JP2008233805A - Silver halide photographic sensitive material and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a technique for increasing sensitivity and to provide a technique for recording digital information on a silver halide photographic sensitive material with high resolution and less degradation. <P>SOLUTION: The silver halide photographic sensitive material includes, on a transparent support, blue-sensitive, green-sensitive and red-sensitive photosensitive unit layers each comprising a plurality of layers substantial same in color sensitivity but different in photosensitivity, wherein silver halide grains contained in a silver halide emulsion of at least one layer of the plurality of layers different in photosensitivity have two or more maximums in a grain diameter distribution curve thereof because the silver halide grains have two or more grain diameters. The sensitivity of silver halide grains having the largest maximum grain diameter is higher than the sensitivity of silver halide grains having the smallest maximum grain diameter, and the sensitivity of a mixture of the silver halide grains having the largest maximum grain diameter and the silver halide grains having the smallest maximum grain diameter is substantially higher than the sensitivity of the silver halide grains having the largest maximum grain diameter. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an image forming technique using a silver halide photographic light-sensitive material, and more particularly, to realize an image forming method for recording digital information on a silver halide photographic light-sensitive material with high resolution and little deterioration, and the image forming method. And a high-sensitivity silver halide photographic light-sensitive material.

  Here, recording with little deterioration in the present invention means to suppress the disappearance of the image structure included in the digital image information at the time of recording, and to further suppress the change at the time of the recording of the color information.

  Conventional movie production is a method in which image information shot using a negative film for shooting is used as a master image, a copy is produced by printing on an intermediate film, and this is further printed on a positive film for movie use for projection. It was taken.

  In many cases, intermediate films for replicating are used twice. The original negative film is printed on a negative intermediate film to create a master positive. The master positive is then printed again on the intermediate film to create a duplicate negative. Finally, the duplicate negative is printed on motion picture positive film to produce a screen print.

  In recent years, in the production of this movie, digitization has been rapidly spreading, in which an original image is digitally synthesized and edited, and converted into an analog image again on a film recorder. This is because by combining and editing by a computer, it is possible to create a video that is impossible in reality and to expand the degree of freedom of video expression. As the original image, it is possible to use various information such as image information photographed on a photographing negative film as digital image information by a film scanner, image information photographed by an HD video camera, computer graphics, and the like.

  As described above, when the original image is produced as digital information with good convenience and this is shown in the conventional analog projection, the original image produced as digital information is printed on an intermediate film, which is the same as the conventional method. The process of printing on movie positive film is performed.

  However, when the above method is used, a new problem occurs with the increase in resolution of digital information. When an original image is printed on a silver halide photographic light-sensitive material, there is a problem that image quality is deteriorated and sufficient film quality cannot be maintained. There has been a need to improve image quality degradation due to photographic characteristics of analog silver halide photosensitive materials, such as blurring, sharpness degradation, and color reproducibility degradation. Patent Document 1 discloses a silver halide color photographic light-sensitive material characterized in that the N value of a magenta image by laser scanning exposure is 100 μm to 200 μm. The N value is an amount corresponding to the blur of the image, and it is shown that the blur of characters is reduced in recording on color photographic paper. However, the pixel size is 12 μm or less at a resolution of 2000 dpi or higher, which has been used in recent years in the field of movie production, and the above N value is clearly inappropriate for resolving fine image information. Therefore, a method for recording digital information on a silver halide photographic material without deteriorating the digital information has been strongly desired.

On the other hand, in the field of silver halide color photographic light-sensitive materials, increasing the sensitivity without increasing the grain size of silver halide emulsion grains has been a long-standing problem. In general, photographic sensitivity is determined by the grain size of silver halide emulsion grains. The larger the emulsion grains, the more the photographic speed increases. However, the blur and graininess deteriorate as the grain size of the silver halide grains increases, so that the sensitivity and the graininess are in a trade-off relationship. Increasing the sensitivity without increasing the silver halide grain size in the industry is the most fundamental and important issue for improving the image quality of photographic materials. It was sought after.
Japanese Patent Laid-Open No. 10-20461

  An object of the present invention is to provide a technique for recording digital information on a silver halide photographic light-sensitive material with high resolution and little deterioration, and in the silver halide photographic light-sensitive material capable of realizing the technique, the particle size of silver halide grains It is an object of the present invention to provide a technique capable of increasing sensitivity without increasing the sensitivity.

