hydrogen atom, an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an amino group, an acylamino group, a sulfonamido group, or a heterocyclic group; R4 is a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an aralkyl group, -CORS, -SO2R5, -NHCOR6, or -NHS02R6; R5 is an alkyl group, an aryl group, a cycloalkyl group, an aralkyl group, or an amino group; R6, is an alkyl group, an aryl group, a cycloalkyl group, or an aralkyl group; and M has the same meaning as mentioned above.
[0096] The specific examples of the nitrogen-containing heterocyclic mercapto compound will be given below. The compound to be used in the present invention are not limited to those given below.
Exemplified Compound
[0097]
The compounds represented by Formula II can be, prepared by methods described in Japanese Patent O.P.I. Publication No. 111846/1981, British Patent No. 1,275,701, U.S. Patent Nos. 3,266,897 and 2,403,927, or by methods which are similar to these methods.
[0098] The compounds represented by Formula III can be prepared by methods described in U.S. Patent No. 2,824,001, Japanese Patent Examined Publication No. 28496/1965, and Journal of Chemical Society Vols. 4237 (1952) and 1723 (1951), or by methods which are similar to these methods.
[0099] The compounds represented by Formula IV can be prepared by methods described in U.S. Patent Nos. 2,843,491, 3,017,270, British Patent No. 940,169, Japanese Patent O.P.I. Publication Nos. 59463/1980 and 102639/1976, or methods which are similar to these methods.
[0100] Generally, it is difficult to determine the amount of a nitrogen-containing heterocyclic mercapto compound to be added. In the present invention, it is preferable to add the mercapto compound in such an amount that the addition will make a light-sensitive material desensitized by not more than 0.20, preferably not more than 0.10, in terms of OIogH.
[0103] As the binder to be used in silver halide emulsion layers, gelatin may advantageously be employed.
[0104] Emulsion layers and other hydrophilic layers may be hardened. Further, a plastizizer or a dispersed product (latex) of a synthetic polymer which is insoluble or slightly soluble in water may be contained in emulsion layers.
[0105] In the present invention, a coupler is employed in the emulsion layers of a silver halide color light-sensitive material.
[0106] As the cyan coupler, an ureidophenol type cyan coupler may preferably be employed from the view point of the preservabilities of light-sensitive material and latent image. An ureidophenol type cyan coupler means a phenol-type cyan coupler having an ureido group at the 2-position. In the present invention, it is preferable to employ an ureidophenol-type cyan coupler represented by the following Formula CU.
wherein X is a hydrogen atom or a group capable of being split-off upon a coupling reaction with an oxidized aromatic primary amine color development agent; R' is an aryl group or a heterocyclic group; R2 is an aliphatic group or an aryl group; R1 and R2 each may have a substituent; R' and R2 each may include groups capable of forming polymers larger than dimers by R' or R2. The shape and size of R' and R2 are such that R' and R2 can, singly or in combination, allows a coupler represented by Formula CU and a dye formed by said coupler to have a anti-diffusibility.
[0107] AS the aryl group represented by R1 or R2, there may preferably be employed a phenyl group or a naphthyl group.
[0108] As the substituent for R1 or R2, there may be mentioned a halogen atom, a nitro group, a cyano group, an alkyl group, an aryl group, an amino group, a hydroxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxysulfonyl group, an aryloxysul- fonyl group, a carbamoyl group, a sulfamoyl group, an acyloxy group, a carbonamido group, and a sulfonamido group. The number of said substituent may preferably be 1 to 5. When the number of the substituent is 2 or more, said substituents may either be identical or different.
[0109] As the substituent for R1, it is preferable to empoly a halogen atom, an alkylsulfonyl group, and a cyano group.
[0110] The preferred examples of R2 are those represented by the following Formula CU-II.
wherein J is an oxygen atom or a sulfur atom; k is an integer of 0 to 4; ℓ is 0 or 1; when k is 2 or more, R4 may either be identical or different; R3 is an alkylene group; and. R4 is a substituent. '
[0111] As the substituent represented by R4, there may be mentioned for example, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a hydroxy group, an acyloxy group, an alkylcalbonyloxy group, an arylcarbonyloxy group, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an acyl group, an acylamino group, a sulfonamido group, a carbamoyl group, and a sulfamoyl group.
[0112] As the split-off substituent represented by X, there may be mentioned a halogen atom; groups such as an aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group, an acyloxy group, a sulfonamido group, and a succinimide group, in each of said groups, an oxygen atom or a nitrogen atom is directly bounded to a coupling position of coupler residue. The specific examples of such group are described in U.S. Patent Nos. 3,476,563 and 3,749,735, Japanese Patent O.P.I. Publication Nos. 37425/1972, 10135/1975, 117422/1975, 130441/1975, 108841/1976, 120334/1975, 18315/1977, 105226/1978, and Japanese Patent Examined Publication No. 36894/1973.
[0113] A phenol-type cyan coupler containing an ureido group at the 2-position may be used in combination with other cyan couplers. In this case, the phenol-type cyan coupler containing an ureido group at the 2- position may preferably be employed in an amount of 10 mol% or more with respect to the total amount of cyan couplers employed.
[0114] The following are the specific examples of the phenol-type cyan couplers containing an ureido group at the 2-position. These examples are given only for the purpose of illustration.
[0115] Other examples than those mentioned above of an ureido group-containing phenol-type cyan coupler are described, for example, in Japanese Patent O.P.I. Publication Nos. 65134/1981, 204543/1982, 204544/1982, 204545/1982, 33249/1983, 33253/1983, 98731/1983, 118643/1983, 179838/1983, 187928/1983, 65844/1984, 71051/1984, 86048/1984, 105644/1984, 111643/1984, 111644/1984, 131939/1984, 165058/1884, 177558/1984, 180559/1984, 198455/1984, 35731/1985, 37557/1985, 49335/1985, 49336/1985, 50533/1985, 91355/1985, 107649/1985, 107650/1985, and 2757/1985.
[0116] It is preferred that an ureido group-containing phenol-type cyan coupler is added in a red-sensitive silver halide emulsion layer. The amount of this coupler may preferably be 1.0 x 10-3 to 1.0 mol, more preferably 5.0 x 10-3 to 8.0 x 10-1 mol, per mol of a silver halide.
[0117] Meanwhile, by the use of a 5-pyrazolone-type two-equivalent magenta coupler, lowering in the optical density of a color image can be suppressed to a minimum level even under atmosphere conditions with formalin. However, when a 5-pyrazolone-type two-equivalent magenta coupler is used in a green-sensitive layer, the preservability of an unexposed photosensitive material and that of a latent image formed in an exposed photosensitive material are significantly deteriorated. In order to solve the above problem, in one embodiment of the present invention, a green-sensitive layer has a single-layer structure and contains a DIR compound and a 5-pyrazolone-type two-equivalent magenta coupler.
[0118] The 5-pyrazolone-type two-equivalent magenta coupler is represented by the following Formula M.
wherein Cp is a residue of a 5-pyrazolone-type coupler; * represents a coupling position of a coupler; and X is a substituent which can be split-off when a dye is formed by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.
[0119] As the substituent represented by X, there may be mentioned a halogen atom; a monovalent group such as an alkoxy group, an aryloxy group, a heterocyclicoxy group, an acyloxy group, an alkythio group; an arylthio group, a heterocyclic thio group, an
group, wherein X is a group of atoms which are necessary to form a 5- or 6-membered ring with the nitrogen atom shown in the formula and atoms selected from a carbon atom; an oxygen atom, a nitrogen atom, and a sulfur atom, an acylamino group and a sulfonamido group; and a divalent group such as an alkylene group. When X is a divalent group, a dimer is formed with X.
[0120] The specific examples of the group represented by X are given below. Halogen atom: chlorine, bromine, fluorine
Alkoxy group:
Aryloxy group:
Heterocyclic oxy group:
Acyloxy group:
Alkylthio group:
Arylthio group:
Heterocyclic thio group:
Pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group:
Acylamino group:
Sulfonamido group:
Alkylene group:
[0131]
As the 5-pyrazolone-type magenta coupler, it is preferable to use those represented by the following Formulae M-1 and M-2.
[0132] In the above Formulae, R2 is a hydrogen atom or a substituent; R3 is a substituent; X has the same meaning as mentioned in Formula M; and ℓ is for 1 to 5, and when ℓ is 2 or more, R2 may either be same or different.
[0133] As the substituent represented by R2, there may be mentioned a halogen atom, and a group such as an alkyl group, a cycloalkyl group, an aryl group and a heterocyclic group, which are combined with the phenyl group directly or via a divalent atom or a divalent group.
[0134] Examples of the above-mentioned divalent atom or divalent group include an oxygen atom, a nitrogen atom, a sulfur atom, a carbonylamido group, an aminocarbonyl group, a sulfonylamino group, an aminosulfonyl group, an amino group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a ureylene group, a thioureylene group, a thiocarbonylamino group, a sulfonyl group, and a sulfonyloxy group.
[0135] The alkyl group, the cycloalkyl group, the aryl group and the heterocyclic group which can be used as the substituent represented by R2 may have a substituent. As such substituent, there may be mentioned a halogen atom, a nitro group, a cyano group, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a ureido group, a urethane group, a sulfonamido group, a heterocyclic group, an arylsulfonyl group, an alkylsulfonyl group, an arylthio group, an alkylthio group, an alkylamino group, an anilino group, a hydroxy group, an imido group, and an acyl group.
[0136] As the group represented by R3, there may be mentioned, for example, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group. These groups each may have a substituent. When these groups have a substituent, the groups mentioned above as the examples of R2 may be used as the substituent.
[0137] The especially preferred examples of the split-off group represented by X include an alkylthio group, an arylthio group, an aryloxy group, an acyloxy group,
(Xi is as defined above), and an alkylene group.
[0138] The specific examples of a pyrazolone-type coupler usable in the present invention are given below. These examples are given only for the purpose of illustration.
[0139] A 5-pyrazolone-type two-equivalent magenta coupler may be added preferably in an amount of 2 x 10-5 to 1 x 10-3 mol/m2, more preferably 5 x 10-5 to 1 x 10-3 mol/m2. The above-mentioned two-equivalent magenta coupler may be used in combination with a four-equivalent coupler. In this case, a two-equivalent coupler may be employed preferably in amount of 50 to 100 mol%, more preferably 70 to 100 mol%, most preferably 100 mol%, of the total amount, namely the whole amount, of couplers.
[0140] The term "four-equivalent coupler" as referred to herein means a coupler which does not have a substituent at a coupling position. As the four-equivalent magenta coupler, there may be mentioned indazolones, cyanoacetyls, 5-pyrazolones, and pyrazoloazoles such as pyrazoloimidazole and pyrazolotriazole. Of them, 5-pyrazolones and pyrazoloazoles are preferable.
[0141] On the other hand, in Japanese Patent O.P.I. Publication No. 145243/1987, there is disclosed a coupler which releases a dye or a precursor thereof by a coupling reaction with an oxidized product of an aromatic primary amine color development agent, wherein said dye or said precursor is bounded, directly or via a TIMING group, to an active position of said coupler. In this coupler, the absorption maxima of a dye to be released or a dye to be formed from a precursor is shifted to the side of short, wavelengths. In this publication, there is a description to the effect that the use of this coupler leads to an increase in optical density and improvement in color reproducibility.
[0142] Further, in Japanese Patent O.P.I. Publication No. 71844/1988, there is a description to the effect that the graininess of an image can be improved by using a DIR coupler in combination with the above-mentioned coupler. However, even when a DIR coupler is used in combination with the above-mentioned coupler, there are still problems in preservability and stability against changes of processing conditions. By the present invention, these problems has been effectively solved.
