Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/0051—Tabular grain emulsions
  • G03C2001/0055—Aspect ratio of tabular grains in general; High aspect ratio; Intermediate aspect ratio; Low aspect ratio
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C3/00—Packages of films for inserting into cameras, e.g. roll-films, film-packs; Wrapping materials for light-sensitive plates, films or papers, e.g. materials characterised by the use of special dyes, printing inks, adhesives
  • G03C2003/006—Film with lens-disposable camera
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
  • G03C2007/3024—Ratio silver to coupler
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
  • G03C2007/3025—Silver content
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C2200/00—Details
  • G03C2200/26—Gamma
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C3/00—Packages of films for inserting into cameras, e.g. roll-films, film-packs; Wrapping materials for light-sensitive plates, films or papers, e.g. materials characterised by the use of special dyes, printing inks, adhesives
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains

Definitions

• the present invention relates to a silver halide color photographic material. More particularly, the present invention relates to a high sensitive silver halide color photographic material which is excellent in tone and skin reproduction and color saturation at various exposure ranges.
• Image capturing systems making use of a CCD such as a digital still camera, offer convenient merits for users which conventional silver halide photo-capturing systems, such as color negative film cannot. These merits are e.g.: 1) scenery and exposure condition can be checked immediately after picture shooting; 2) unnecessary pictures can be erased. Furthermore this technique offers new possibilities of image display by combination with digital manipulation.
• the gradation of color negative films is in most of the cases designed to produce an optimal result for various exposure conditions and in various cameras. This is especially important for the amateur and semi-professional market where the same film is used for both outdoor and indoor scenes and in (compact) cameras with zoom lenses and in single-use-cameras with fixed shutter speeds and fixed apertures. Generally a somewhat hard gradation is chosen that minimizes the chance of unsuccessful result especially in case of shooting under insufficient exposure conditions. A second aspect is that a hard gradation yields bright saturated colors which are generally preferred by the average customer.
• US2002/0055072A1, US6551771B1 and US6447986B1 disclose that the productivity of printing is improved by use of a color negative film with a softer gradation because the density on the negative at the over-exposure area is reduced.
• W02004/012011A1 claims a color negative film with a soft gradation of which the development stability is improved.
• JP-A-1997/179255 discloses that specific gradations at white light and separated single color exposures improves color and tone reproduction.
• EP-A-0 684 511 describes a motion picture film having a low gradation which faithfully reproduces blacks and whites.
• EP-A-1 324 127, US 6,696,232, EP 0 969 318 and US 6,686,136 disclose a color negative film with a soft gradation and low gamma ratio values suitable for conversion into electronic form.
• the present invention has been developed with a view toward solving the problems of the prior art described above. It is an object of the present invention to provide a high sensitive silver halide color photographic material which is excellent in color and skin tone reproduction, and color saturation at various exposure ranges. It is a further object of this invention to provide a silver halide color photographic material that has an outstanding sharpness, favorable properties in respect to process stability and aging behavior.
• a silver halide color negative photographic light sensitive material comprising at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer on a support, wherein the gamma ratio of the green-sensitive layer is at least 1.9, preferably higher than 2.1.
• E is used to indicate exposure in lux-seconds.
• the exposure amount is expressed as logE, sometimes referred to as logH.
• gamma (signified by the Greek letter y) is a measure of contrast of photographic materials. Hurter and Driffield, the pioneers of the scientific study of sensitometry, named the gradient of the straight-line portion of the characteristic curve gamma in 1890. The gammas usually aimed for in practice around the start of the 20th Century were 0.8 for portraits, 1.0 for architecture and 1.3 for landscapes, although these would all be thought high contrast nowadays. Most ground pictorial subjects call for film with a gamma value around 0.75, varying from 0.65 to 0.90.
• gamma is employed to indicate the incremental increase in image density (DELTA D) produced by a corresponding incremental increase in log exposure (DELTA logE) as discussed in more detail in 'The theory of the photographic process', Fourth edition, T.H. James, p.502.
• the gamma is measured over an exposure range extending between a first characteristic curve reference point lying at a density of 0.20 above fog (or minimum density) and a second characteristic curve reference point lying at a density of 1.20 above fog (or minimum density).
• ⁇ R , G , B ( D R , G , B fog + 1.2 ⁇ D R , G , B fog + 0.2 ) log ( a R , G , B ) ⁇ log ( b R , G , B )
• D R,G,B is the density value of R, G or B respectively
• a R,G,B is the exposure amount (white light) that corresponds with the minimum density level (fog) of R, G, or B + 1.2
• b R,G,B is the exposure amount (white light) that corresponds with the minimum density level (fog) of R, G, or B + 0.2.
• the gamma can be determined for a characteristic curve of a color layer after exposure by white light followed by processing but also for a characteristic curve of the same color layer after exposure by light of the corresponding color followed by processing, e.g. of the green layer after exposure by green light.
• gamma ratio when applied to a color recording layer unit refers to the ratio determined by dividing the gamma of a specific color layer after exposure to light of that specific color followed by processing that enables development of primarily that layer by the gamma of the same color layer unit after exposure by white light followed by processing that enables development of all layers. This term relates to the degree of color correction and color saturation available from that color layer unit generally provided by interlayer interimage effects directed towards conventional optical printing. Larger values of the gamma ratio indicate enhanced degrees of color saturation under optical printing conditions.
• a very suitable method for determining the gamma and the Dyelmage gammas for a sample from the characteristic curves comprises the simultaneous exposure by white light and by red, green and blue light, each onto a separate part of the sample through a wedge that comprises the corresponding color filters as is described in detail in EP-A-1 083 460, the disclosure of which is incorporated herein by reference.