As a result of intensive studies to solve the above problems, it was found that the problems can be achieved by the following.
(1) A halogen having a blue-sensitive photosensitive unit layer, a green-sensitive photosensitive unit layer, and a red-sensitive photosensitive unit layer each having a plurality of layers having the same color sensitivity but different sensitivities on the transparent support. In the silver halide photographic light-sensitive material, the silver halide grains contained in the silver halide emulsion of at least one of the plurality of layers having different sensitivities have two or more particle diameters, whereby the particle diameter A silver halide grain having a maximum grain size (D1) having two or more maxima in the distribution curve and having the largest grain size (D1) among the two or more maxima is a grain having the smallest grain size. Higher than the sensitivity of the silver halide grains having the diameter (D2) and having the largest grain diameter (D1) and the halogen having the largest grain diameter (D2) having the smallest grain diameter When silver halide grains are mixed The silver halide photographic light-sensitive material is characterized in that the sensitivity of the silver halide is substantially higher than the sensitivity of the silver halide grains having the maximum particle size (D1) having the largest particle size.

  (2) The maximum particle size (D1) having the largest particle size and the maximum particle size (D2) having the smallest particle size satisfy the following formula (I): Silver halide photographic light-sensitive material.

Formula (I)
D2 / D1 <0.7
(3) The silver halide photographic light-sensitive material as described in (1) or (2), wherein the maximum particle size (D2) having the smallest particle size satisfies the following formula (II).

Formula (II)
D2 <0.1 μm
(4) The silver halide photographic light-sensitive material as described in (1) or (2), wherein the maximum particle size (D2) having the smallest particle size satisfies the following formula (III):

Formula (III)
D2 <0.05 μm
(5) The silver halide photographic light-sensitive material as described in any one of (1) to (4), wherein the image information is recorded with little deterioration in an image forming method for recording digital image information at a resolution of 2000 dpi or more. .

  (6) The silver halide photographic light-sensitive material as described in any one of (1) to (4), wherein digital image information of 3 million pixels or more is recorded with little deterioration.

  (7) The silver halide photographic light-sensitive material as described in any one of (1) to (6), wherein the blur k during image recording satisfies the following formula (A).

k <4.5 × (D−0.2) ² (A)
In formula (A),
D: Color density blur of silver halide photographic material k: Bleeding at color density D (μm)
(8) The silver halide photographic light-sensitive material as described in any one of (1) to (7), wherein the color purity ratio is 80% or more in color reproduction during image recording.

  (9) An image forming method in which the silver halide photographic light-sensitive material according to any one of (1) to (8) is further recorded on the silver halide photographic light-sensitive material by an analog method.

The present invention will be described in detail.
(Bleeding evaluation method)
In the present invention, the blur k during image recording preferably satisfies the following formula (A).

k <4.5 × (D−0.2) ² (A)
In formula (A),
D: Color density blur of silver halide photographic material k: Bleeding at color density D (μm)
Here, the formula (A) needs to hold for all exposure light sources used during image recording. For example, when the exposure light source uses a three-color light source of red, green, and blue, the single color exposure is performed for each of these colors, and the color density D at that time and the blur k at that density satisfy the formula (A). .

  D at this time is evaluated based on two points of color density Dmin + 1 and Dmin + 2, and it is necessary to satisfy the formula (A) at any density. Dmin is the density when the photosensitive material is developed without being exposed.

  As shown in FIG. 1, the blur k is a blur width of the color image in the surface direction of the photosensitive material at a density of Dmin + 0.2 when the exposure amount is adjusted so that the photosensitive material develops a color density D as shown in FIG. Is measured and set as k.

  In the present invention, in order to record with little deterioration, the blur k during image recording preferably satisfies the above formula (A), more preferably satisfies the following formula (A-2), and the following formula (A- It is more preferable to satisfy 3).

k <4.0 × (D−0.2) ² (A-2)
k <3.5 × (D−0.2) ² (A-3)
(Evaluation method of color purity rate)
In the present invention, the color purity rate means sensitometric exposure for each of red, green, and blue, and the image density obtained for the main color density in the single color exposure is a, and the color density is mixed. It is expressed by the following formula (B) where b is the color density of another color different from the main color density and a high density color.