[0143] Now, an explanation will be given on the above-mentioned coupler which releases a dye or its precursor by a coupling reaction with an oxidized product of an aromatic primary amine color development agent, wherein said dye or said precursor is bounded, directly or via a TIMING group, to an active position of said reaction, characterized in that a dye to be released or a dye to be formed from said precursor has its absorption maxima shifted to the short wavelength region before being released (this coupler will be referred to as "shift coupler").
[0144] There is no restriction as to the kind of a coupler in which a dye or its precursor is bounded to said active position. Use can be made of anything as long as it can release a dye or its precursor by a coupling reaction with an oxidized product of an aromatic primary amine color developing agent. For example, it is possible to employ a yellow coupler, a magenta coupler, and a cyan coupler, which are generally used in a silver halide photosensitive material for color photography, which is to be subjected to color development. It is also possible to employ a residue of a coupler which does not produce essentially an image-producing dye. The preferred examples of such coupler are given below.
[0145] In the above Formula la, R1 is an alkyl group, an aryl group, or an arylamino group; and R2 is an aryl group or an alkyl group.
[0146] In the above Formula Ib, R3 is an alkyl group or an aryl group; R4 is an alkyl group, an acylamino group, an arylamino group, an arylureido group, or an alkylureido group.
[0147] In the above Formula Ic, R4 has the same meaning as that of R4 shown in Formula Ib, Rs is an acylamino group, a sulfonamido group, an alkyl group, an alkoxy group, or a halogen atom.
[0148] In the above Formulae Id and le, R6 is an alkyl group or an aryl group; and R7 is an alkyl group, an aryl group, an acylamino group, an arylamino group, an alkoxy group, an arylureido group or an alkylureido group.
[0149] In the above Formula If, R8 is a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamido group; and Rs is an acylamino group, a carbamoyl group, or an arylureido group.
[0150] In the above Formula Ig, R9 has the same meaning as that of Rg shown in Formula If; and R10 is an amino group, a carbonamido group, a sulfonamido group or a hydroxyl group.
[0151] In the above Formula Ih, R1 is a nitro group, an acylamino group, a succinimido group, a sulfonamido group, an alkoxy group, an alkyl group, a halogen atom or a cyano group.
[0152] In the above Formulae, t shown in Formula Ic is an integer of 0 to 3; n shown in If and Ih is an integer of 0 to 2; and m shown in Ig is an integer of 0 to 1. When each of I and n is 2 or more, RsS, RsS and R11S each may be same or different.
[0153] The above groups may include ones being substituted. As the preferable substituent, there may be mentioned a halogen atom, a nitro group, a cyano group, a sulfonamido group, a hydroxyl group, a carboxy group, an alkyl group, an alkoxy group, a carbonyloxy group, an acylamino group, and an aryl group. It is also preferable to employ a substituent containing a coupler portion which constitutes a so-called bis-type coupler or a polymer coupler.
[0154] There is no restriction as to the lipophylicity of groups of R1 to R11 shown in the above Formulae. R1 to R11 each may have an appropriate lopophylicity according to purposes.
[0155] In the case of ordinary image-producing couplers, the total number of carbon atoms of R1 to R10 preferably be 10 to 60, more preferably 15 to 30. When a color-forming dye is needed to move appropriately in a light-sensitive material, it is preferred that the total number of carbon atoms of R1 to R10 is 15 or less.
[0156] The term "a coupler which does not essentially produce an image-producing dye" as referred to herein means not only a coupler which does not produce a color-forming dye but also a coupler in which a dye image does not remain after development.
[0157] Examples of a coupler which does not leave a color image after development include a coupler forming a dye which effuses from a photosensitive material into a processing liquid and a coupler forming a dye which is bleached by a reaction with ingredients of a processing liquid. In the former coupler, the total number of R1 to R10 may preferably be 15 or less. Further, the former coupler may preferably contain, as the substituent for each of R1 to Rio, at least one carboxyl group, at least one alkylsulfonamido group, or at least one alkylsulfonamido group.
[0158] The preferable examples of the timing group are given below.
wherein B is a group of atoms necessary for the formation of a benzene ring or a naphthalene ring; Y is -0-, -S-, or
which will be bounded to an active position of a coupler residue; and R12, R11 and R11 each is a hydrogen atom, an alkyl group or an aryl group.
[0159] One side of the above-described
group is substituted at the ortho- or para-position relative to Y, and the other side of said group is bounded to the above-mentioned dye or its precursor.
wherein Y, R12 and R13 are as defined above; Ris is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfo group, an alkoxycarbonyl group or a heterocyclic residue; and R16 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acid-amido group, a sulfonamido group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group or a cyano group. Y is bounded to an active point of a coupler residue and
is bounded to a dye or its precursor.
[0160] As the timing group which releases a dye or its precursor by an intermolecular nucleophilic substitution reaction, there may be mentioned those represented by the following Formula. Formula Ik -Mu-D-E-wherein Mu represents a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom, which group is bounded to an active position of a coupler residue; E is an electron attractive group containing an electron deficient group such as a carbonyl group, a thiocarbonyl group, a phosphinyl group and a thiophosphinyl group; An electron attractive group represented by E is bounded to a hetero atom of a dye or its precursor; and D is a bonding group connecting D and Mu, which group is subjected to, after Mu is released from a coupler residue, an intramolecular nucleophilic displacement reaction caused by the formation of 3- or 7-membered ring, thereby releasing a dye or its precursor.
[0161] As the precursor, there may be employed precursors in which auxochromes of a dye are protected by a group which is released under alkaline conditions.
[0162] As the dye-releasing shift coupler, it is preferable to employ couplers in which auxochromes of a dye are bounded to a coupler residue or a timing group. In the case of a shift coupler releasing a precursor, a portion being bounded to a coupler residue or a timing group may either be auxochromes or non- auxochromes. As the auxochromes, there may be mentioned hetero atoms such as an oxygen atom, a nitrogen atom and a sulfur atom.
[0163] As the above-mentioned dye, use can be made of dyes described in J. Fabian and H. Hartmann, "Light Absorption of Organic Colorants" (Springer Verlag).
[0164] Preferable dyes are those having an appropriate hue in a condition where auxochromes are released. Especially preferable dyes are a hydroxy group-substituted aromatic azo dye and a hydroxy group-substituted heterocyclic aromatic azo dye. These dyes are represented by the following Formula. HX-Y1-N =N-Z wherein HX is auxochromes; Y1 is a group of atoms containing at least one unsaturated bond which is conjugated with an azo group, in which atoms constituting said unsaturated bond is combined with X; and Z is a group of atoms containing at least one unsaturated bond which is conjugated with an azo dye. The total number of carbon atoms contained in Y1 and Z may preferably 10 or more.
[0165] X may preferably be an oxygen atom or a sulfur atom Y1 and Z preferably be an aromatic group or an unsaturated heterocyclic group. As the heterocyclic group, a phenyl group or a naphthyl group is preferable. As the unsaturated heterocyclic group, a 4- to 7-membered heterocyclic group containing a hetero atom selected from a nitrogen atom, a sulfur atom and an oxygen atom is preferable. This group may be a benzene condensed ring.
[0166] Y1 and Z may be substituted. As the substituent, there may be mentioned an aliphatic group, an aromatic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, an alkylthio group, an arylthio group, a heterocyclic group, a sulfonyl group, a sulfonamido group, an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyl group, an amino group, a ureido group, a sulfamoyl group, a carbamoyl group, a hydrazinyl group, a halogen atom, a nitro group, a nitroso group, a cyano group, a sulfoxyl group, and a hydroxyl group.
[0167] Of the dyes represented by Formula DY, the following are preferable.
wherein X is an oxygen atom or a sulfur atom; W is a substituent selected from those listed as the substituent for Y in Formula DY; q is 0 to 2; s is 0 to 3; r is 0 to 4; B1 to B4 each is a hydrogen atom or the same substituent as that mentioned with respect to W; and B1 and B2, B3 and B4. may respectively combine to form a benzene condensed ring. Said benzene condensed ring may have a substituent represented by W.
[0169] V1 stands for an oxygen atom, a sulfur atom or an imino group. Said imino group may includes ones having a substituent.
[0170] V2 stands for an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. V2 may includes ones having a substituent. As the substituent, there may be mentioned substituents listed as the substituent for Y in Formula DY.
[0171] V3 is an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, a heterocyclic group, a halogen atom, a cyano group, an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkoxy group, an aryloxy group, an acylamino group, a diacylamino group, an N-alkylacylamino group, an N-arylamylamino group, un ureido group, an amino group, a cyclic amino group, or a sulfonamido group. These groups have a carbon number of 1 to 32, preferably 1 to 22. These groups may be substituted. As the substituent, there may be mentioned those listed as the substituent for Y in Formula DY.
[0172] Za, Zb and Zc each are methyne group including those containing a substituent, = N-, or -NH-. One of the Za-Zb bond and the Zb-Zc bond is a double bond, and the other is a single bond. It is not possible that all of Za, Zb and Zc are = N- or -NH-. When Zb-Zc is a carbon-carbon double bond, it may constitute part of an. aromatic ring. This atomatic ring may be substituted. As the substituent, there may be mentioned those listed as the substituent for Y.
[0173] Examples of a shift coupler producing a yellow dye and its precursor
Examples of a shift coupler producing a magenta dye and its precursor
Examples of a shift coupler producing a cyan dye and its precursor
[0174] Of the above-mentioned shift couplers, preferred are those represented by Formula S. Formula S Coup (̵Time)̵a X-D' wherein Coup is a coupler residue which can release by a reaction with an oxidized product of an aromatic primary amine color developing agent; Time is a timing group; a is 0 or an positive integer; 0 is a dye residue; and X is an auxochromatic group.
[0175] The amount of the shift coupler may preferably be 0.005 to 2 g/m2, more preferably 0.01 to 1 g/m2.
[0176] In a light-sensitive material,it is possible to add a polymer mordant to a shift coupler-containing layer or layers adjacent to said shift coupler-containing layer.
[0177] In the present invention, it is also possible to employ, in combination with a shift coupler, a coupler other than a shift coupler in the same color-sensitive layer. In this case, a coupler other than a shift coupler may preferably be employed in an amount of 0.01 to 20 mol, more preferably 0.01 to 10 mol, per mol of a shift coupler.
[0178] By adding into at least one layer constituting a light-sensitive material of the present invention, in which at least one color-sensitive layer has a single-layer structure, a compound capable of splitting off a bleaching accelerator or its precursor by a reaction with an oxidized product of a color developing agent, the desilvering-readiness and stability to processing conditions of the light-sensitive material can be improved, as compared with the case of a photosensitive material having no such single-layered color-sensitive layer.
[0179] The bleaching accelerator releasing compound (BAR compound) may preferably be represented by the following formula. Formula BAR-I
wherein A is a coupler residue which can be subjected to a coupling reaction with an oxidized product of a color developing agent, or a residue of an oxidation-reduction nucleus which can be. cross-oxidized with an oxidized product of a color developing agent; TIME is a timing group; BA is a bleaching accelerator or its precursor; m" is 0 or 1; and when A is a coupler residue, t is 0, and when A is a residue of an oxidation-reduction nucleus, is 0 or 1.
[0180] Of the BAR compounds represented by Formula BAR-I, preferable are those represented by Formulae BAR-II and BAR-III.
wherein Cp is a coupler residue which can be subjected to a coupling reaction with an oxidized product of a color developing agent; * is a coupling position of a coupler; TIME is a timing group; R1 is an aliphatic group, an aromatic group, a saturated heterocyclic group or a 5- or 6-membered aromatic nitrogen-containing heterocyclic group; R2 is a water solubilizing substituent or its precursor; R3 is a hydrogen atom, a cyano group, -COR4, -CSR4,
or a heterocyclic group, in which R4 is an aliphatic group or an aromatic group, Rs, R6 and R7 each are a hydrogen atom, an aliphatic group or an aromatic group; and m and n each are 0 or 1.