• the gamma ratio is the ratio of the Dye image gamma (of R, G or B) and the white light exposed gamma (of R, G or B) and may be defined as:
• Gamma ratio R , G , B ⁇ DyeImage R , G , B ⁇ R , G , B
• dynamic range is used for the useable log-exposure range of a color layer. It is the range for which a certain difference in exposure amount results in a significant different density value. This parameter can be determined for each color layer from the characteristic curve.
• the main part of the curve is a more or less straight line, the slope of this line is the gradation corresponding to the gamma defined above. At the toe part and at the high density part the slope of the curve decreases which denotes the exposure condition at which the discrimination of details becomes less.
• the minimum log-exposure value is defined as the exposure amount at which the density is 0.1 units higher than the extrapolated line that connects the two points as defined above for the gamma when exposed with white light.
• maximum value is taken the exposure amount (white light) at which the density is 0.1 units lower than the extrapolated line that connects the two points as defmed above for the gamma.
• development inhibitor releasing compound indicates a compound that cleaves to release a development inhibitor during color development.
• DIR's include dye-forming couplers and other compounds that utilize anchimeric and timed releasing mechanisms.
• one-time-use camera is used to indicate a camera supplied to the user preloaded with a light sensitive silver halide photographic element and having a lens and shutter.
• single-use camera film-with-lens unit
• dispenser camera dispenser-sensitive camera
• QualitySnap® Quality of Service
• color negative films currently available on the market generally have a gradation which for most exposure conditions yield pictures with bright saturated colors. This is especially true for general-purpose films that are designed for use under a variety of circumstances. Specific gradations (hard or soft) are applied mainly in professional films that require controlled exposure and sophisticated equipment in order to give good results in the hands of highly skilled photographers. However the average gradations of general-purpose films often lead to washed-out images when a flash is used or under bright sunlight conditions. These drawbacks are most striking for images of people with tanned or dark-colored skin. For optimal reproduction of skin tones a more smooth gradation is preferred especially when the exposure conditions are contrasty.
• a typical situation in which this occurs is when a flashlight is used and the object stands quite close to the photographer: usually the face is overexposed while the background is dark and does not reveal details.
• a professional photographer has means to prevent or limit these effects by selecting a very high sensitive film which renders the use of a flash unnecessary, by flashing indirectly or by using diffusers.
• the present invention provides a film of soft gradation that gives images with excellent skin tones also under difficult circumstances as described above.
• Reducing the gradation of a color negative film can be achieved in several ways, such as decreasing the amounts of silver halide emulsion, decreasing the amount of image coupler and/or increasing the amount of DIR compounds for each of the color layers.
• a serious shortcoming of a softer than average gradation is that the pictures become flat when the light conditions are low in contrast, which is the case e.g. in cloudy weather. This is the reason that the majority of color negative films available in the market do not have a soft gradation. After extensive studies, the present inventors were able to provide a film that overcomes these contradictory demands.
• the present inventors surmise that the reason for this phenomenon is the fact that the human eye is most sensitive for green and magenta colors, while for a good skin tone reproduction the reddish colors are very important and are preferably in balance with the other colors.
• the gamma ratio of the green layer in the color photographic material of the present invention - after standard development - is at least 1.9, preferably at least 2.0, and more preferably at least 2.1.
• the gamma ratio of the red layer is preferably smaller than 1.60, more preferably smaller than 1.50, most preferably below 1.40.
• the gamma ratio of the blue layer is not particularly limited and preferably has a value between 0.90 and 1.40, more preferably between 1.00 and 1.30.
• a very suitable parameter to indicate the quality of a soft gradation film in combination with excellent skin tone and color reproduction is the ratio of the DyeImage gamma of the green sensitive layer and the DyeImage gamma of the red sensitive layer, ⁇ DyeImage,G / ⁇ DyeImage,R .
• this ratio is larger than 1.3, more preferably larger than 1.4. most preferably larger than 1.5.
• the preferred gamma ratios can be realized by changing the type and the quantity of DIR couplers and/or colored masking couplers. It is also recognized that the gamma ratios may be attained in other ways. In one concrete example, judicious choice and balancing of light sensitive emulsion halide content may be employed to optimize the gamma ratio by controlling the interaction of individual color records during development. Emulsion iodide content may be particularly critical in this role. Selection of the quantity of emulsion to be employed in each light sensitive layer and the sensitization conditions employed may also be critical.
• interlayers which may affect the flow of development inhibitors or of development by-products, such as halide ion, between layers may also enable one to achieve the desired condition.
• fine-grained, non-light sensitive silver halide e.g., Lippmann emulsion sols
• silver particles e.g., gray silver sols or Carey Lea silver sols
• couplers and/or non-coupling compounds which enhance chemical interactions between color layers, may be advantageously employed in the practice of the invention to adjust gamma ratios.
• a preferred method is increasing the level of DIR coupler in one or more color layers.
• the DIR content in the layers closest to the green layer is increased.
• green sensitive layer denotes all sublayers that are sensitive to green light. The most effective measure depends among other things on the layer arrangement. As a typical example - in which the order of the light sensitive layers from the position most remote from a support toward the support is blue, green and red, and an emulsion layer having a higher sensitivity is positioned farther from the support than a layer of lower speed sensitive to the same color - the light sensitive layers closest to the green sensitive layer are the highest red sensitive layer and the lowest blue sensitive layer.
• the level of DIR coupler needed to achieve the desired gamma ratio depends on a multitude of factors such as type and quantity of silver halide emulsion, thickness of intermediate layers, reactivity of the DIR couplers applied and of the dye forming couplers, the presence of compounds affecting the development speed, and many more.
• a suitable parameter to indicate the content of DIR couplers for a given layout and composition of a color negative light sensitive material is the ratio of DIR coupler and silver for each (sub)layer.