Color purity ratio (%) = (a−b) / a × 100 (B)
The requirement that the color purity ratio represented by the formula (B) is equal to or higher than a specific value needs to hold for all the regions where the main color density is from Dmin + 0.1 to Dmax, and single color exposure of red, green, and blue is performed. It is necessary to hold in either case. Dmin represents the minimum value of color density in the photosensitive material and corresponds to the density after processing of the unexposed film. Dmax represents the maximum value of the color density in the photosensitive material. The maximum value of the color density is made to correspond to the maximum value of the density of the digital image information. In the case of the widely used Cineon format, the maximum density is about Dmin + 2.

  In the present invention, in order to record with little deterioration, the color purity is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.

  Although there is no particular limitation on an apparatus for recording digital information on a silver halide photographic light-sensitive material, a so-called film recorder, which can be used in the method of the present invention, a commercially available apparatus can be used.

For example, ARRI ARSERSER, ARRILASER HD using BGR laser as the light source method, CELCO FURY, FIRETORM using CRT method, IMAGICA realtime, HSR high-speed recorder using COS method, CINEVATIONor One, Cinevater Five, etc. are raised.

  In order to achieve the present invention, as a result of intensive studies, it has become clear that it is extremely effective to use a silver halide photographic light-sensitive material designed so as to reduce image deterioration during recording. The main cause of image blur is the scattering of the recording light inside the photosensitive material, and the blur of the image can be remarkably improved by reducing the scattered light. Since light scattering is greatly affected by the silver halide fine particles in the photosensitive material, it is effective to reduce the amount of silver halide fine particles used as much as possible, but it is also effective to reduce the size of the silver halide fine particles It is. Since all of these means cause a decrease in sensitivity of the photosensitive material, it is preferable to increase the sensitivity of the silver halide fine particles. Further, it is known that a dye can be used to absorb scattered light, and it can be preferably used in the present invention. There are water-soluble dyes and oil-soluble dyes. Water-soluble dyes are widely used in conventional light-sensitive materials, but it is considered that surprising effects can be obtained by using oil-soluble dyes. The result became clear. For example, when using an oil-soluble cyan dye that absorbs red light, it is effective to use it in an upper layer as close as possible to the red color-sensitive layer. This is presumed that the influence of the scattered light is minimized by removing the red light scattered in the photosensitive material immediately before reaching the red color-sensitive layer. In order to increase color purity, it is effective to prevent color mixing. The color mixing inhibitor used in the intermediate layer between each color-sensitive layer generates processing color mixing when the amount used is insufficient, but if it is too much, the sensitivity of the photosensitive material is lowered, so it is set optimally. It is effective. It is also important to reduce spectral color mixing caused by exposure of a color-sensitive layer different from the exposure color. For example, the spectral color mixture can be reduced by increasing the difference between the green and blue sensitivities of the red color-sensitive layer with respect to the red sensitivity. For this purpose, the red light at the time of recording matches the red sensitivity wavelength of the photosensitive material. Is extremely effective.

The silver halide emulsion of the present invention will be described in detail.
The silver halide emulsion of the present invention contains at least one of a plurality of layers having different sensitivities constituting the silver halide photographic light-sensitive material of the present invention, and contains two or more silver halide grains having different particle sizes. Contains. Therefore, the grain size distribution curve of silver halide grains has two or more maximums.

  The grain size of silver halide grains is the diameter of spherical silver halide grains, and the diameter of a projected image converted to a circular image of the same area in the case of grains having a shape other than a cube or a sphere. In the case of tabular grains, the average value of the diameters when the volume is converted to a sphere equivalent. The shape and projected image of the silver halide grains can be observed with a microscope or an electron microscope.

  In the silver halide emulsion of the present invention, the grain size distribution curve of silver halide grains has two or more maximums. In order for the silver halide grain size distribution curve to have two or more maximums, it may be composed of two or more types of polydisperse emulsions having different grain sizes, but it must contain at least one type of monodisperse emulsion. And most preferably composed of two or more types of monodisperse emulsions having different particle sizes.