[0181] As the coupler residue represented by Cp, there may be mentioned residues capable of forming yellow, magenta or cyan dyes and residues forming substantially colorless products by the coupling reaction.
[0182] The representative examples of a yellow coupler residue are described in U.S. Patent Nos. 2,298,443, 2,407,210, 2,875,057, 3,048,194, 3,265,506, 3,447,928, and Farbkuppler eine Literaturuversiecht Agfa Mitteilung (Band II) pp112 -126 (1961). Of them acylaceloanilides such as benzolacetoanilide and pyvaloylacetoanilide are preferable.
[0183] The representative examples of a magenta coupler residue are described in U.S. Patent Nos. 2,369,489, 2,343,703, 2,311,182, 2,600,788, 2,908,573, 3,062,653, 3,152,986, 3,519,429, 3,725,067, 4,540,654, Japanese Patent O.P.I. Publication No. 162548/1984 and in the above-mentioned Agfa Mitteilung (Band II) pp126 - 156 (1961). Of them, pyrazolone and pyrazoloazoles, e.g., pyrazoloimidazole, pyrazolotriazole, are preferable.
[0184] The representative examples of a cyan coupler residue are described in U.S. Patent Nos. 2,367,531, 2,423,730, 2,474,293, 2,772,162, 2,395,826, 3,002,836, 3,034,892, 3,041,236, 4,666,999, and in the above-mentioned Agfa Mitteilung (Band II), pp156 - 175 (1961). Of them, phenols and naphthols are preferable.
[0185] The representative examples of a coupler residue which forms substantially colorless products are described in British Patent No. 861,138 and U.S. Patent Nos. 3,632,345, 3,928,041, 3,958,993, and 3,961,959. Of them a cyclic carbonyl compound is preferable.
[0186] A timing group represented by TIME is a group which allows a bleaching accelerator and its precursor (BA) to be split-off from Cp, while controlling time. This group may contain a group capable of controlling the rate of a reaction between Cp and an oxidized product of a color developing agent, the rate of diffusion of -TIME-BA split-off from Cp, and the rate of splitting off of BA.
[0188] (*) is a portion to be bounded to an active position of Cp; and (*) (*) is a portion to which -S-R1-R2 or
is bound. (1) A group which causes a cleavage reaction by using an electron transfer reaction along with a conjugated system.
[0189] Examples of such group include those described in Japanese Patent O.P.I. Publication Nos. 114,946/1981, 154,234/1982, 188,035/1982, 98,728/1983, 160,954/1983, 162,949/1983, 209,736/1983, 209,737/1983, 209,738/1983, 209,739/1983, 209,740/1983, 86,361/1987 amd 87,958/1987.
[0190] Of them, groups represented by the following Formulae TIME-I and TIME-II are preferable.
wherein B is a group of atoms necessary for the formation of a benzene ring or a naphthalene ring; Y is -0-, -S- or
and R12, R13 and R14 each are a hydrogen atom, an alkyl group or an aryl group.
[0191] The above-described
group is substituted at the orth- or para-position relative to Y.
wherein Y, R12 and R13 are as defined above; R15 is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfo group, an alkoxycarbonyl group or a heterocyclic group; and R16 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an amino group, an acylamino group, a sulfonamido group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group or a cyano group.
(2) A group which causes a cleavage reaction by using an intramolecular nucleophilic substitution reaction.
[0192] Examples of such group include those described in U.S. Patent No. 4,248,962 and Japanese Patent O.P.I. Publication No. 56,837/1982. Of them, preferable are those represented by Formulae TIME-III, TIME-IV and TIME-V.
wherein Z1 is
; and
wherein R19 is a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R17 is a hydrogen atom, an alkyl group or an aryl group; and R18 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group,
, a cyano group, a halogen atom or a nitro group. R20 and R21 may either identical or different and each are the same group as that represented by R19; p is an integer of 1 to 4, q is 0, 1 or 2; r is an integer of 1 to 4; to is an integer of 1 to 3; when r or t is 2 or more, R18 may either be same or different; and when r or t is 2 or more, R18S may combined each other to form a ring.
(3) A group which uses a cleavage reaction of hemiacetal
[0193] Examples of such group include those described in U.S. Patent No. 4,146,396, Japanese Patent O.P.I. Publication Nos. 249,148 and 249,149.
[0194] Of them, groups represented by the following Formula TIME-VI are preferable.
wherein Z3 is
(*)-OCH2-O, or (*)-OCH2-S-; R17, R18 and R19 each have the same meaning as that mentioned in Formulae TIME-III, TIME-IV and TIME-V.
[0195] (4) A group represented by the following Formula TIME-VII, and described in German Patent (OSL) No. 2,626,315 and U.S. Patent No. 4,546,073.
wherein Z4 is (*)-0-, (*)-S- or
Zs is an oxygen atom, a sulfur atom or = N-R22; and R22 is a hydrogen atom or a substituent.
[0196] The alipahtic group represented by R1 of Formulae BAR-II and -III may be a saturated or unsaturated, straight-chain, branched-chain or cyclic aliphatic group having a carbon number of 1 to 8. This group may either be substituted or unsubstituted.
[0197] The aromatic group represented by R1 may preferably be an aromatic group having a carbon number of 6 to 10, more preferably a substituted or unsubstituted phenylene group.
[0198] The saturated heterocyclic group represented by R1 may be a 3- to 8-membered, preferably a 4- to 6- membered saturated heterocyclic group having a carbon number of 1 to 7, preferably 1 to 5, and containing at least one selected from an oxygen atom, a nitrogen atom and a sulfur atom.
[0199] The 5- or 6-membered aromatic nitrogen-containing heterocyclic group represented by R1 may preferably be represented by the following Formula H-I and H-II.
wherein a, b, c, e, f, g, h and i each are a nitrogen atom or a methyne group; d is an oxygen atom, a sulfur atom or an imino group; (*) is a position to which
is bounded; and (*) (*) is a position to which R3-S- or R2 is bound
[0201] R, may more preferably be an aliphatic group or
wherein L is a divalent aliphatic group or a phenylene group having a carbon number of 1 to 8.
[0203] The preferred examples of an water-solubilizing substituent or its precursor represented by R2 include - COOH, - COONa, - COOCH3, - COOC2H5, - NHS02CH3, - NHCOOCH3, - NHCOOC2Hs, - S03H, - SO3K, - OH,
-SO2NH2 , -NR10R11 wherein R10 and R11 each are a hydrogen atom or an alkyl group having a carbon number of 1 to 4, -CONHz, -COCH3, -NHCOCH3, -CH2CH2COOH, -CH2CH2NH2, -SCH2COOH,
-CH2COOH, -SCH2CONH2, -SCH2COCH3, -SCH2CH2COOH and -S-R1-R2
[0204] The especially preferred examples of a bleaching accelerator or its precursor represented by -S-R1-R2 include
and
[0205] The preferred examples of R3 include H, -CN, -COH, -COCH3, -COCH20CH3, -COCF3, -CSCH3, -CON(CH3)2, -CON(C2Hs)2, -CSN-(CH3)2,
-SCH3, -SCH2CH2N(CH3)2, -SCH2CH2OH, -SCH2CH2COOH, -NHCH3, -NHCH2CH2COOH and
[0206] The especially preferred examples of a bleaching accelerator or its precursor represented by
-OCOCH2CH2SH, -OCH2CH2SH,
-OCOCH2CH2SCOCH3,-OCOCH2CH2SCSCH3, -OCOCH2CH2SSCH2CH2COOH -OCH2CH2SSCH2CH2OH, -OCOCH2CH2SCN.
[0207] The specific examples of a BAR compound to be used in the present invention are given below. These examples are given only for the purpose of illustration.
[0208] There is no restriction as to the kind of layers to which a BAR compound is added. A BAR compound may be added to not only a silver halide light-sensitive emulsion layer but also an anti-halation layer, an intermediate layer, a yellow colloidal silver filter layer, and a protective layer. However, a BAR compound may preferably be added to a silver halide photosensitive emulsion layer.
[0209] A BAR compound can be added to a hydrophilic colloidal layer of a light-sensitive material for color photography by the following method: A BAR compound is dissolved, singly or in combination with another kind of a BAR compound, to a mixture of a high-boiling point solvent such as dibutyl phthalate, tricresyl phosphate and dinonyl phenol and a low boiling point solvent such as butyl acetate and propionic acid. The resultant is mixed with an aqueous solution of gelatin containing a surface active agent, and subsequently emulsified by means of a high-speed revolution mixer, a colloid mill or an ultrasonic dispersing machine. The resultant may be directly added to a coating liquid. Alternatively, it may be coagulated, cut into small pieces, washed with water and then added to a coating liquid.
[0210] The amount of a BAR compound to be added may preferably be 0.0005 to 5.0 mole, more preferably 0.005 mole to 1.0 mole, per mole of a silver halide.
[0212] In the present invention, it is also possible to employ a colored coupler contributing to color compensation, a competitive coupler, or other compounds capable of splitting off, by a coupling reaction with an oxidized product of a color developing agent, photographically usuful substances such as a developer, a solvent for a silver halide, a toning agent, a hardener, an anti-fogging agent, a chemical sensitizer, a spectral sensitizer and a desensitizer.
[0213] In the present invention, by adding at least one kind of high-boiling point solvent having a dielectric constant of 4.00 or more (at 25 C, 10 KHz), the preservability of a light-sensitive material can be improved. The preservability of a photosensitive material is further enhanced by the combined effect of the above-mentioned specific high boiling point solvent and at least two color-sensitive layers each being the single-layer structure.
[0214] As the above-mentioned high-boiling point solvent, it is preferable to employ solvents having a boiling point of 150°C or more and showing no miscibility with water. For instance, solvents represented by the following Formulae A to D are preferable. Formula A R1 -COOR2
Formula D R1 -O-R2 wherein Ri, R2 and R3 each are an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group; in Formula D, R1 and R2 may combine to form a ring; R4 is a group the same as Ri, -OR1 or -SR1; n is an integer of 1 to 5, and when n is 2 or more, R4 may either be same or different.
[0215] As the alkyl group represented by R1 to R3, there may be mentioned a methyl group, a butyl group, an octyl group, a nonyl group and an octadecyl group. Said alkyl group includes one having a substituent. As the substituent, there may be mentioned a halogen atom, a cycloalkyl group, an aryl group, an ester or the like.
[0216] As the cycloalkyl group represented by R1 to R3, there may be mentioned 5- or 6-membered cycloalkyl groups. Examples of such cycloalkyl group include those having a substituent such as an alkoxycarbonyl group and an aryloxycarbonyl group. As the alkenyl group represented by R1 to R3, there may be employed, for example, C4H7-, C6H11-, and C8H15 - and C18H35-. Said alkenyl group may include one having a substituent such as a halogen atom, an alkoxy group, an aryl group, a cycloalkyloxy group, an alkyl group and an aryloxy group. As the aryl group represented by R1 to R3, there may be mentioned a phenyl group or a naphthyl group. Said aryl group may include one having a substituent such as an alkoxycarbonyl group, an aryloxycarbonyl group, and a cyclohexyloxycarbonyl group.
[0217] As the condensed ring formed by R1 and R2, there may be mentioned oxane, oxasilane and oxolane.
[0218] The dielectric constant of a high-boiling point solvent can be measured by, for example, the transformer-bridging technique.
[0219] In the present invention, it is preferred that a high-boiling point solvent has a dielectric constant of 15.0 or less.
[0220] Examples of a high-boiling point solvent are given below. These examples are given only for the purpose of illustration. The dielectric constant is given in parenthesis.
[0221] The high-boiling point organic solvent may preferably be employed as the solvent for dispersing a coupler. In this case, said solvent may preferably be employed in an amount 0.05 to 20 times larger than the amount of a coupler in weight ratio.