• the ratio of DIR coupler and silver in the blue sensitive layer having the lowest sensitivity is - for example - preferably larger than 0.10 mmol/g, more preferably larger than 0.25 mmol/g, most preferably more than 0.40 mmol/g.
• the ratio of DIR coupler and silver in the red sensitive layer having the highest sensitivity is preferably larger than 0.06 mmol/g, more preferably larger than 0.08 mmol/g.
• a soft gradation is characterized by the values of the gamma of the characteristic curve of the color layers.
• the gamma of the green light sensitive layer in the color photographic material of the present invention is preferably less than 0.55, and preferably greater than 0.30, more preferably less than 0.53, but greater than 0.35, and most preferably less than 0.50 but greater than 0.40.
• the ratio of the gamma values of the blue layer and the green layer (gamma B/gamma G) and of the gamma values of the red layer and the green layer (gamma R/ gamma G) in the color photographic material of the present invention is preferably not smaller than 0.75 and preferably not larger than 1.25.
• the gradation of the three color layers should not be designed too different from each other in order to attain a good color balance over the full exposure range.
• Another benefit of a softer gradation is an enhanced detail in both highlight and shadow part provided that the film is exposed correctly. This is particularly noticeable in pictures that are taken with a flash. Compared to films with an average gradation the films of the invention exhibit more fine details in the lightest and the darkest parts of the image.
• a high sensitivity of the light sensitive material is beneficial for the overall quality of the product.
• a high sensitivity enlarges the dynamic range of the material and allows high image quality even under reduced lighting conditions.
• An effective approach to improve the shadow details is to increase the sensitivity of the film by increasing the sensitivity of the silver halide emulsions in the highest sensitive layer, usually in combination with other techniques such as increasing the reactivity of the dye forming couplers, decreasing the amount of DIR compounds, etc.
• features such as sharpness and graininess are mainly determined by the properties of the silver halide grains used.
• grains of tabular form having one or two or more parallel twin planes are applied.
• a tabular grain is a silver halide grain having two opposing, parallel (111) main planes.
• a tabular grain of the present invention has one twin plane or two or more parallel twin planes.
• the twin plane is a (111) plane on the two sides of which ions at all lattice points have a mirror image relationship.
• this tabular grain is viewed in a direction perpendicular to the main planes of the grain, it has any of triangular, square, hexagonal, and intermediate truncated triangular shapes, each having parallel outer surfaces.
• the silver halide grains not comprehended in the tabular grains include regular crystal grains and grains having two or more nonparallel twin planes.
• the grains having two nonparallel twin planes include those having the configuration of a triangular pyramid or a rod. These are collectively referred to as "nontabular grains".
• the nontabular grains are not favorable because the specific surface area thereof is so small that using them at a high proportion would cause a sensitivity enhancement to be difficult.
• the color photographic light-sensitive material of the present invention comprises a support and, superimposed thereon, at least a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer and a protective layer. Further, it is preferred that the color photographic light-sensitive material be provided with not only the light-sensitive emulsion layers and protective layer but also various non-light-sensitive layers, such as a color mixing prevention layer, a yellow filter layer (simultaneously functioning as a color mixing prevention layer) and an antihalation layer.
• a color photographic light-sensitive material comprising, arranged in the following sequence from the position most remote from a support toward the support: a protective layer, two or more blue-sensitive emulsion layers, a yellow filter layer (simultaneously functioning as a color mixing prevention layer), two or more green-sensitive emulsion layers, a color mixing prevention layer, two or more red-sensitive emulsion layers, a color mixing prevention layer and an antihalation layer.
• each color-sensitive layer unit is composed of emulsion layers of different speeds, although the order of layer arrangement is not particularly limited, it is common practice to dispose an emulsion layer of higher speed at a position more remote from the support.
• the blue-sensitive silver halide emulsion layer unit when it means a unit composed of two or more blue-sensitive layers of different speeds, it is not necessary to dispose the two or more blue-sensitive layers adjacent to each other.
• the green-sensitive silver halide emulsion layer unit and red-sensitive silver halide emulsion layer unit have the same function as the above blue-sensitive silver halide emulsion layer unit except that these emulsion layers are sensitive to green and red light, respectively.
• Other layer arrangements may be used examples of which are given in e.g. US2004/086812 the contents of which are incorporated herein by reference.
• Each of these silver halide emulsion layers preferably comprises a plurality of silver halide emulsion sublayers whose speeds are different from each other, wherein preferably 50% or more of the total projected area of silver halide grains contained in at least one of the highest-speed emulsion sublayers comprises tabular silver halide grains.
• the tabular silver halide grains preferably have an average aspect ratio of 5 or more, more preferably 10 or more, and most preferably 12 or more.
• the upper limit of the aspect ratio is 50.
• a soft gradation is that less silver is needed to make the product, although a high gamma ratio i.e. a large DyeImage gamma reduces this benefit.
• a higher sensitivity usually requires a larger amount of silver.
• tabular grains By applying tabular grains a higher sensitivity can be realized while keeping the amount of silver used the same.
• all highest speed emulsion sublayers comprise tabular grains. These tabular silver halide grains preferably account for 50% or more of the total projected area of silver halide grains and preferably have an average aspect ratio of 3 or more, more preferably 5 or more.
• the highest speed emulsion sublayers comprise tabular silver halide grains but also the sublayers of intermediate speed for those color layers that comprise at least three sublayers.
• 50% or more of the total projected area of silver halide grains in the sublayers of intermediate speed comprises tabular silver halide grains with an average aspect ratio of preferably 2 or more, more preferably 3 or more.
• the sublayers of the lowest speed comprise tabular grains.