  The grain size of the silver halide emulsion preferable in the present invention is the largest grain size (D2) having the smallest grain size among the two or more maximums in the grain size distribution curve of the silver halide grains. The ratio to the maximum particle size (D1) is less than 0.7, more preferably less than 0.5.

  The grain size of the silver halide emulsion preferred in the present invention is preferably the maximum grain size (D1) having the largest grain size, preferably 0.35 μm or less, more preferably 0.2 μm or less, and even more preferably 0.15 μm or less. It is. The maximum particle size (D2) having the smallest particle size is preferably less than 0.1 μm, more preferably less than 0.05 μm.

  In the silver halide photographic light-sensitive material of the present invention, at least one of the plurality of layers having different sensitivities contains the emulsion of the present invention containing two or more silver halide grains having different particle sizes. The emulsion of the present invention is preferably contained in the layer having the highest photosensitivity.

  The silver halide emulsion of the present invention is a grain having a maximum grain size (D2) having the smallest grain size in terms of silver amount (hereinafter also referred to as “D2 grain” or “D2 silver halide grain”). The addition amount is 1 to 50% of the addition amount of grains having the maximum particle diameter (D1) having the largest particle diameter (hereinafter also referred to as “D1 grains” or “D1 silver halide grains”). Is preferable, it is more preferable that it is 2-35%, and it is most preferable that it is 3-20%.

  As described in the section of the prior art, photographic sensitivity is generally determined by the size of silver halide emulsion grains. The larger the emulsion grains, the more the photographic speed increases. However, since graininess and blurring deteriorate as the size of silver halide grains increases, sensitivity, graininess, and blurring are in a trade-off relationship.

  In addition to increasing the size of the silver halide emulsion grains described above, sensitivity can be increased by methods such as increasing the activation of couplers and reducing the amount of development inhibitor releasing couplers (DIR couplers). Although it is possible, when the sensitivity is increased by these methods, the graininess and blurring deteriorate at the same time. These methods, such as emulsion grain size change, coupler activity adjustment, and DIR coupler quantity adjustment, increase the sensitivity and increase the graininess and blurring in the relationship between sensitivity and graininess, sensitivity and blurring. It is merely an “adjustment means” for improving the graininess or improving the graininess and bleeding while reducing the sensitivity.

  In the silver halide emulsion of the present invention, the sensitivity of D1 silver halide grains is higher than that of D2 silver halide grains. Further, the sensitivity when D1 silver halide grains and D2 silver halide grains are mixed is substantially higher than the sensitivity of the maximum silver halide grains having the largest particle diameter.

“High sensitivity” described in the claims of the present invention is not a method of increasing sensitivity accompanied by the above-described granular deterioration that occurs in the sensitivity increase.
The method for increasing the sensitivity of the present invention is a method for increasing the sensitivity without deterioration of graininess or blurring, or a method for increasing sensitivity, in which the increase in sensitivity is large compared to the deterioration of graininess or blurring. If the increase in sensitivity, graininess, or sensitivity increase and blurring occur at the same time, the sensitivity is compared after adjusting the graininess and blurring using the above-mentioned “adjustment means”. It is necessary to see an increase.

  The sensitivity is substantially high when the photosensitive material is coated with an equal amount of silver, the photosensitive material is exposed through a continuous wedge, and the sensitivity is compared with the logarithm of the reciprocal of the exposure amount giving the minimum density +0.35. The sensitivity difference is defined as 0.02 or more.

  The preferred silver halide used in the photosensitive layer of the present invention is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% of silver iodide.

  Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedrons, tetradecahedrons, irregular crystal shapes such as spheres and plates, twin planes, etc. However, in the present invention, a cubic emulsion is preferably used.

  Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643 (December 1978), pages 22-23, I. Emulsion preparation and types, and No. 18716 (November 1979), 648, No. 307105 (November 1989), 863-865, and Grafkide's "Physics and Chemistry of Photography", published by Paul Monter (P. Glafkides, Chimie et Phisique Photographiques, Paul Montel, 1967), "Photo Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photographic Emulsion Chemistry, Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., Focal It can be prepared using the method described in Press (VL Zelikman, et al., Making and Coating Photographic Emulsion, Focal Press, 164).

  Monodispersed emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferred.