[0222] In the present invention, it is possible to provide auxiliary layers such as a filter layer, an anti-halation layer, and an anti-irradiation layer in a silver halide light-sensitive material. These layers and/or emulsion layers may contain, a dye which may be effused from a light-sensitive material or bleached during processing.
[0223] A light-sensitive material of the invention may have-a layer containing silver halide grains which substantially does not have light-sensitivity at a position farther from a support than silver halide light-sensitive emulsion layers. Such light-sensitive material is excellent not only in the preservability of a photosensitive material but also in the stability to processing conditions, especially to changes of the temperature of a processing liquid. When two or more of the blue-, green- and red-sensitive layers of the above-mentioned light-sensitive material each has a single-layer structure, the preservability and stability can be remarkably improved.
[0224] The expression "silver halide grains substantially does not have light-sensitivity" means that any latent images are not formed in the silver halide grains when a light-sensitive material containing such grains is exposed to light sufficient to form latent images in a light-sensitive emulsion layer of the light-sensitive material having the lowest sensitivity. Specifically, the sensitivity to light of such silver halide grains may preferably be at least one-tenth, more preferably one-hundredth or less, that of the light-sensitive emulsion layer of the light-sensitive material having the lowest sensitivity.
[0225] There is no restriction as to the halide composition of the above-mentioned silver halide grains which do not have light-sensitivity (hereinafter referred to as "non-light-sensitive silver halide grains"). As the non-light-sensitive silver halide grains, there may be employed silver chloride, silver bromide, silver iodide, silver chloro-bromide, silver iodo-bromide, and silver chloro-iodo bromide. Of them, silver iodo-bromide is preferable since it has a low development activity.
[0226] It is preferred that the grain size of a non-light-sensitive silver halide grain is relatively small, since silver halide grains of smaller grain size have lower sensitivity to light. The average grain size of non-light-sensitive silver halide grains may preferably be 0.3 u.m or less, more preferably 0.15 u.m or less, most preferably 0.01 to 0.10 µm.
[0227] There is no restriction as to the grain size distribution of the non-light-sensitive silver halide grains. The non light-sensitive emulsion may either be monodispersed or polydispersed. It is preferred that a non-light-sensitive silver halide grains has a narrower grain size distribution.
[0228] A non-light-sensitive silver halide grains can be prepared by known methods, such as the acid method, the neutral method and ammonia method. As the method of reacting a soluble silver salt with a soluble halogen salt, there may be employed the ordinary mixing method, the simultaneous mixing method and the combination thereof. The controlled double-jet method as one mode of the simultaneous mixing method is preferable due to its contribution to the formation of grains with a narrower grain size distribution.
[0229] There is no restriction as to the shape of grains. Use can be made of grains with a regular crystal shape, such as cubic, octahedral, dodecahedral and tetradecahedral granules. It is also possible to employ grains with an irregular crystal shape.
[0230] In a non-light-sensitive silver halide grains, the halogen composition of the interior portion and that of the surface portion may either be same or different.
[0231] It is possible to add into non-light-sensitive silver halide emulsion ions such as a Cd ion, a Pb ion, an Ir ion, and Rh ion and an Os ion. Silver halide grains containing inside of them, desentizers such as an Rh ion and an Os ion are preferable since light-sensitivity of the grains are significantly lowered. A latent image may be formed either inside or on the surface of a non-light-sensitive silver halide grain. Said non-light-sensitive silver halide grain may have a fogging nucleus in its inside.
[0232] The non-light-sensitive silver halide grains may be subjected to chemical sensitization as long as the sensitivity of the layer containing these grains is kept at 1/100 to 1/10 that of a silver halide emulsion layer of the lowest sensitivity. As the method of chemical sensitization, there may be mentioned sulfur sensitization, gold sensitization, and reduction sensitization. However, it is preferred that a non-light-sensitive silver halide grains is not chemically sensitized.
[0233] It is possible to add to a layer containing a non-light-sensitive emulsion dyes such as cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styrene dyes and hemioxanol dyes. It is also possible to add to the non-light-sensitive emulsion layer such substances as an anti-fogging agent and a stabilizer. Examples of these substances include azoles, heterocyclic mercapto compounds, thioketo compounds, azaindenes, benzene thiosulfonic acids and benzene fulfinic acids.
[0234] The coating amount of silver contained in a non-light-sensitive silver halide emulsion layer may preferably be 0.01 to 5 g/m2, more preferably 0.01 to 1.5 g/m2.
[0235] There is no restriction as to the binder for a non-light-sensitive silver halide emulsion layer, as long as it is a hydrophilic polymer. An especially preferable binder is gelatin.
[0236] In a light-sensitive material of the present invention, formalin scavenger, an optical bleaching agent, a matting agent, a lubricant, an image stabilizer, a surface active agent, an anti-color-fogging agent, a development accelerator, a development retarger, and bleaching accelerator may be added.
[0237] As the support, there may be employed a polyethylene laminated paper, a polyethylene terephthalate film, a baryta paper and cellulose triacetate.
[0238] When a silver halide light-sensitive material of the present invention is employed, a dye image can be obtained by subjecting the light-sensitive material to conventional color photographic processing, after exposure to light.
[0239] Meanwhile, "Torezo-kun", a light-sensitive material package being manufactured by the applicant, has been widely employed recently. This product is provided with in its inside a silver halide light-sensitive material and has a function of a camera. These packages are being sold mainly at tourist resorts, which are unfavorable environments for the preservation of a light-sensitive material. Hence, these package are expected to have a better preservability.
[0240] When a light-sensitive silver halide material of the present invention is employed in such camera-type package, this product can be preserved stably even under unfavorable conditions, and is capable of producing images excellent in gradation, color-reproducibility and tone-reproducibility.
[0241] The above-mentioned product is provided with the 1 st chamber where a roll of unexposed light-sensitive material is housed, the 2nd chamber where an exposed light-sensitive material is housed (Patrone chamber), a lens, a shutter, and other functions neccessary for photographing.
[0242] An unexposed light-sensitive material is directly or indirectly, for example, in a state of being housed in a Patrone or a cartridge, housed in the 1st chamber.
[0243] There is no restriction as to the size of a light-sensitive material to be used in such package. Various sizes, such as 110, 135, 126 (sizes of a disc type light-sensitive material) may be employed.
[0244] In the light-sensitive material of the invention in which at least two kinds of silver halide grains contained in the layer with a single-layer structure are each composed of two or more phases differing in silver iodide content such that the average silver iodide content of interior phases is larger than that of exterior phases, hereinafter such light-sensitive material is called as "material of type A", it is preferred that a nitrogen-containing heterocyclic mercapto compound is contained in the light-sensitive material for improving the preservability of the material and the preservability of latent image.
[0245] In the light-sensitive material type A or a light-sensitive material containing a nitrogen containing heterocyclic compound in at least one of silver halide emulsion layer thereof, hereinafter such light-sensitive material is called as "material of type B", it is preferred that at least one of the light-sensitive layers contains a phenol type cyan coupler having a ureido group at the 2-position of the phenol ring of the coupler for further improving the preservability of the material and the preservability of latent image.
[0246] In the light-sensitive material of type A or B, it is preferred that the green-sensitive layer in each materials has a single layer structure and contains a DIR compound and a 5 pyrazolone type two-equivalent magenta coupler for improving the dye image density reduction caused by storage under an atmosphere with formalin, the preservability of the material and the preservability of latent image.
[0247] In the material of type A or B, it is preferred that these materials each contains a coupler which is capable of releasing a dye or a precursor thereof by a coupling reaction with an oxidized product of an aromatic primary amine type color developing agent for improving the optical density, color reproducibility and the graininess of images formed in the materials, the preservability of materials, the preservability of latent image and the stability against changes of processing conditions. The dye or the precursor is bounded, directly or through a timing group, to an active position of the coupler and the absorption maxima of the dye tobe released or formed from the precursor is shifted to the side of short wavelength.
[0248] In the material of type A or B, it is preferred that the materials each contains a compound capable of splitting off a bleaching accelerator or its precursor by a reaction with an oxidized product of a color developing agent for improving the desilvering-readiness and the stability to processing conditions.
[0249] In the material of type A or B, it is preferred that the materials each contains at least one kind of high-boiling point solvent having a dielectric constant of 4.00 or more at 25 °C, 10 KHz for improving the preservability of the materials.
[0250] In the material of type A or B, it is preferred that the materials each has a layer containing substantially non-light-sensitive silver halide grains at a position further form the support than all of the light-sensitive silver halide emulsion layers for improving the preservability of the materials and the stability to processing conditions.
[0251] In the material of type A containing at least one high-boiling point solvent having a dielectric constant of 4.00 or more at 250 C, 10 KHz, and having the layer containing substantiall non-light-sensitive silver halide grains at a position further from a support than all the light-sensitive emulsion layers, hereinafter such light-sensitive material is called as "material of type C", it is preferred that a nitrogen-containing heterocyclic compound is contained in the material for improving the preservabilities of the material and latent image.
[0252] In the material of type C or the material of type A in which at least one of the silver halide emulsion layers contains a nitrogen-containing heterocyclic compound, hereinafter such light-sensitive material is called as "material of type D", it is preferred that at least one of light-sensitive layers of each materials contains a phenol type cyan coupler having a ureido group at the 2-position of the phenol ring for improving the preservabilities of the material and latent image.
[0253] In the material type C or D, it is preferred that the green-sensitive layer has a single layer structure and contains a DIR compound and a 5 pyrazolone type two-equivalent magenta coupler for improving the dye image density reduction caused by storage under an atmosphere with formalin, the preservabilities of the material and the latent image.
[0254] In the material of type C or D, it is preferred that these materials each contains a coupler which is capable of releasing a dye or a precursor thereof by a coupling reaction with an oxidized product of an aromatic primary amine type color developing agent for improving the optical density, color reproducibility and the graininess of images formed in the materials, preservability of the materials, the preservability of latent image and the stability against changes of processing conditions. The dye or the precursor is bounded, directly or through a timing group, to an active position of the coupler and the absorption maxima of the dye tobe released or formed from the precursor is shifted to the side of short wavelength.
[0255] In the material of type C or D, it is preferred that the materials each contains a compound capable of splitting off a bleaching accelerator or its precursor by a reaction with an oxidized product of a color developing agent for improving the desilvering-readiness and the stability to processing conditions.
EXAMPLES
[0256] The present invention is hereinafter described in more detail by means of the following working examples, but the mode of embodiment of the invention is not limited thereto.
[0257] In the examples given below, figures for the amount of coating are expressed in the unit of g/m2 as silver content for silver halide and colloidal silver, in the unit of g/m2 for additives and gelatin, and in molar number per mol silver halide in the same layer for sensitizing dyes, coupler and DIR compounds.
[0258] Note that the emulsion contained in each color-sensitive emulsion layer was appropriately sensitized with chloroauric acid or sodium thiosulfate.
Example 1
[0259] A subbed cellulose acetate support was coated with multilayer color light-sensitive material No. 1-1 having the following composition.
[0260] The layers of the compositions shown above are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, B-1 and Pro-2 as given above.
<Preparation of Samples Nos. 1-2 through 1-10>
[0261] Sample Nos. 1-2 and 1-3 were prepared in the same manner as with Sample No. 1-1 except that emulsions listed in Table 1-1 were used in place of the emulsion contained in G-1 and B-1 of Sample No. 1-1. When two or more emulsions were present in G-1 and B-1, they were mixed together each in an equal amount and then sensitized..
[0262] Sample Nos. 1-4 through 1-6 were prepared by adding DIR compounds listed in Table 1-1 to G-1 and B-1 of Sample Nos. 1-1 through 1-3.
[0263] Sample No. 1-7 through 1-10 were prepared by changing the DIR compounds in Sample Nos. 1-5 and 1-6 to those listed in Table 1-1.
[0264] Each sample was subjected to exposure through a optical wedge and a charge of MTF determination and then processed by the following processing procedures.