• 50% or more of the total projected area of silver halide grains in the sublayers of lowest speed comprises tabular silver halide grains with an average aspect ratio of preferably 2 or more, more preferably 3 or more. Details about the preferred types of tabular grains are described below.
• the terminology “aspect ratio” means the ratio of diameter to thickness of the grain. Formulated differently, it is the diameter divided by the thickness of each individual silver halide grain.
• the terminology “diameter” used herein refers to the diameter of a circle having an area equal to the projected area of a grain as obtained when observing silver halide grains through a microscope or an electron microscope.
• the method of taking a transmission electron micrograph by the replica technique and measuring the equivalent circular diameter and thickness of each individual grain can be mentioned as an example of aspect ratio determining method. In the above-mentioned method, the thickness is calculated from the length of replica shadow.
• the highest sensitive layers preferably comprise tabular grains.
• the lower sensitive layers may also contain mainly tabular grains but also mixtures with regular grains or layers without tabular grains may be applied. Especially for the lowest sensitive layers the advantages of applying tabular grains is less pronounced and good results can be obtained with other types of grains.
• Silver halide grains that can be used in a photographic emulsion can be selected from regular crystals such as cubic, octahedral, or tetradecahedral crystals, irregular crystals such as spherical or tabular crystals, crystals having crystal defects such as twin planes, or composite shapes thereof.
• a silver halide can consist of fine grains having a grain size of about 0.2 ⁇ m or less or large grains having a projected area diameter of about 10 ⁇ m, and an emulsion can be either a polydisperse or monodisperse emulsion.
• Silver halide photographic emulsions usable in the present invention can be prepared by methods described in, e.g., "I.
• Tabular grains having an aspect ratio (the value obtained by dividing the equivalent-circle diameter of a tabular grain by the grain thickness) of about 3 or more can also be used in the present invention.
• Tabular grains can be easily prepared by methods described in Gutoff, "Photographic Science and Engineering", Vol. 14, pp. 248 to 257 (1970); and U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048, 4,439,520, 5,567,571 and GB 2,112,157, the disclosures of which are incorporated herein by reference.
• the tabular grain emulsions of the invention are preferably composed of silver iodobromide or silver chloroiodobromide.
• silver chloride may be present, the silver chloride content is preferably 8 mol % or less, more preferably 3 mol % or less, or most preferably 0 mol %.
• the silver iodide content is preferably 20 mol % or less inasmuch as the variation coefficient of the grain size distribution of the tabular grain emulsion is preferably 30% or less. The lowering of the variation coefficient of the distribution of equivalent circular diameter of the tabular grain emulsion can be facilitated by lowering the silver iodide content.
• the variation coefficient of the grain size distribution of the tabular grain emulsion is more preferably 20% or less, and the silver iodide content is more preferably 10 mol % or less.
• the variation coefficient of the grain size distribution is a value obtained by dividing the standard deviation of the grain size distribution of tabular grains by the average grain size, and multiplying the resultant quotient by 100.
• the tabular grain emulsions have some intragranular structure with respect to the silver iodide distribution.
• the silver iodide distribution may have a double structure, a treble structure, a quadruple structure or a structure of higher order.
• the tabular grains preferably have dislocation lines.
• thin tabular grains are used without any growth ring structure in the core portion of the grain and with shell portions having 10 or more dislocation lines at fringe areas thereof.
• the growth ring structure refers to a growth ring pattern observed when tabular grains are produced by carrying out growth of silver iodobromide according to the common Double Jet (main plane jet) method. It is considered as a transition of twinned crystal introduced by the presence of iodide ions, and considered as providing unwanted electron traps on grain surfaces.
• the growth ring structure is observed as lines parallel to grain sides.
• the core portions and the shell portions can be distinguished from each other by observing an extremely thin cross section of tabular grains, the cross section perpendicular to the main planes of the tabular grains, through a transmission electron microscope, and hence the core portion thickness can be measured.
• the method to observe the core and shell portions in a grain, the growth ring structure and dislocation lines is described in more detail in US2004/086812 the contents of which are incorporated herein by reference.
• the introduction of dislocation lines in the tabular grains can be accomplished by disposing a specified phase of high silver iodide content within the grains.
• the phase of high silver iodide content may be provided with discontinuous regions of high silver iodide content.
• the phase of high silver iodide content within the grains can be obtained by first preparing base grains (core portions), then providing them with a phase of high silver iodide content and thereafter covering the outside thereof with a phase of silver iodide content lower than that of the phase of high silver iodide content.
• Silver halide emulsions of the present invention can also be subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.
• Reduction sensitization can be selected from a method of adding reduction sensitizers to a silver halide emulsion, a method called silver ripening in which grains are grown or ripened in a low-pAg ambient at pAg 1 to 7, and a method called high-pH ripening in which grains are grown or ripened in a high-pH ambient at pH 8 to 11. Two or more of these methods can also be used together.
• the method of adding reduction sensitizers is preferred in that the level of reduction sensitization can be finely adjusted.
• Preferred compounds as reduction sensitizers are stannous chloride, thiourea dioxide, dimethylamineborane, and ascorbic acid and its derivative.
• an oxidizer for silver is a compound having the effect of converting metallic silver into silver ions.
• a particularly effective compound is the one that converts very fine silver grains, formed as a by-product in the process of formation and chemical sensitization of silver halide grains, into silver ions.
• Preferred oxidizers of the present invention are inorganic oxidizers such as ozone, hydrogen peroxide and its adduct, a halogen element, and thiosulfonate, and organic oxidizers such as quinones.
• the reduction sensitization described above and the oxidizer for silver are preferable to use.
• the reduction sensitization can be performed after the oxidizer is used or vice versa, or the oxidizer can be used simultaneously with the reduction sensitization.