  Tabular grains having an aspect ratio of about 3 or more can also be preferably used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering, Vol. 14, 248-257 (1970); US Pat. Nos. 4,434,226, 4,414,310, 4,433,048. No. 4,439,520 and British Patent No. 2,112,157.

  The crystal structure may be uniform, the inside and outside may be composed of different halogen compositions, or a layered structure may be formed. Silver halides having different compositions may be bonded by epitaxial bonding, and may be bonded to a compound other than silver halide, such as rhodium silver or lead oxide. A mixture of particles having various crystal forms may be used.

  The above emulsion may have dislocations. In particular, tabular grains preferably have dislocations in the fringes. As a method for introducing dislocations, a method of forming a high silver iodide layer by adding an aqueous solution of alkali iodide or the like, a method of adding AgI fine particles, a method described in JP-A-5-323487, or the like is used. Can do.

  The above emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which the latent image is formed inside the grain, or a type having a latent image on both the surface and the inside. It is necessary to be. Among the internal latent image types, the core / shell type internal latent image type emulsion described in JP-A-63-264740 may be used, and the preparation method thereof is described in JP-A-59-133542. . Although the thickness of the shell of this emulsion varies depending on the development processing or the like, it is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

The contents relating to the overall emulsion of the present invention will be described below.
The reduction sensitization preferably used in the present invention is a method of adding a reduction sensitizer to silver halide, a method of growing or ripening silver halide grains in a low pAg atmosphere of pAg 1 to 7 called silver ripening. Any of the methods of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can also be selected. Also, two or more of these methods can be used in combination.

  In particular, the method of adding a reduction sensitizer is a preferable method in that the level of reduction sensitization can be finely adjusted.

As a reduction sensitizer, stannous salt, ascorbic acid and derivatives thereof, hydroquinone and derivatives thereof, catechol and derivatives thereof, hydroxylamine and derivatives thereof, amines and polyamines, hydrazine and derivatives thereof, paraphenylenediamine and derivatives thereof, form Examples include amidine sulfinic acid (thiourea dioxide), silane compounds, and borane compounds. These reduction sensitizers can be selected and used in the reduction sensitization of the present invention, and two or more compounds can be used in combination. Regarding the method of reduction sensitization, U.S. Pat. Nos. 2,518,698, 3,201,254, 3,411,917, 3,779,777, 3,930, Regarding the method disclosed in No. 867 and the method of using a reducing agent, the methods disclosed in JP-B-57-33572, JP-A-58-1410 and JP-A-57-179835 can be used. Catechol and its derivatives, hydroxylamine and its derivatives, and formamidine sulfinic acid (thiourea dioxide) are preferred compounds as reduction sensitizers. The following general formulas (IV) and (V) are also preferable reduction sensitizers.

In the general formulas (IV) and (V), W ₅₁ and W ₅₂ represent a sulfo group or a hydrogen atom. However, at least one of W ₅₁ and W ₅₂ represents a sulfo group. The sulfo group is generally an alkali metal salt such as sodium or potassium, or a water-soluble salt such as an ammonium salt. Specific examples of preferable compounds include 3,5-disulfocatechol disodium salt, 4-sulfocatechol ammonium salt, 2,3-dihydroxy-7-sulfonaphthalene sodium salt, 2,3-dihydroxy-6,7-di And sulfonaphthalene potassium salt.

Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but a range of 10 ⁻⁷ to 10 ⁻¹ mol per mol of silver halide is appropriate. The reduction sensitizer is dissolved in water or a solvent such as alcohols, glycols, ketones, esters and amides and added during particle growth.

  Examples of the silver halide solvent that can be used in the present invention include U.S. Pat. Nos. 3,271,157, 3,531,289, 3,574,628, and JP-A-54-1019. (B) thiourea derivatives described in JP-A-53-82408, JP-A-55-77737, JP-A-55-2982, etc. (C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A No. 53-144319, and (d) imidazoles as described in JP-A No. 54-1000071 (E) ammonia, (f) thiocyanate and the like.

Particularly preferred solvents include thiocyanate, ammonia and tetramethylthiourea. The amount of the solvent used varies depending on the type. For example, in the case of thiocyanate, a preferable amount is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol of silver halide.