[0265] The processing solutions used in these processing procedures had the following compositions, respectively.
[0266] The blue- and green-sensitive emulsion layers of the processed samples were subjected to sensitometry calculate the exposure latitude of each sample.
[0268] The sharpness improving effect was rated as the MTF (modulation transfer function) of color images; the MTF value at 30 lines/mm was expressed as relative to the value obtained in Sample No. 1-1 taken as 100.
[0269] RMS values were obtained in standard deviation for the variation of density occurring when an image having an optical density exceeding the minimum density by 1.2 was scanned with a microdensitometer of 25 µm in circular scanning diameter, as relative to the value obtained in Sample No. 1-1 taken as 100.
[0272] As is evident from Table 1-3, the samples prepared according to the present invention possessed good graininess and sharpness, wide latitude and excellent processing stability.
Example 2
[0273] Sample Nos. 1-11 through 1-20 were prepared in the same manner as with Sample Nos. 1-1 through 1-10 except that the R-2 layer of Sample Nos. 1-1 through 1-10 was removed, the emulsion in R-1 was changed from EM-2 to an equimolar mixture of EM-1, EM-2 and EM-3, and the coating amount of each component of R-2 was increased to 1.5 times that of Sample Nos. 1-1 through 1-10.
[0274] The samples thus obtained were rated in the same manner as in Example 1. The obtained results are shown in Table 1-4.
[0276] As is evident from Table 1-4, the samples prepared in accordance with the present invention are excellent in exposure latitude, graininess, sharpness and processing stability.
Example 3
Preparation of seed emulsion
[0277] 500 m ℓ of a 2.0% aqueous solution of gelatin was heated to 40 C. To this solution were added 250 m ℓ of an aqueous solution of 4 M (molar concentration) AgNO3 and 250 m of an aqueous solution of 4 M KBr by the controlled double jet method in accordance with the method described in Japanese Patent O.P.I. Publication No. 45437/1975 at a pAg of 9.0 and pH 2.0 over a period of 35 minutes. The aqueous solution of gelatin containing the above-mentioned AgX grains in an amount corresponding to the entire amount of added silver was adjusted to pH 5.5 with an aqueous solution of potassium carbonate, and then coagulated by the addition of 364 mℓ of a 5% aqueous solution of Demol N, produced by Kao Atlas Co. as a floculating agent and 244 m ℓ of a 20% aqueous solution of magnesium sulfate for multivalent ions, and this was followed by precipitation by keeping the mixed solution to stand. After supernatant decantation, 1400 m of distilled water was added for re-dispersion. To the resulting dispersion was added 26.4 m of a 20% aqueous solution of magnesium sulfate to cause re-floculation. After the precipitated supernatant was decanted, an aqueous solution containing 28 g of ossein gelatin was added to reach a total volume of 424 mℓ, and this was followed by dispersion at 40° C for 40 minutes to yield an AgX seed emulsion.
[0278] This emulsion is referred to as NE-1. Electron microscopy revealed that NE-1 is a monodispersibie emulsion comprising cubic grains of 0.093 µm in average grain size.
(production Example 1)
[0279] Using the seven solutions shown below, a silver iodobromide emulsion of the core-shell type was prepared which had Agl contents of 15 mol%, 5 mol% and 3 mol% distributed in this order from grain core, with an average grain size of 0.38 µm and an average Agl content of 8.46 mol%.
(Solution A-l)
(Solution F.1)
(Solution G.1)
[0284] To Solution A-1 were added Solutions E-1 and B-1 at 40°C by the simultaneous mixing method using the mixing agitator described in Japanese Patent O.P.I. Publication Nos. 92523/1982 and 92524/1982. When the addition of B-1 was completed, C-1 was added without delay; when the addition of C-1 was completed, D-1 was added without delay. During the simultaneous mixing, pAg and pH and the addition rates for Solutions E-1, B-1, C-1 and D-1 were maintained at levels shown in Table 3-1.
[0285] Control of pAg and pH were achieved by varying the flow rates of Solutions F-1 and G-1 by means of a roller tube pump with variable flow discharge capacity.
[0286] After completion of the addition of Solution E-1, pH adjustment, pAg adjustment, desalting and washing, and re-dispersion were conducted.
(Production Example 2)
[0288] In accordance with Production Example 1, a silver iodobromide emulsion of the core/shell type was prepared which had Agl contents of 15 mol%, 5 mol% and 3 mol% distributed in this order from grain core, with an average grain size of 0.65 nm and an average Agl content of 7.164 mol%. This emulsion is referred to as EM-5.
(Production Example 3)
[0289] In accordance with Production Examples 1 and 2, two silver iodobromide emulsions were prepared which both had a uniform iodine distribution and an average Agl content of 3 mol% and which respectively had average grain sizes of 0.38 µm and 0.65 µm. The obtained emulsions are referred to as EM-6 and EM-7, respectively.
Preparation of Comparative Sample No. 3-101
[0291] A subbed cellulose acetate support was coated with vertically double structure multilayer color light sensitive material No. 3-101 having the following composition.
[0293] The layers of the compositions shown above are hereinafter respectively represented by the abbreviations NC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 shown above.
Preparation of Sample No. 3-102
[0294] Sample No. 3-102 was prepared in the same manner as with Sample No. 3-101 except that EM-4 was replaced by EM-6 and EM-5 was replaced by EM-7.
Preparation of Sample No. 3-103
[0295] Sample No. 3-103 was prepared in the same manner as with Sample No. 3-101 except that G-2 was removed, the emulsion in G-1 was changed to an equimolar mixture of EM-6 and EM-7, and the amounts of the emulsion, gelatin and TCP in G-1 were each increased by 30%.
Preparation of Sample No. 3-104
[0296] Sample No. 3-104 was prepared in the same manner as with Sample No. 3-103 except that EMG-6 and EM-7 in G-1 were respectively replaced by EM-4 and EM-5.
Preparation of Sample No. 3-105
[0297] Sample No. 3-105 was prepared in the same manner as with Sample No. 3-104 except that B-2 was removed, the emulsion in B-1 was changed to an equimolar mixture of EM-4 and EM-5, and the amounts of the emulsion, gelatin and TCP in B-1 were each increased by 15%.
Preparation of Sample No. 3-106
[0298] Sample No. 3-106 was prepared in the same manner as with Sample No. 3-105 except that R-2 was removed, the emulsion in R-1 was changed to an equimolar mixture of EM-4 and EM-5, and the amounts of the emulsion, gelatin and DOP in R-1 were each increased by 25%.
[0299] Sample Nos. 3-101 through 3-106 thus obtained were subjected to exposure through an optical wedge in accordance with an ordinary method and then processed in the same manner as in Example 1.
[0300] The sharpness (MTF), preservability and processing stability of each processed sample were rated.
[0302] For values of sharpness, the MTF of dye images at 10 lines/mm was determined and expressed in relative values (relative to the values obtained with Sample Nos. 3-101 and 3-102, each taken as 100).
[0304] As is evident from the results shown in Tables 3-4 and 3-5, the samples prepared in accordance with the present invention noticeably surpasses the comparison samples in sharpness, preservability and processing stability.
[0305] It has been demonstrated that the sharpness, preservability and processing stability were improved by the use of a single layer structure; the property improving effect of single layer structure; the property improving effect of single layer structure is noticeably enhanced when using silver halide emulsions having a core portion of a silver halide content higher than that in the surface of silver halide grains.
Preparation of Comparative Sample No. 4-101
[0307] A subbed cellulose acetate support was coated with double layer structure multilayer color light-sensitive material No. 4-101 having the following composition.
[0309] The layers of the compositions shown above are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 shown above.
Preparation of Comparative Sample No. 4-102 and invention Sample Nos. 4-103 through 4-111
[0311] First, Sample No. 4-102 was prepared in the same manner as with Sample No. 4-101 except tht the compounds listed in Table 4-1 were respectively added to G-1 and G-2 of Sample No. 4-101.
[0312] As for Sample Nos. 4-103 and 4-104, they were prepared in the same manner as with Sample No. 4-101, except that G-2 of Sample No. 4-101 was removed, the emulsion in G-1 was replaced by an equimolar mixture of EM-5 and EM-4, and the amounts of the emulsion, gelatin and TCP in G-1 were each increased by 30%, and in addition, for Sample No. 4-104 alone, the compound shown in Table 4-1 was added to G-1. However, the amounts of the sensitizing dyes, couplers and DIR compounds in. G-1 per mol silver halide were the same as those of Sample No. 4-101.
[0313] Sample Nos. 4-105 through 4-111 were prepared in the same manner as with Sample No. 4-103 except that B-2 of Sample No. 4-103 was removed, the emulsion in B-1 was replaced by an equimolar mixture of EM-5 and EM-4, the amounts of the emulsion, gelatin and TCP in B-1 were each increased by 15% and the emulsion and compound in G-1 were changed as shown in Table 4-1. However, the amounts of the sensitizing dyes and couplers in B-1 per mol silver halide were the same as those of Sample No. 4-103.
[0315] The amount of each compound shown in Table 4-1 as contained in green-sensitive layer was 2 x 10-4 mol per mol silver halide in green-sensitive layer.
[0316] The compounds A-1, A-2 and A-3 shown in Table 4-1 respectively have the following structures:
[0317] Sample Nos. 4-101 through 4-111 thus obtained were each cut into small pieces of appropriate size. Two parts of each sample were subjected to exposure through an optical wedge using white light in accordance with an ordinary method. One part of this exposed sample was stored in a refrigerator at 5° C for 15 days as a reference, while the other one part was stored at 25° C and relative humidity of 80% for 15 days; these two parts were then processed in the same processing procedures as those in Example 1.
[0318] Each processed sample was then subjected to densitometry in accordance with an ordinary method to draw a characteristic curve, based on which gradation variance associated with latent image retention was evaluated.
[0319] The evaluation method for the gradation preservability is hereinafter described by means of some drawings.
[0320] Fig. 1 shows a characteristic curve for reference (dotted line) and another characteristic curve for the subjected of rating (solid line). Fig. 2 shows the gamma value on each exposure point taken by every ΔIogH=0.15 between the exposure point A of a density exceeding the minimum density by 0.1 as obtained in Fig. 1 and the exposure point B + 3.0 in ΔogH higher than A. From Fig. 2 is obtained the absolute value by Δγ of the difference in the gamma value on each exposure point between the reference characteristic curve and the characteristic curve to be evaluated. The average value of Δγ was multiplied by 1000 (Δγ) and the standard deviation A of A-y was multiplied by 1000 (E); these two values were used as index of gradation. preservability. In other words, the difference of gamma values between the two characteristic curves increases as Δγ value increases, and gradation preservability decreases as Σ value increases or as the change in gradation becomes less uniform.
[0321] Sample Nos. 4-101 through 4-111 thus obtained were each cut into small pieces of appropriate size; two parts of each sample was used without exposure. One part of each unexposed sample was stored in a refrigerator at 5°C for 7 days as reference, while the other one part was stored at 40°C and relative humidity of 80% for 7 days. Each part was then subjected to wedge using white light in accordance with an ordinary method. Each sample was processed, and its characteristic curve was drawn, based on which the gradation variance associated with the light sensitive material preservability was evaluated in the same manner as in the rating of the gradation variance associated with latent image retention.
[0323] As is evident from Table 4-2, the samples in accordance with the present invention have a small variance of gradation between the high light and shadow portions of the characteristic curve and good gradation retention associated with light-sensitive material preservability and that associated with latent image preservability. The samples were also found to have a wide exposure latitude of over 3 as DologH.
[0324] It should be noted that the effect of the present invention was obtained even when a polydispersible emulsion having a coefficient of variance of 0.28, though monodispersible emulsions of a coefficient of variance of 0.19 to 0.20 were used in the present example.
[0325] In the present example, properties were evaluated on green-sensitive layer. As well, samples of blue-and red-sensitive layers were prepared and their gradation retention was evaluated; the present invention proved to have an improving effect on gradation retention.