• Metal salts or metal complexes can be added to the silver halide emulsion of the present invention during grain formation, after grain formation and before or during chemical sensitization.
• the metal salt or complex can be doped in an overall grain, only the core portion, or only the shell portion.
• suitable metals are Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi.
• These metals can be added as long as they are in the form of a salt that can be dissolved during grain formation, such as ammonium salt, acetate, nitrate, sulfate, phosphate, hydroxide, hexa-coordinated complex salt, or tetra-coordinated complex salt.
• a salt that can be dissolved during grain formation
• Examples are CdBr 2 , CdCl 2 , Cd(NO 3 ) 2 , Pb(NO 3 ) 2 , Pb(CH 3 COO) 2 , K 3 [Fe(CN) 6 ], (NH 4 ) 4 [Fe(CN) 6 ], K 3 IrCl 6 , (NH 4 ) 3 RhCl 6 , and K 4 Ru(CN) 6 .
• the ligand of a coordination compound may be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. Further examples are disclosed in US 6 537 740, the disclosure of which is incorporated herein by reference. These metal compounds can be used either singly or in the form of a combination of two or more types of them.
• Silver halide emulsions of the present invention are preferably subjected to selenium sensitization.
• selenium sensitizers usable in the present invention selenium compounds disclosed in conventionally known patents can be used.
• a labile selenium compound and/or a non-labile selenium compound is used by adding it to an emulsion and stirring the emulsion at a high temperature, preferably 40 °C or more for a predetermined period of time.
• non-labile selenium compounds it is preferable to use compounds described in, e.g., Jpn. Pat. Appln. KOKOKU Publication No. (hereinafter referred to as JP-B-)44-15748, JP-B-43-13489, and JP-A-4-25832 and JP-A-4-109240, the disclosures of which are incorporated herein by reference.
• the non-labile selenium sensitizer refers to the sensitizer which causes the amount of silver selenide formed upon the addition of non-labile selenium sensitizer only without the use of any nucleophilic agent to be 30% or less based on the amount of added non-labile selenium sensitizer.
• the non-labile selenium sensitizer there can be mentioned compounds described in, for example, JP-B's-46-4553, 52-34492 and 52-34491.
• the non-labile selenium sensitizer it is preferred to simultaneously use a nucleophilic agent.
• the nucleophilic agent there can be mentioned compounds described in, for example, JP-A-9-15776.
• a silver halide solvent usable in the present invention are (a) organic thioethers described in, e.g., U.S.P.'s 3,271,157, 3,531,289, and 3,574,628, and JP-A's-54-1019 and 54-158917, the disclosures of which are incorporated herein by reference, (b) thiourea derivatives described in, e.g., JP-A's-53-82408, 55-77737, and 55-2982, the disclosures of which are incorporated herein by reference, (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, described in, e.g., JP-A-53-144319, the disclosure of which is incorporated herein by reference, (d) imidazoles described in, e.g., JP-A-
• a silver halide solvent are thiocyanate and tetramethylthiourea.
• a preferred amount is, for example, 1 ⁇ 10 -4 to 1 ⁇ 10 -2 mol per mol of a silver halide.
• a gold sensitizer for use in gold sensitization of the present invention can be any compound having an oxidation number of gold of +1 or +3, and it is possible to use gold compounds normally used as gold sensitizers.
• Representative examples are chloroaurate, potassium chloroaurate, aurictrichloride, potassium auricthiocyanate, potassium iodoaurate, tetracyanoauric acid, ammonium aurothiocyanate, pyridyltrichloro gold, gold sulfide, and gold selenide.
• the addition amount of gold sensitizers changes in accordance with various conditions, the amount is preferably 1 ⁇ 10 -7 to 5 ⁇ 10 -5 mol per mol of a silver halide.
• Emulsions of the present invention are preferably subjected to sulfur sensitization during chemical sensitization. This sulfur sensitization is commonly performed by adding sulfur sensitizers and stirring the emulsion for a predetermined time at a high temperature, preferably 40 °C or more.
• Sulfur sensitizers known to those skilled in the art can be used in sulfur sensitization. Examples are thiosulfate, allylthiocarbamidothiourea, allylisothiacyanate, cystine, p-toluenethiosulfonate, and rhodanine.
• sulfur sensitizers described in, e.g., U.S.P.'s 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955, German Patent 1,422,869, JP-B-56-24937, and JP-A-55-45016 the disclosures of which are incorporated herein by reference.
• the addition amount of sulfur sensitizers need only be large enough to effectively increase the sensitivity of an emulsion. This amount changes over a wide range in accordance with various conditions, such as the pH, the temperature, and the size of silver halide grains. However, the amount is preferably 1 ⁇ 10 -7 to 5 ⁇ 10 -5 mol per mol of a silver halide.
• the photographic emulsion of the present invention is preferably subjected to a spectral sensitization with at least one methine dye or the like, from the viewpoint that the effects desired in the present invention can be exerted.
• usable dyes include cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.
• Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes and composite merocyanine dyes. Any of nuclei commonly used in cyanine dyes as basic heterocyclic nuclei can be contained in these dyes.
• nuclei examples include a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus and a pyridine nucleus; nuclei comprising these nuclei fused with alicyclic hydrocarbon rings; and nuclei comprising these nuclei fused with aromatic hydrocarbon rings, such as an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus,
• any of 5 or 6-membered heterocyclic nuclei such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus can be applied as a nucleus having a ketomethylene structure to the merocyanine dye or composite merocyanine dye.
• spectral sensitizing dyes may be used either individually or in combination.