In preparation of the emulsion of the present invention, for example, at the time of grain formation, desalting step, chemical sensitization, it is preferable that a metal ion salt is present before coating, depending on the purpose. When the particles are doped, it is preferably added after the formation of the particles, before the completion of the chemical sensitization after the formation of the particles when used as a particle sensitizer or a chemical sensitizer. As described above, it is possible to select a method of doping the whole particle and a method of doping only the core part of the particle, only the shell part, or only the epitaxial part. For example, 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 can be used. These metals can be added in the form of a salt that can be dissolved during particle formation, such as ammonium salt, acetate salt, nitrate salt, sulfate salt, phosphate salt, hydrate salt, hexacoordinated complex salt, and tetracoordinated complex salt. For _{example, CdBr 2, CdCl 2, Cd} (NO 3) 2, Pb (NO 3) 2, Pb (CH 3 COO) 2, K 4 [Fe (CN) 6], (NH 4) 4 [Fe (CN) ₆ ], K ₂ IrCl ₆ , (NH ₄ ) ₃ RhCl ₆ , K ₄ Ru (CN) ₆ . The ligand of the coordination compound can be selected from halo, aco, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one kind of metal compound, but may be used in combination of two or more kinds.

The metal compound is preferably added after being dissolved in water or a suitable organic solvent such as methanol or acetone. In order to stabilize the solution, a method of adding an aqueous hydrogen halide solution (for example, HCl, HBr) or an alkali halide (for example, KCl, NaCl, KBr, NaBr) can be used. Moreover, you may add an acid, an alkali, etc. as needed. The metal compound can be added to the reaction vessel before particle formation or can be added during particle formation. Further, it can be added to a water-soluble silver salt (for example, AgNO ₃ ) or an alkali halide aqueous solution (for example, NaCl, KBr, KI) and continuously added during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and alkali halide may be prepared and added continuously at an appropriate time during grain formation. It is also preferable to combine various addition methods.

A method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,772,031 may be useful. In addition to S, Se, and Te, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.
The silver halide grains of the present invention may contain at least one of sulfur sensitization, selenium sensitization, tellurium sensitization, gold sensitization, palladium sensitization, noble metal sensitization, and reduction sensitization in any step of the silver halide emulsion production process. Can be applied in the process. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are types that embed chemical sensitization nuclei inside the particles, types that embed in a shallow position from the particle surface, or types that make chemical sensitization nuclei on the surface. In the emulsion of the present invention, the location of chemical sensitization nuclei can be selected according to the purpose, but generally preferred is the case where at least one chemical sensitization nucleus is formed in the vicinity of the surface.

  Among the silver halide grains of the present invention, the maximum silver halide grain having the smallest particle size may be chemically sensitized, but more preferably not chemically sensitized.

  One chemical sensitization that can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan. 1977, (TH James, The Theory of the Photographic Process, 4th ed, Macmillan, 1977), pages 67-76, and can also be performed using active gelatin. Disclosure, 120, April 1974, 12008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3, No. 772,031, No. 3,857,711, No. 3,90 714, 4,266,018 and 3,904,415, and British Patent 1,315,755, pAg 5-10, pH 5-8 and temperature 30 At ˜80 ° C., sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers can be used. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium, iridium and the like can be used, and gold sensitization, palladium sensitization and the combined use of both are particularly preferable.

  In gold sensitization, P.I. Gold salts described by Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.

  Specifically, in addition to chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, US Pat. No. 2,642,361 (such as gold sulfide and gold selenide), 3503749 (such as gold thiolate having a water-soluble group), No. 5049484 (bis (methylhydantoinato) gold complex, etc.), No. 5049485 (mesoionic thiolate gold complex, such as 1,4,5-trimethyl-1,2,4-triazolium-3-thiolate gold complex) ), Macrocyclic heterocyclic complexes of 5252455 and 5391727, 5620841, 5700651, 5759760, 5759761, 5912111, 5912112, 5939245, and JP-A-1-147537. No., 8-69074, No. 8-69075, No. -269554, Japanese Patent Publication No. 45-29274, German Patent DD-264524A, 264525A, 265474A, 298321A, JP-A-2001-75214, 2001-75215, 2001-75216, 2001-75217. Gold compounds described in JP-A-2001-75218 can also be used.

The palladium compound means a palladium divalent salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdCl ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂ PdBr ₄ is preferable. Gold compounds and palladium compounds are preferably used in combination with thiocyanate or selenocyanate.