[0326] The effect of the present invention was also noted in the samples prepared using Z-1, Z-4, Z-6, Z-7, Z-8, Z-9 and Z-10 in place of Z-3 of Sample No. 4-109; those prepared using Z-11, Z-12, Z-21 and Z-23 in place of Z-14 of Sample No. 4-110; and those prepared using Z-24, Z-27 and Z-31 in place of Z-32 of Sample No. 4-111.
[0327] The effect of the present invention was also noted in the samples prepared using (D-29), (D-4) and (D-2) in place of (D-42) in (B-2) of Sample No. 4-104; those prepared using (D-6), (D-2) and (D-10) in place of (D-23) in (G-1) of Sample No. 111; and those prepared using (D-2) and (D-17) in place of (D-23) in (R-1) of Sample No. 109 and (D-19) and (D-21) in place of (D-42) in (R-1) of Sample No. 109, respectively.
Example 5
Preparation of Comparative Sample No. 5-101
[0328] A subbed cellulose acetate support was coated with a multilayer color light-sensitive material No. 5-101 having exactly the same vertically double layer structure as that of Sample No. 4-101 in Example 4.
[0329] The layers of Sample No. 5-101 are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 as in the case of Sample No. 4-101.
Preparation of Comparative Sample Nos. 5-102 through 5-104
[0330] Sample Nos. 5-102 through 5-104 were respectively prepared in the same manner as with Sample No. 5-101 except that the cyan couplers listed in Table 5-1 were used in place of CU-4 in R-1 and R-2 of Sample No. 5-101.
Preparation of Comparative Sample Nos. 5-105 through 5-109
[0331] Sample Nos. 5-105 through 5-109 were respectively prepared in the same manner as with Sample No. 5-101 except that R-2 of Sample No. 5-101 was removed, the emulsion in R-1 was replaced by an equimolar mixture of EM-4 and EM-5, the amounts of the emulsion, gelatin and DOP in R-1 were each increased by 25%, and the cyan couplers listed in Table 5-1 were used. The amounts of the sensitizing dyes, couplers and DIR compounds in R-1 per mol silver halide were the same as those of Sample No. 5-101.
Preparation of Inventive Sample No. 5-110
[0332] Sample No. 5-110 was prepared in the same manner as with Sample No. 5-105 except that B-2 and G-2 of Sample No. 5-105 were removed, the couplers and emulsions in B-1 and G-1 were replaced by those listed in Table 5-1, the amounts of the emulsion, gelatin and TCP in B-1 were each increased by 15%, and the amounts of the emulsion, emulsion, gelatin and TCP in G-1 were each increased by 30%. The amounts of the sensitizing dyes, couplers and DIR compounds in B-1 and G-1 per mol silver halide were the same as those in Sample No. 5-105.
[0334] The latent image preservability and light-sensitive material preservability in the red-sensitive layer of each sample were evaluated in the same manner as in Example 4. The results are shown in Table 5-2.
[0335] As is evident from Table 5-2, the samples in accordance with the present invention have a small variance of gradation between the high light and shadow portions of the characteristic curve and good gradation preservability in retention to light-sensitive material preservability and latent image preservability.
[0337] Among the samples in accordance with the present invention, Sample No. 5-110, with all light-sensitive layers prepared as single-structure layers, is preferable because of its considerable property improving effect.
[0338] The effect of the present invention was obtained in the sampled prepared using (D-29), (D-4) and (D-2) in place of (D-42) in B-2 of Sample No. 5-105; those prepared using (D-6), (D-2) and (D-10) in place of (D-23) in (G-1) of Sample No. 5-106; and those prepared using (D-2) and (D-17) in place of (D-23) in R-1 of Sample No. 5-107 and (D-19) and (D-21) in place of (D-42) in (R-1) of Sample No. 5-107, respectively.
Example 6
Preparation of Comparative Sample No. 6-101
[0339] A subbed cellulose acetate support was coated with double layer structure multilayer color light-sensitive material No. 6-101 of the following composition.
[0341] The layers of the compositions shown above are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 shown above.
[0343] Sample Nos. 6-102 through 6-104 were prepared in the same manner as with Sample No. 6-101 except that the 2-equivalent 5-pyrrazolone couplers listed in Table 6-1 were used in place of M-1 and G-1 and G-2 of Sample No. 6-101 and the amounts of EM-5 and EM-4 were changed to 1.0 g/m2.
[0344] The amounts of the sensitizing dyes, couplers and DIR compounds in G-1 per mol silver halide were the same as those of Sample No. 6-101.
[0345] Sample Nos. 6-105 through 6-107 were prepared in the same manner as with Sample No. 6-101 except that G-2 of Sample No. 6-101 was removed and the emulsion in G-1 and M-1 were changed as shown in Table 6-1.
[0346] Sample Nos. 6-108 through 6-110 were prepared in the same manner as with Sample No. 6-101 except that B-2 and G-2 of Sample No. 6-101 were removed, the amounts of the emulsion, gelatin and TCP in B-1 were each increased by 15%, the amounts of the sensitizing dyes and couplers in B-1 per mol silver halide were the same as those of Sample No. 6-101, and the emulsion and couplers in G-1 were changed as shown in Table 6-1. The same emulsion as that in G-1 was used in B-1 as well except that the sensitizing dyes were changed.
[0347] Sample No. 6-111 was prepared in the same manner as with Sample No. 6-108 except that R-2 of Sample No. 6-108 was removed, the amounts of the emulsion, gelatin and TCP in R-1 were each increased by 20%, the amounts of the sensitizing dyes, couplers and DIR compounds in R-1 per mol silver halide were the same as those of Sample No. 6-108, and the emulsion and couplers in G-1 were changed as shown in Table 6-1. The same emulsion as in G-1 was used in R-1 as well except that the sensitizing dyes were changed.
[0349] Sample Nos. 6-101 through 6-111 thus obtained were evaluated as to light-sensitive material preservability and latent image retention in the same manner as in Example 4 and as to preservability in a gaseous formalin atmosphere (hereinafter referred to as formalin resistance) by the method described below. The results are shown in Table 6-2.
Formalin resistance
[0350] Each sample was divided into two parts. One part was left at 30 C for 3 days in a tight container containing 300 mℓ of a 35% aqueous solution of glycerol and filled with air as equilibrated thereto, while the other one part was left at 30 °C for 3 days under the same conditions as above except that 6 m of a 40% aqueous solution of formaldehyde was added to the aqueous solution of glycerol. Each part was then subjected to exposure through an optical wedge and processing, and then density reduction under formalin atmosphere was determined.
[0351] The density of samples stored under the conditions with formalin atmosphere was determined at the exposure level at which a density measure by green light of 1.0 is obtained in samples stored under formalin-free conditions. Formalin resistance was evaluated on the basis of the degree of density reduction. Table 6-2 shows relative values of density reduction in comparison with the value obtained in Sample No. 6-101, taken as 100. The degree of density reduction in storage under the conditions with formalin decreases, i.e., formalin resistance increases, as the value decreases.
[0352] As is evident from Table 6-2, the samples in accordance with the present invention show slight density reduction due to formalin and are excellent in ligh-tsensitive material preservability and latent image retention. The samples were also found to have a wide exposure latitude of over 3 as ΔlogH.
[0353] When the 4-equivalent coupler in green-sensitive layer of double-layer structure was replaced by a 2- equivalent coupler, the light-sensitive material preservability and latent image retention were degraded as seen in the comparison of Sample No. 6-101 and Sample Nos. 6-102 through 6-104. It was also found that when the green-sensitive layer was changed to have a single-layer structure, these properties improved and exceeded those of Sample No. 6-101. This improvement occurred unexpectedly.
[0354] Among the samples in accordance with the present invention, those whose blue- and green-sensitive emulsion layers were changed to have a single-layer structure, Sample Nos. 6-108, 6-109 and 6-110, showed a considerable improving effect on gradation retention associated with light-sensitive material preservability and gradation retention associated with latent image retention, and are thus preferable. The sample whose light-sensitive layers were all changed to have a single-layer structure, Sample No. 6-111, had a still higher improving effect and is thus still more preferable.
[0355] The effect of the present invention was also noted in the samples prepared using MC-6, MC-13 and MC-14 in place of the coupler MC-2 used in Sample No. 6-105.
[0356] The effect of the present invention was also noted in the samples prepared using D-6, D-2 and D-10 in place of D-23 in G-1 of Sample No. 6-106; those prepared using D-23, D-19 and D-10 in B-1 of Sample No. 6-108 at a ratio of 0.003 mol per mol silver halide; and those prepared using D-17, D-19 and D-19 and D-21 in place of D-42 in R-1 of Sample No. 6-111, respectively.
Example 7
Preparation of Comparative Sample No. 7-101
[0357] A subbed cellulose acetate support was coated with multilayer color light-sensitive material No. 7-101 having exactly the same vertically double layer structure as that of Sample No. 6-101 in Example 6.
[0358] The layers of the compositions shown above are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 shown above.
[0360] Sample No. 7-102 was prepared in the same manner as with Sample No. 7-101 except that B-2 of Sample No. 7-101 was removed, the emulsion in B-1 was replaced by an equimolar mixture of EM-4 and EMS, and the amounts of the emulsion, gelatin and TCP were increased by 25%. The amounts of the sensitizing dyes and couplers in B-1 per mol silver halide were the same as those of Sample No. 7-101.
[0361] Sample No. 7-103 was prepared in the same manner as with Sample No. 7-102 except that G-2 of Sample No. 7-102 was removed, the emulsion in G-1 was replaced by an equimolar mixture of EM-4 and EM-5, and the amounts of the emulsion, gelatin and TCP in G-1 were increased by 25%. The amounts of the sensitizing dyes, couplers and DIR compounds in G-1 per mol silver halide were the same as those of Sample No. 7-102.
[0362] One part of each sample was stored in a refrigerator at 5 C for 17 days, while the other one part was left at 40 C and relative humidity of 80% for 17 days. These two parts were then subjected to exposure through an optical wedge in accordance with an ordinary method and then developed by the same processing procedure as in Example 4. The effect of samples storage conditions on gradation retention was rated by the evaluation method described in Example 4. Table 7-2 shows the results for green-sensitive layer.
[0363] As is evident from Table 7-2, the sample in accordance with the present invention is excellent in gradation retention between the high light and shadow portions of the characteristic curve in relation to light-sensitive material preservability. The .samples were also found to have a wide exposure latitude of over 3 as ΔIogH. It was also found that the improving effect on gradation retention is enhanced when two color sensitive layers have a single-layer structure, in comparison with Sample No. 7-102, in which one color sensitive layer has a single-layer structure. It is preferable that all the blue-, green- and red-sensitive layers have a single-layer structure, since gradation retention is further improved.
[0364] Each sample stored in the refrigerator was subjected to exposure through an optical wedge in accordance with an ordinary method and then processed in the same processing procedure as that described above except that the processing temperature was 41 C. The effect of processing solution temperature on gradation retention was then determined. Table 7-3 shows the values of Δγ and E for green-sensitive layer at a processing temperature of 41 ` C relative to the reference values obtained at a processing temperature of 38. C.
[0365] As seen in Table 7-3, the light-sensitive material of the present invention is excellent in gradation retention against the change in processing solution temperature, as well as in light-sensitive material preservability shown in Table 7-2.
[0366] The effect of the present invention was also noted in the samples prepared using D-6, D-2 and D-10 in place of D-23 in G-1 of Sample No. 7-103; and those prepared using D-2 and D-17 in place of D-23 in R-1 of Sample No. 7-103 and D-19 and D-21 in place of D-42 in R-1 of Sample No. 7-103 respectively.