• the spectral sensitizing dyes are often used in combination for the purpose of attaining supersensitization. Representative examples thereof are described in U.S.P.'s 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377; 3,769,301, 3,814,609, 3,837,862 and 4,026,707, and GB 1,344,281 and 1,507,803, JP-B's-43-4936 and 53-12375 and JP-A's-52-110618 and 52-109925.
• the emulsion of the present invention may be doped with a dye which itself exerts no spectral sensitizing effect or a substance which absorbs substantially none of visible radiation and exhibits supersensitization, together with the above spectral sensitizing dye.
• the emulsion may be doped with the spectral sensitizing dye at any stage of the process for preparing the emulsion which is known as being useful. Although the doping is most usually conducted at a stage between the completion of the chemical sensitization and before the coating, the spectral sensitizing dye can be added simultaneously with the chemical sensitizer to thereby simultaneously effect the spectral sensitization and the chemical sensitization as described in U.S.P.'s. 3,628,969 and 4,225,666.
• the spectral sensitization can be conducted prior to the chemical sensitization as described in JP-A-58-113928, and also, the spectral sensitizing dye can be added prior to the completion of silver halide grain precipitation to thereby initiate the spectral sensitization.
• the above compound can be divided prior to addition, that is, part of the compound can be added prior to the chemical sensitization with the rest of the compound added after the chemical sensitization as taught in U.S.P. 4,225,666.
• the spectral sensitizing dye can be added at any stage during the formation of silver halide grains, such as the method disclosed in U.S.P. 4,183,756 and other methods.
• the addition amount of sensitizing dyes can be 4 ⁇ 10 -6 to 8 ⁇ 10 -3 mol per mol of a silver halide.
• an addition amount of about 5 ⁇ 10 -5 to 2 ⁇ 10 -3 mol is more effective.
• Fog occurring while a silver halide emulsion of the present invention is aged can be improved by adding and dissolving a previously prepared silver iodobromide emulsion during chemical sensitization.
• This silver iodobromide emulsion can be added at any timing during chemical sensitization. However, it is preferable to first add and dissolve the silver iodobromide emulsion and then add sensitizing dyes and chemical sensitizers in this order.
• the silver iodobromide emulsion used has an silver iodide content lower than the surface silver iodide content of a host grain, and is preferably a pure silver bromide emulsion.
• the size of this silver iodobromide emulsion is not limited as long as the emulsion can be completely dissolved.
• the equivalent-sphere diameter is preferably 0.1 ⁇ m or less, and more preferably, 0.05 ⁇ m or less.
• the addition amount of the silver iodobromide emulsion changes in accordance with a host grain used, the amount is basically preferably 0.005 to 5 mol%, and more preferably, 0.1 to 1 mol% per mol of silver.
• a non-light-sensitive fine-grain silver halide is preferably used.
• the non-light-sensitive fine-grain silver halide preferably consists of silver halide grains which do not absorb light during imagewise exposure for obtaining a dye image and consequently are not substantially developed during development. These silver halide grains are preferably not fogged in advance.
• the content of silver bromide is 0 to 100 mol%, and silver chloride and/or silver iodide can be added if necessary.
• the non-light-sensitive fine-grain silver halide preferably contains 0.5 to 10 mol% of silver iodide.
• the average grain size (the average value of equivalent-circle diameters of projected areas) of the fine-grain silver halide is preferably 0.01 to 0.5 ⁇ m, and more preferably, 0.02 to 0.2 ⁇ m.
• Photographic additives that can be used in the present invention are also described in Research Disclosures (RD) 17643 (December 1978), 18716 (November 1979), 307105 (November 1989) and 308119 (December 1989), the entire contents of which are incorporated herein by reference. The relevant portions are summarized in the following table.
• the ISO speed of the color photographic material of the present invention is preferably at least 400, and more preferably at least 600, and most preferably at least 640.
• the dynamic range of the color photographic material of the present invention is preferably at least 3.5 in LogE unit, more preferably at least 3.8, most preferably at least 4.1 for the green sensitive layer, preferably at least 3.3, more preferably at least 3.6 for the blue layer and for the red layer the dynamic range is preferably at least 3.6 in logE units, more preferably at least 3.9, and most preferably at least 4.1, since this allows for a comfortable margin of error in exposure level selection by a photographer. Very large exposure latitudes are especially preferred for elements preloaded in one-time-use cameras, since the ability to obtain accurate image reproduction with rudimentary exposure control is realized.
• the total amount of silver contained in the color photographic material of the present invention is preferably in the range of 3.0 to 9.0 g/m 2 , and more preferably in the range of 4.0 to 6.0 g/m 2 , in terms of coated amount.
• the terminology "silver content” used herein means the total amount, in terms of silver, of contained silvers such as silver halides and metallic silver.
• the total thickness of the sensitized layers, interlayers and protective layers on the exposure face of the support are preferably less than 35 ⁇ m. It is more preferred that the total layer thickness be less than 28 ⁇ m.
• One of the preferable embodiments of the present invention is a color photographic material which comprises at least one cyan sensitive silver halide emulsion layer.
• This layer upgrades the color reproduction as a donor layer of interlayer effect having a spectral sensitivity distribution different from those of the main light sensitive layers BL, GL and RL as described in US patents 4,663,271, 4,705,744 and 4,707,436 and JP-A-62-160448 and JP-A-63-89850.
• This cyan sensitive layer is preferably arranged adjacent to or close to the main light sensitive layers.
• Thrust cartridges are disclosed by U.S. Pat. Nos. 5,226,613 to Kataoka et al. ; 5,200,777 to Zander; 5,031,852 to Dowling et al.; 5,003,334 to Pagano et al. ; and 4,834,306 to Robertson et al.
• These thrust cartridges can be employed in reloadable cameras designed specifically to accept them, in cameras fitted with an adapter designed to accept such film cassettes or in one-time-use cameras designed to accept them.