  In sulfur sensitization, unstable sulfur compounds are used. The unstable sulfur compounds described in Grafkides, Chimie et Physique Photographic (published by Paul Momtel, 1987, 5th edition), Research Disclosure 307, 307105, and the like can be used.

  Specifically, thiosulfate (for example, hypo), thioureas (for example, diphenylthiourea, triethylthiourea, N-ethyl-N ′-(4-methyl-2-thiazolyl) thiourea, dicarboxymethyl- Dimethylthiourea, carboxymethyl-trimethylthiourea), thioamides (eg, thioacetamide), rhodanines (eg, diethylrhodanine, 5-benzylidene-N-ethylrhodanine), phosphine sulfides (eg, trimethylphosphine) Sulfide), thiohydantoins, 4-oxo-oxazolidine-2-thiones, disulfides or polysulfides (eg, dimorpholine disulfide, cystine, hexathiocan-thione), mercapto compounds (eg, cysteine), polythionates, Elemental Such known sulfur compounds and active gelatin, such as yellow may also be used. Particularly preferred are thiosulfates, thioureas, phosphine sulfides and rhodanines.

  In selenium sensitization, unstable selenium compounds are used, and Japanese Patent Publication Nos. 43-13489, 44-15748, JP-A-4-25832, 4-109340, 4-271341, and 5-40324. 5-11385, JP-A-6-51415, 6-175258, 6-180478, 6-208186, 6-208184, 6-317867, 7-92599, Selenium compounds described in JP-A-7-98483 and JP-A-7-140579 can be used.

  Specifically, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, trifluoromethylcarbonyl-trimethylselenourea, acetyl-trimethylselenourea), selenoamides (for example, selenoamide, N, N -Diethylphenylselenamide), phosphine selenides (eg triphenylphosphine selenide, pentafluorophenyl-triphenylphosphine selenide), selenophosphates (eg tri-p-tolylselenophosphate, Tri-n-butylselenophosphate), selenoketones (for example, selenobenzophenone), isoselenocyanates, selenocarboxylic acids, selenoesters (for example, methoxyphenylselenocarboxy-2,2-dimethoxycyclohexa) Ester), or the like may be used diacylselenides. Furthermore, non-labile selenium compounds described in JP-B Nos. 46-4553 and 52-34492, such as selenious acid, selenocyanic acids (for example, potassium selenocyanate), selenazoles, selenides, and the like may be used. I can do it. In particular, phosphine selenides, selenoureas, selenoesters and selenocyanic acids are preferred.

  In tellurium sensitization, unstable tellurium compounds are used, and JP-A-4-224595, JP-A-4-271341, JP-A-4-3333043, JP-A-5-303157, JP-A-6-27573, JP-A-6-175258. 6-180478, 6-208186, 6-208184, 6-317867, 7-140579, etc. can be used.

  Specifically, phosphine tellurides (for example, butyl-diisopropylphosphine telluride, tributylphosphine telluride, tributoxyphosphine telluride, ethoxydiphenylphosphine telluride), diacyl (di) tellurides ( For example, bis (diphenylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) ditelluride, bis (N-phenyl-N-methylcarbamoyl) telluride, bis (N-phenyl-N-benzylcarbamoyl) telluride, bis ( Ethoxycarbonyl) telluride), telluroureas (for example, N, N′-dimethylethylenetellurourea, N, N′-diphenylethylenetellurourea) telluramides, telluroesters, etc. may be used.

  Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during the process of chemical sensitization, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers are disclosed in U.S. Pat. Nos. 2,131,038, 3,411,914, 3,554,757, JP-A-58-126526, and the above-mentioned daffine. It is described in the book “photographic emulsion chemistry”, pp. 138-143.

The amount of gold sensitizer and chalcogen sensitizer used in the present invention varies depending on the silver halide grains used, chemical sensitization conditions, etc., but is 10 ⁻⁸ to 10 ⁻² mol per mol of silver halide, Preferably, about 10 ⁻⁷ to 10 ⁻³ mol can be used.

  The conditions for chemical sensitization in the present invention are not particularly limited, but pAg is 6 to 11, preferably 7 to 10, pH is 4 to 10, preferably 5 to 8, and temperature is 40 ° C to 40 ° C. 95 ° C, preferably 45 ° C to 85 ° C.