Example 8
Preparation of Comparative Sample No. 8-101
[0367] A subbed cellulose acetate support was coated with vertically double structure multilayer color light-sensitive material No. 8-101 in the same manner as with Sample No. 6-101 except that all high boiling point organic solvents used in Sample No. 6-101 were replaced by the following compound HB-A.
[0368] The layers of the compositions shown above are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2.
[0370] Sample Nos. 8-102 through 8-106 were prepared in the same manner as with Sample No. 8-101 except that the high boiling point organic solvent HB-A contained in each layer was replaced by those listed in Table 8-1.
[0371] Sample No. 8-102 was prepared in the same manner as with Sample No. 8-101 except that G-2 and B-2 in Sample No. 8-101 were removed.
[0372] Sample Nos. 8-108 through 8-112 were prepared in the same manner as with Sample No. 8-107 except that the high boiling point organic solvent HB-A contained in each layer was replaced by those listed in Table 8-1.
[0374] Sample Nos. 8-101 through 8-112 thus obtained were each divided into two parts. To evaluate the light-sensitive material preservability, these two parts were subjected to exposure through an optical wedge in an ordinary method and processed by the processing procedure described in Example 4 immediately after drying one part as reference and after drying and then leaving the other one part at 25° C and 80%RH for 15 days.
[0376] As is evident from Table 8-2, the samples in accordance with the present invention have a small variance of gradation retention between the high light and shadow portions of the characteristic curve in relation to light-sensitive material preservability, and are thus excellent in gradation retention. The samples were also found to have a wide exposure latitude of over 3 as ΔlogH.
[0377] As seen in the comparisons of Sample Nos. 8-101 and 8-107 and of Sample Nos. 8-102 and 8-108, when HB-A and HB-B were used as high boiling point organic solvent, a property improving effect was obtained by increasing two color-sensitive layers to have a single-layer structure. Moreover, as seen in the comparisons of Sample Nos. 8-103 and 8-109, of Sample Nos. 8-104 and 8-110, of Sample Nos. 8-105 and 8-111, and of Sample Nos. 8-106 and 8-112, when the preferable high boiling point organic solvent of the present invention was used, further improvement was obtained. The samples in accordance with the present invention showed good color forming property.
[0378] The effect of the present invention was noted in all exemplified compounds as well as in the high boiling point organic solvent used in the working examples.
[0379] This effect was most enhanced when all the blue-, green- and red-sensitive layers were changed to have a single-layer structure.
[0380] The effect of the present invention was also noted in the samples prepared using D-2, D-6 and D-10 in place of The DIR compound D-26 in G-1 of Sample No. 8-110; and those prepared using D-17, D-19 and D-21 in place of the DIR compound D-23 in R-1 of Sample No, 8-112, respectively.
Example 9
[0381] A subbed cellulose acetate support was coated with multilayer color light-sensitive material No. 9-101 having exactly the same vertically double structure as that of Sample No. 3-101 in Example 3.
[0382] The layers are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 as in the case of Sample No. 3-101 in Example 3.
Preparation of Comparative Sample No. 9-102
[0383] Sample No. 9-102 was prepared in exactly the same manner as with Sample No. 9-101 except that an example compound BAR-22 was added to the R-1 layer of Sample No. 9-101 at 0.03 mol/mol Ag.
Preparation of Invention Sample No. 9-103
[0384] Sample Nos. 9-103 was prepared in exactly the same manner as with Sample No. 9-101 except that the B-2 layer of Sample No. 9-101 was removed and a 1:1 mixture of EM-4 and EM-4 was used in place of EM-4 in the B-1 layer after sensitivity optimization.
Preparation of Invention Sample No. 9-104
[0385] Sample No. 9-104 was prepared in exactly the same manner as with Sample No. 9-103 except that an example compound BAR-22 was added to the R-1 layer of Sample No. 9-103 at 0.03 mol/mol Ag.
[0386] Each sample was subjected to exposure through an optical wedge using blue light and then developed by the same processing procedure as in Example 4. The effects of the BAR compound on bleach ability and processing stability was then determined.
[0388] Bleach ability is expressed in relative values of Sample Nos. 9-102 and 9-104, both containing the BAR compound, relative to the desilvering amounts in Sample Nos. 9-101 and 9-103, taken as 100 for reference values. The improving effect on bleach ability increases as the value increases. Measurements of silver were made by fluorescent X-ray analysis.
[0389] Processing stability is expressed in relative values of Sample Nos. 9-102 and 9-104, both containing the BAR compound, relative to the difference between the y value obtained in the development of Sample Nos. 9-101 and 9-103 with a color developer at pH10.02 and the y value obtained in development at pH9.8, taken as 100. The improving effect on processing stability to pH fluctuation increases as the value decreases. Here, y represents the gradient of the linear line connecting two points on the sensitometry curve, namely the point of fog + 0.3 and the point of fog + 0.8.
[0390] As seen in Table 9-1, the addition of the BAR compound noticeably improved the bleach ability and processing stability in the samples in accordance with the present invention, having a light-sensitive layer of single-layer structure, in comparison with the samples having double-layer structure in all light-sensitive layers.
[0391] The same effect was obtained by the addition of the BAR compound in the sample prepared in the same manner as with Sample No. 9-101 except that the G-2 layer of Sample No. 9-101 was removed and EM-4 in the G-1 layer was replaced by 1:1 mixture of EM-4 and EM-5.
Preparation of Comparative Sample No. 9-202
[0393] Sample No. 9-202 was prepared in the same manner as with Sample No. 9-102 except that BAR-22 in the R-1 layer of Sample No. 9-102 was replaced by BAR-23.
Preparation of Inventive Sample No. 9-203
[0394] Sample No. 9-203 was prepared in exactly the same manner as with Sample No. 9-101 except that the R-2, G-2 and B-2 layers of Sample No. 9-101 were removed, and a 1:1 mixture of Em-4 in the R-1, G-1 and B-1 layers.
Preparation of Inventive Sample No. 9-204
[0395] Sample No. 9-204 was prepared in exactly the same manner as with Sample No. 9-203 except that an example compound BAR-23 was added to the R-1 layer of Sample No. 9-203 at 0.02 mol/mol Ag.
[0396] Sample Nos. 9-101 and 9-202 through 9-204 were subjected to exposure through an optical wedge using blue light and then processed. The bleach ability and processing stability of each developed sample were.then determined. The results are shown in Table 9-2.
[0397] Bleach ability and processing stability are expressed in relative values of Sample Nos. 9-202 and 9-204, both containing the BAR compound, relative to the reference values obtained in Sample Nos. 9-101 and 9-203, taken as 100.
[0398] As seen in Table 9-2, the samples in accordance with the present invention show a noticeable property improving effect of BAR compound, and this effect is further enhanced when all color-sensitive layers are changed to have a single-layer structure as in Sample No. 9-104.
[0399] Qualitatively the same effect as in blue light exposure was obtained in the case of green light exposure and red light exposure.
Preparation of Comparative Sample No. 9-302
[0401] Sample No. 9-302 was prepared in exactly the same manner as with Sample No. 9-202 except that BAR-23 in the R-1 layer of Sample No. 9-202 was removed, and BAR-28 was added to the IL-2 layer.
Preparation of Inventive Sample No. 9-304
[0402] Sample No. 9-304 was prepared in exactly the same manner as with Sample No. 9-204 except that the BAR-23 in the R-1 layer of Sample No. 9-204 was removed and BAR-28 was added to the IL-2 layer.
[0403] Sample Nos. 9-101, 9-203, 9-302 and 9-304 were subjected to exposure through an optical wedge using blue light and then processed. The bleach ability and processing stability of each developed sample were rated. The results are shown in Table 9-3.
[0404] Bleach ability and processing stability are expressed in relative values of Sample Nos. 9-302 and 9-304, both containing the BAR compound, relative to the reference values obtained in Sample Nos. 9-101 and 9-203, taken as 100.
[0405] As seen in Table 9-3, the samples in accordance with the present invention show a noticeable improving effect on bleach ability and processing stability, which is similar to that obtained by adding the BAR compound to the emulsion layer.
[0406] The same improving effect was noted in the case of green light exposure, red light exposure and white light exposure as well. This improving effect was also noted in other BAR compounds. Note that the samples prepared in accordance with the present invention in Example 9 all had an exposure latitude of over 3 as DologH.
Example 10
Preparation of Comparative Sample No. 10-101
[0407] Sample No. 10-101 was prepared in the same manner as with Sample No. 4-101 in Example 4 except that the 0.29 part of the coupler (Y-1) in the B-1 layer of Sample No. 4-101 in Example 4 was replaced by 0.18 part of the coupler (SY-1) and the 0.08 part of the coupler (Y-1) in the B-2 layer was replaced by 0.05 part of the coupler (SY-1).
[0408] The layers of Sample No. 10-101 are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 as in the case of Sample No. 4-101 in Example 4.
Comparative Sample Nos. 10-102 through 10-104
[0409] Sample Nos. 10-102 through 10-104 were prepared in the same manner as with Sample No. 10-101 except that SY-1 in B-1 and B-2 of Sample No. 10-101 was replaced by the couplers listed in Table 10-1.
Inventive Sample Nos. 10-105 through 10-109
[0410] Sample Nos. 10-105 through 10-109 were prepared in the same manner as with Sample No. 10-101 except that B-2 of Sample No. 10-101 was removed, the emulsion in B-1 was replaced by an equimolar mixture of EM-4 and EM-5, the amount of the emulsion, gelatin and DOP in B-1 were increased by 15%, and the couplers listed in Table 10-1 were used. The amounts of the sensitizing dyes and couplers in B-1 per mol silver halide were the same as those in Sample No. 10-101.
Inventive Sample No. 10-110
[0411] Sample Nos. 10-105 was prepared in the same manner as with Sample No. 10-105 except that G-2 and R-2 of Sample No. 10-105 were removed, the emulsion in G-1 and R-1 was replaced by an equimolar mixture of EM-4 and EM-5, the amount of the emulsion, gelatin and TCP in G-1 were increased by 30%. The amounts of the emulsion, gelatin and DOP in R-1 were increased by 25%. The amounts of the sensitizing dyes, couplers and DIR compounds in G-1 and R-1 per mol silver halide were the same as those in Sample No. 10-105.
[0413] Each sample was divided into two parts. One part was stored in a refrigerator at 5. C as a reference, while the other one part was left at 25 C and relative humidity of 80% for 7 days. These two parts were then subjected to exposure through an optical wedge in accordance with a ordinary method and then processed by the processing procedure described in Example 4. The effect of ambient conditions on gradation retention was rated.
[Gradation retention]
[0416] Each sample was divided into two parts and subjected to exposure through an optical wedge. One part of each sample was processed by the above-mentioned processing procedure as reference; the other one part was processed in the same manner as above except that the pH of the developer was changed to 9.8. The effect of change in the pH of the developer on gradation retention was determined by the same method as above.
[0418] As is evident from Table 10-2, the samples in accordance with the present invention have a small variance of gradation between the ligh light and shadow portions of the characteristic curve in retention to changes in storage conditions and processing conditions, and are thus excellent in gradation retention. The samples were also found to have a wide exposure latitude of over 3 as ΔIogH.
[0419] Of the samples in accordance with the present invention, Sample No. 10-110, whose light-sensitive layers all have a single-layer structure, ranks highest in property improving effect and is thus preferable..
[0420] The effect of the present invention was also noted when SY-7, SY-9, SY-11, SY-14 and SY-17 were respectively used in place of the coupler SY-1 of the present invention in B-1 of Sample No. 10-105.
Example 11
Comparative Sample Nos. 11-101 through 11-104
[0421] Sample Nos. 11-101 through 11-104 were prepared in the same manner as with Sample Nos. 10-101 through 10-104 in Example 10 except that the coupler SY-1 in the B-1 and B-2 of Sample Nos. 10-101 through 10-104 was replaced by Y-1, in a molar amount 1.6 times that of SY-1, with the amount of TCP multiplied by 1.6, and the magenta coupler M-1 in G-1 and G-2 was replaced by a coupler listed in Table 11-1, in a molar amount 0.6 time that of M1-, with the amount of TCP multiplied by 0.6.