• Narrow-bodied one-time-use cameras suitable for employing thrust cartridges are described in U.S. Pat. No. 5,692,221 to Tobioka et al. While the film can be mounted in a one-time-use camera in any manner known in the art, it is especially preferred to mount the film in the one-time-use camera such that it is taken up on exposure by a thrust cartridge. Film supplied in a thrust cartridge can be supplied in any convenient width. Widths of about 24 mm as employed in the Advanced Photo SystemTM (APS) are contemplated as well as wider formats, such as 35 mm or even wider.
• APS Advanced Photo SystemTM
• the specific features of the photographic light sensitive material according to this invention make it very suitable for use in one-time-use cameras.
• the smooth soft gradation in combination with the high sensitivity allow for a wide exposure latitude and gives high quality pictures with fine details in highlights and shadows even under low light conditions.
• the material according to the invention can be employed in any one-time-use camera known in the art.
• These cameras can provide specific features as known in the art such as shutter means, film winding means, film advance means, waterproof housings, single or multiple lenses, lens selection means, variable aperture, focus or focal length lenses, means for monitoring lighting conditions, means for adjusting shutter times or lens characteristics based on lighting conditions or user provided instructions, and means for camera recording use conditions directly on the film.
• These features include, but are not limited to: providing simplified mechanisms for manually or automatically advancing film and resetting shutters as described at Skarman U.S. Pat. No. 4,226,517; providing apparatus for automatic exposure control as described at Matterson et al, U.S. Pat. No.
• the light sensitive material according to the present invention can be developed by conventional methods described in the aforementioned RD No. 17643 (December 1978), pages 28 and 29; RD No. 18716 (November 1979), page 651, left to right columns, RD No. 307105 (November 1989), pages 880 and 881, as well as in RD No. 308119 (December 1989) and RD No. 38957 (September 1996), the contents of which are incorporated herein by reference.
• An example of widely used processing chemical for color negative light sensitive materials is FUJICOLOR JUST-IT CN-16LTM.
• a color negative film processing solution that is suitable for use in the present invention will be described below.
• Preferred color developing agents for use in especially rapid processing are 2-methyl-4-[N-ethyl-N-(2-hydroxyethyl)amino]aniline, 2-methyl-4-[N-ethyl-N-(3-hydroxypropyl)amino]aniline and 2-methyl-4-[N-ethyl-N-(4-hydroxybutyl)amino]aniline.
• color developing agents are preferably used in an amount of 0.01 to 0.08 mol, more preferably 0.015 to 0.06 mol, and most preferably 0.02 to 0.05 mol per liter (hereinafter also referred to as "L") of the color developing solution.
• the replenisher of the color developing solution preferably contains the color developing agent in an amount corresponding to 1.1 to 3 times the above concentration, more preferably 1.3 to 2.5 times the above concentration.
• Hydroxylamine can widely be used as a preservative of the color developing solution.
• hydroxylamine derivatives having substituents such as alkyl, hydroxyalkyl, sulfoalkyl and carboxyalkyl groups.
• Preferred examples thereof include N,N-di(sulfoethyl)hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine and N,N-di(carboxyethyl)hydroxylamine.
• N,N-di(sulfoehtyl)hydroxylamine is most preferred. Although these may be used in combination with hydroxylamine, it is preferred that one or two or more members thereof be used in place of hydroxylamine.
• preservatives are preferably used in an amount of 0.02 to 0.2 mol, more preferably 0.03 to 0.15 mol, and most preferably 0.04 to 0.1 mol per L of the color developing solution.
• the replenisher of the color developing solution preferably contains the preservatives in an amount corresponding to 1.1 to 3 times the concentration of the mother liquor (processing tank solution) as in the color developing agent.
• a color developer preferably contains sulfite as an agent for preventing oxidized color developing agent from changing into tar.
• the amount of this sulfite that is used is preferably 0.01 to 0.05 mol, and more preferably, 0.02 to 0.04 mol per L of color developer.
• sulfite is preferably used at a concentration 1.1 to 3 times the above concentration.
• the pH value of the color developing solution preferably ranges from 9.8 to 11.0, more preferably from 10.0 to 10.5.
• the pH of the replenisher is preferably set for a value 0.1 to 1.0 higher than the above value.
• Common buffers such as carbonic acid salts, phosphoric acid salts, sulfosalicylic acid salts and boric acid salts, are used for stabilizing the above pH value.
• the amount of the replenisher of the color developing solution preferably ranges from 80 to 1300 mL per m 2 of the light-sensitive material, the employment of smaller amount is desirable from the viewpoint of reduction of environmental pollution load. Specifically, the amount of the replenisher more preferably ranges from 80 to 600 mL, most preferably from 80 to 400 mL.
• a development accelerator such as pyrazolidones represented by 1-phenyl-3-pyrazolidone and 1-phenyl-2-methyl-2-hydroxylmethyl-3-pyrazolidone, or a thioether compound represented by 3,6-dithia-1,8-octandiol.
• Development is typically carried out by contacting the material preferably for up to about 240 seconds, more preferably for up to about 200 seconds, at a temperature above about 30° C, and generally at from about 35 to about 65° C, and preferably at from about 38 to about 50° C with a color developing solution in suitable processing equipment, to produce the desired developed image.
• a higher temperature range can be used to accelerate processing, reducing the processing time.
• a lower temperature range can be used to improve the picture quality or the stability of the processing solutions.
• the overall processing time (from development to final rinse or wash) can be from about 45 seconds to about 20 minutes. Shorter overall processing times, that is, less than about 8 minutes, are desired for processing photographic color negative films according to this invention.
• the photographic emulsion layer which has been color-developed is normally subjected to bleach.