Invention Sample Nos. 11-105 through 11-108
[0422] Sample No. 11-105 through 11-108 were prepared in the same manner as with Sample No. 11-101 except that G-2 of Sample Nos. 11-101 was removed, the emulsion in G-1 was replaced by an equimolar mixture of EM-4 and EM-5, the amounts of the emulsion and gelatin in G-1 were increased by 30%, and M-1 in G-1 was replaced as shown in Table 11-1. The amounts of the sensitizing dyes, couplers and DIR compounds in G-1 per mol silver halide were the same as those in Sample No. 11-101.
Inventive Sample Nos. 11-109 through 11-111
[0423] Sample Nos. 11-109 through 11-111 were prepared in the same manner as with Sample No. 10-105 except that the green-sensitive layer of Sample No. 10-105 was replaced by G-1 of Sample No. 11-105 and the coupler in G-1 of Sample No. 11-105 was replaced by a coupler listed in Table 11-1.
[0424] The light-sensitive material preservability and processing stability of each sample were rated in the same manner as in Example 10.
[0426] As is evident from Table 11-2, the sample in accordance with the present invention have a small variance of gradation between the high light and shadow portions of the characteristic curve in retention light-sensitive material preservability and processing variance, and are thus excellent in gradation retention. The samples were also found to have a wide exposure latitude of over 3 as ΔlogH.
[0427] Also, Sample Nos. 11-109 through 11-111, whose blue-and green-sensitive layers both have a single-layer structure, show a particularly high improving effect, and are thus preferable.
[0428] The effect of the present invention was also noted in the samples prepared using D-2, D-4 and D-29 in place of D-42 in B-2 of Sample No. 11-105; and those prepared using D-6 and D-10 in place of D-23 in G-1 of Sample No. 11-109, respectively.
Example 12
Preparation of Comparative Sample No. 12-101
[0429] A subbed cellulose acetate support was coated with multilayer color light-sensitive material No. 12-101 having exactly the same vertically double layer structure as that of Sample No. 6-101 in Example 6.
[0430] The layers of Sample No. 12-101 are hereinafter respectively represented by the abbreviations HC, IL-1, R-1, R-2, IL-2, G-1, G-2, YC, B-1, B-2, Pro-1 and Pro-2 as used in Example 6.
Inventive Sample No. 12-102
[0431] Sample No. 12-102 was prepared in the same manner as with Sample No. 12-101 except that B-2 and G-2 of Sample No. 12-101 were removed, the emulsion in B-1 and G-1 was replaced by an equimolar mixture of EM-4 and EM-5, the amounts of the emulsion, gelatin and TCP in B-1 were increased by 15%, and the amounts of the emulsion, gelatin and TCP in G-1 were increased by 30%. The amount of the sensitizing dyes, couplers and DIR compounds in B-1 and G-1 per mol silver halide were the same as those in Sample No 12-101.
[0432] Each sample was cut into a strip of a length corresponding to 24 frames of the 35 mm size. This sheet was rolled so that the light-sensitive layer face was the inside face and placed directly into the film container of a lens-equipped pack unit as disclosed in Japanese Patent O.P.I Publication No. 194255/1988. With the outside end fixed to a cartridge for the 35 mm size film, the strip was placed in the cartridge chamber to yield a photographic ligh-sensitive material pack unit having a picture taking function (fixed focus F = 8; shutter speed 1/100 sec.).
[0433] One unit containing each photographic light-sensitive material sample was stored in a refrigerator at 5 C for 1 month as a reference, while another unit was stored at 37° C and relative humidity of 80% for 1 month.
[0434] After taking pictures of the subject of continuous wedge, each unit sample was processed by the processing procedure described in Example 4.
[0435] Sample Nos. 12-101 and 12-102 were rated as to gradation retention during storage by the evaluating method described in Example 4.
[0437] As is evident from Table 12-2, the photographic light-sensitive material pack unit of the present invention has a small variance of tone between the high light and shadow portions of the characteristic curve during storage, and is thus excellent in gradation reproducibility. This pack unit was also found to have a wide exposure latitude of over 3 as ΔlogH.
[0438] Also, this effect was found to be further enhanced when all the blue-, green and red-sensitive layers have a single-layer structure.
[0439] The effect of the present invention was also noted in the samples prepared using (D-6), (D-2) and (D-10) in place of (D-23) in G-1 of Sample No. 12-102; and those prepared using (D-2) and (D-17) in place of (D-23) in R-1 of Sample No. 12-102; and (D-19) and (D-21) in place of (D-24) in R-1 of Sample No. 12-102; respectively.
1. A silver halide color photographic light-sensitive material comprising a blue-sensitive,
a green-sensitive and a red-sensitive silver halide emulsion layers provided on a
support and at least one of said color-sensitive silver halide emulsion layers has
a single-layer structure, wherein at least one of said silver halide emulsion layers
has a single-layer structure and said silver halide emulsion layer having a single-layer
structure comprises at least two kinds of silver halide grains deffering in average
grain size, and contains a development inhibitor releasing (DIR) compound and the
exposure latitude of said emulsion layer having a single-layer structure is 3.0 or
more.
2. The material of claim 1, wherein said silver halide grains are each composed of
two or more phases differing in silver iodide content and the average silver iodide
content of interior phases is larger than that of exterior phases.
3. The material of claim 1, wherein at least one of said color-sensitive emulsion
layers contains a nitrogen-containing heterocyclic mercapto compound.
4. The material of claim 1, wherein at least one of said color-sensitive emulsion
layers contains a phenol-type cyan coupler having a ureido group at the 2-position
of the phenol group of said coupler.
5. The material of claim 1, wherein said green-sensitive emulsion layer has a single-layer
structure and contains said DIR compound a 5-pyrazolone-type two-equivalent magenta
coupler.
6. The material of claim 1, wherein said material contains a coupler capable of splitting
off a dye or precursor thereof by a coupling reaction with an oxidized product of
an aromatic primary amine color developing agent, in which said dye or said precursor
is bound, directly or through a timing group, to an active position of said coupler
and the absorption maxima of dye to be split off or a dye to be formed from said precursor
is shifted to the side of short wavelength.
7. The material of claim 1, wherein said material contains a compound capable of splitting
off a bleaching accelerator or its precursor by a reaction with an axidized product
of a color developing agent.
8. The material of claim 1, wherein said material contains a high-boiling solvent
having a dielectric constant of 4.00 or more.
9. The material of claim 1, wherein said material has a layer containing silver halide
grains which are substantially does not have light-sensitivity at a position further
from a support than all of said silver halide emulsion layers.
10. The material of claim 1, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure.
11. The material of claim 2, wherein, at least two of said color-sensitive emulsion
layers each has a single-layer structure; and silver halide grains contained said
silver halide emulsion layers with single-layer structure contains silver halide grains
comprising an interior phase having a silver iodide content of from 10 mol% to 40
mil% and the outermost phase having a silver iodide content of smaller than 6 mol%.
12. The material of claim 3, wherein at least two of said color-sensitive emulsion
layers each has a silgle-layer structure; and said nitrogen-containing mercapto compound
is a compound represented by the following Formula I:
wherein Z is a group of atoms necessary for forming a 5- or 6-membered heterocyclic ring comprising a atoms selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom; said heterocyclic ring may be condensed with anothe ring; and M is a hydrogen atom, an alkali metal atom or an ammonium group.
wherein Z is a group of atoms necessary for forming a 5- or 6-membered heterocyclic ring comprising a atoms selected from a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom; said heterocyclic ring may be condensed with anothe ring; and M is a hydrogen atom, an alkali metal atom or an ammonium group.
13. The material of claim 4, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure; and said said phenol type cyan coupler is
a compound represented by the following Formula CU:
wherein X is a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of an aromatic primary amine color developing agent; R1 is an aryl group or a heterocyclic group; R2 is an aliphatic group or an aryl group.
wherein X is a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of an aromatic primary amine color developing agent; R1 is an aryl group or a heterocyclic group; R2 is an aliphatic group or an aryl group.
14. The material of claim 5, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure; and said magenta coupler is a compound represented
by the following Formula M:
wherein Cp is a residue of a 5-pyrazolone-type coupler; * represents a coupling position of said coupler; and X is a substituent capable of splitting off upon a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.
wherein Cp is a residue of a 5-pyrazolone-type coupler; * represents a coupling position of said coupler; and X is a substituent capable of splitting off upon a coupling reaction with an oxidized product of an aromatic primary amine color developing agent.
15. The material of claim 6, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure; and said coupler capable of splitting off
a dye or precursor thereof is a compound represented by the following Formula S:
Coup - (Time) a- X - D (S)
wherein Coup is a coupler residue capable of splitting off - (Time) a-X-D group upon a coupling reaction with an oxidized product of an aromatic primary amine color developing agent; Time is a timing group; a is zero or a positive integer; D' is a dye residue; and X is an auxochromatic group.
Coup - (Time) a- X - D (S)
wherein Coup is a coupler residue capable of splitting off - (Time) a-X-D group upon a coupling reaction with an oxidized product of an aromatic primary amine color developing agent; Time is a timing group; a is zero or a positive integer; D' is a dye residue; and X is an auxochromatic group.
16. The material of claim 7, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure; and said compound capable of splitting off
a bleaching accelerator or precursor thereof is a compound represented by the following
Formula BAR-I: o II , A - ( C )I - (TIME)m - BA (BAR-I) wherein A is a residue capable
of splitting of -(C)ℓ-(TIME)m'-BA group upon a coupling reaction or a cross- oxidizing
reaction with an oxidized product of an aromatic primary amine color developing agent;
TIME is a timing group; BA is a bleaching accelerator of its precursor; m is zero
or 1; and ℓ is 0 or 1, provided that when A is a residue capable of being subjected
to a coupling reaction, ℓ is zero and when A is a residue being subjected to a cross-oxidation
reaction, ℓ is zero or 1.
17. The material of claim 8, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure; said solvent is a compound represented by
the following Formula A, B, C or D* Ri - COOR2 (A)
Ri - 0 - R2 (D) wherein Ri, R2 and R3 are each an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, provided that in Formula D, R1 and R2 are allowed to combine for forming a ring; R4 is a group the same as R1 an -OR1 group or an -SRi group; n is an integer of 1 to 5, provided that when n is 2 or more, R4s may be either the same with or different from each other.
Ri - 0 - R2 (D) wherein Ri, R2 and R3 are each an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group, provided that in Formula D, R1 and R2 are allowed to combine for forming a ring; R4 is a group the same as R1 an -OR1 group or an -SRi group; n is an integer of 1 to 5, provided that when n is 2 or more, R4s may be either the same with or different from each other.
18. The material of claim 9, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure; and said silver halide grains substantially
not having light-sensitivity comprises silver iodobromide and ave an average grain
size from 0.01µm to 0.10u.m.
19. The material of claim 1, wherein all of said color-sensitive emulsion layer each
has a single-layer structure.
20. A package of a photographic light-sensitive material having a photographic camera
function and including a silver halide color photographic light-sensitive material
comprising a blue-sensitive, a green-sensitive and a red-sensitive silver halide emulsion
layers provided on a support and at least one of said color-sensitive emulsion layers
has a single-layer structure, wherein at least one of said silver halide emulsion
layers has a single-layer structure, and said silver halide emulsion layer having
a single layer structure comprises at least two kinds of silver halide grains deffering
in average grain size and contains a development inhibitor releasing (DIR) compound,
and the exposure latitude of said silver halide emulsion layer having sigle-layer
structure is 3.0 or more.
21 The package of claim 20, wherein at least two of said color-sensitive emulsion
layers each has a single-layer structure.