• Bleach may be effected simultaneously with fixation - a process also referred to as desilvering - (i.e., blix), or these two steps may be carried out separately.
• desilvering - i.e., blix
• bleach may be followed by blix.
• any of an embodiment wherein two blix baths connected in series are used, an embodiment wherein blix is preceded by fixation, and an embodiment wherein blix is followed by bleach may be selected arbitrarily according to the purpose.
• the bleaching bath, blix bath or a prebath thereof can contain, if desired, a bleaching accelerator and the bleaching or blix solution preferably contains an organic acid.
• the thus desilvered silver halide color photosensitive material of the present invention is subjected to washing and/or stabilization.
• washing and/or stabilization examples of bleaching agents, bleaching accelerators, fixing agents, organic acids, and other useful compounds and details about suitable process conditions are given in US 2004/086811, the contents of which are incorporated herein by reference.
• the number corresponding to each component indicates the coating amount in units of g/m 2 , except for the amount of sensitizing dye and further unless expressly indicated otherwise.
• the coating amount of a silver halide is expressed as the amount of silver (in g/m 2 ).
• the coating amount of each sensitizing dye is indicated in units of mols per mol of silver halide in the same layer.
• the individual layers contained W-1 to W-11, B-4 to B-6, F-1 to F-19, lead salt, platinum salt, iridium salt, and rhodium salt.
• Table 1 below shows the characteristics of emulsions A to P indicated by abbreviations above.
• the surface iodide content can be checked as follows by using XPS. Each sample was cooled to -115.degree C. in a vacuum of 1 ⁇ 10 -6 Pa or less, and MgK was radiated as probe X-rays at an X-ray source voltage of 8 kV and an X-ray current of 20 mA, thereby measuring Ag3d5/2, Br3d, and I3d5/2 electrons. The integral intensity of the measured peak was corrected by a sensitivity factor. From these intensity ratios, the surface iodide content was calculated.
• Examples 002 to 005 were formed by changing the 3rd, 4th, 5th, 8th, 9th, 10th, 12th and 13th layers of sample 001 as shown in Table 2.
• Comparative example 005 is comparable to a standard amateur film of ISO speed 400 as currently used in the market.
• the reference samples are obtained commercially.
• Table 2 Layer Sample 002 Sample 003 Sample 004 Sample 005 3rd Coating amounttimes 0.85 - Coating amount times 0.85 Coating amount times 1.5 except that emulsion A is replaced by emulsion C and Emulsion B: 0.374 Emulsion C: 0.367 g/m 2 4th Coating amount times 0.85 Coating amount times 0.95 Coating amount times 0.81 Coating amount times 0.5 except Emulsion C: 0.331 Emulsion D: 0.706 g/m 2 5th ExC-6: 0.036 g/m 2 Coating amount times 0.5 Coating amount times 0.5 except ExC-6: 0.036 g/m 2 Coating amount times 0.5 except Emulsion D: 0.291 Emulsion E: 0.575 g/m 2 7th - - - Coating amount times 1.1 8th Coating amount times 0.8
• the obtained samples were sequentially subjected to continuous wedge exposure by white light for 5/1000 sec through Corning filter 5900, followed by color development processing described below.
• the filters SC-62, BPN-53 and BPN-45 (Fuji Photo Film Co., Ltd.) were used respectively.
• After drying the samples were subjected to status M densitometry in order to obtain the characteristic curves, from which the photographic speed and gamma values were determined.
• the ISO speed of the samples was determined independently according ISO standard 5800 (1987). The evaluation result is summarized in Table 3 and 4.
• 135 format cartridges were prepared by use of the obtained color negative samples for picture evaluation.
• Various kinds of picture scene including dark-, yellow- and white-colored skin, gray-rich and colorful objects, were taken under conditions of normal exposure, -2 stop, +3 and +5 stop exposure.
• the 135 format films were processed after photo shooting with color development processing described below.
• Picture prints were prepared by using of the developed color negative films and commercially available Fujicolor paper.
• Comparative example 002 has the same gradation properties but with a higher ISO speed.
• Example 002 can be derived from example 001 by selecting appropriate silver halide emulsions and quantities thereof and by adjusting the ratios of the different silver halide emulsions in the individual color layers and/or by increasing the coated quantity of the sublayers of the highest speed.
• the advantage of a higher speed is a larger dynamic range. Both samples show a good skin tone reproduction but the color saturation is insufficient leading to flat images under low contrast light conditions.
• inventive example 003 was derived by increasing the DIR coupler amounts in the 5th and 12th layer. By this action the gamma ratio of the green sensitive layer increased dramatically with as result a very good tone and color reproduction and vivid pictures under various exposure conditions.
• inventive example 001 was derived from comparative example 002 in a similar way. To fully optimize the balance of the color layers additional small recipe modifications were done by a trial and error method as is a standard procedure in the art. As can be seen from the data presented in table 5 inventive example 001 combines a very good skin tone reproduction and color saturation with excellent highlight-to-shadow tone reproduction.
• compositions of the processing solutions were as follows (all amounts given in grams, unless otherwise indicated).
• Cold developer Diethylenetriaminepentaacetate 1.0 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4-(N-ethyl-N-.beta.-hydroxylethylamino)-2-methylaniline sulphate 4.5 Water to make 1.0 L pH (adjusted by potassium hydroxide and sulfuric acid) 10.05 (Bleach solution) Ferric Sodium ethylenediamine tetraacetate trihydrate 100.0 Disodium ethylenediaminetetraacetate 10.0 3-mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 mL Water to make 1.0 L pH (ad
• the samples which were prepared above were also installed into single-use camera units.
• the unit of Fujicolor QuickSnap Smart Flash manufactured by Fuji Photo Film Co., Ltd was utilized.

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