It is preferable to use an oxidizing agent for silver during the production process of the emulsion of the present invention. The oxidizing agent for silver refers to a compound having an action of acting on metallic silver and converting it into silver ions. Particularly effective are compounds capable of converting extremely fine silver grains by-produced in the process of forming silver halide grains and chemical sensitization into silver ions. The silver ions generated here may form, for example, a silver salt that is hardly soluble in water such as silver halide, silver sulfide, or silver selenide, or a silver salt that is easily soluble in water such as silver nitrate. May be formed. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2NaCO ₃ .3H ₂ O ₂ , Na ₄ P ₂ O ₇ .2H _{2). O 2, 2Na 2 SO 4 ·} H 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P 2 O 8), peroxy complex compound ( For _{example, K 2 [Ti (O 2} ) C 2 O 4] · 3H 2 O, 4K 2 SO 4 · Ti (O 2) OH · SO 4 · 2H 2 O, Na 3 [VO (O 2) (C 2 H ₄ ) ₂ ] · 6H ₂ O), permanganate (eg, KMnO ₄ ), chromate (eg, K ₂ Cr ₂ O ₇ ), oxyacid salts, and halogen elements such as iodine and bromine Perhalogenates (eg potassium periodate), high atoms Metal salts (e.g., hexacyanoferrate potassium ferric acid), and thiosulfonate.

  Examples of organic oxidizing agents include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogens (for example, N-bromosuccinimide, chloramine T, An example is chloramine B).

  Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents, and quinone organic oxidizing agents. It is a preferred embodiment to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver. A method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both can be used. These methods can be selected and used in either the particle formation step or the chemical sensitization step.

  The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the light-sensitive material, or stabilizing the photographic performance. That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; for example, thioketo compounds such as oxadrine thione; azaindenes such as , Triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a, 7) chitraazaindenes), pentaazaindene Known as antifoggants or stabilizers, such as, it can be added to many compounds. For example, those described in US Pat. Nos. 3,954,474, 3,982,947, and Japanese Patent Publication No. 52-28660 can be used. One preferred compound is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, water washing process, dispersion after water washing, chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. In addition to the original antifogging and stabilizing effect added during emulsion preparation, control the crystal wall of grains, reduce grain size, reduce grain solubility, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

  The photographic emulsion used in the present invention is preferably spectrally sensitized with methine dyes or the like in order to exhibit the effects of the present invention. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline nucleus, oxazoline nucleus, thiozoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and Nuclei in which aromatic hydrocarbon rings are fused to these nuclei, for example, indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxador nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole Nuclei, benzimidazole nuclei and quinoline nuclei are applicable. These nuclei may have a substituent on the carbon atom.

  The merocyanine dye or the complex merocyanine dye has a ketomethylene structure as a nucleus, for example, pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine A 5- or 6-membered heterocyclic nucleus of a nucleus or a thiobarbituric acid nucleus can be applied.

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 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, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.

Along with the sensitizing dye, the emulsion itself may contain a dye having no spectral sensitizing action or a substance that does not substantially absorb visible light and exhibits supersensitization. The timing when the sensitizing dye is added to the emulsion may be at any stage of emulsion preparation that has been known to be useful so far. Most commonly, it is carried out after completion of chemical sensitization and before application, but as described in US Pat. Nos. 3,628,969 and 4,225,666, chemical sensitizers are used. Spectral sensitization can be performed simultaneously with chemical sensitization, or prior to chemical sensitization as described in JP-A No. 58-113928, and silver halide grains can be precipitated. Spectral sensitization can be started by adding before completion of the production. Further, as taught in U.S. Pat. No. 4,225,666, these compounds are added separately, i.e. some of these compounds are added prior to chemical sensitization and the remainder is chemically enhanced. It can be added after the sensitization, and may be any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 4,183,756. The addition amount can be 4 × 10 ⁻⁶ to 8 × 10 ⁻³ mol per mol of silver halide.

  The silver halide photographic light-sensitive material of the present invention has a blue-sensitive photosensitive unit layer, a green-sensitive photosensitive unit layer, and a red-sensitive layer each including a plurality of layers having the same color sensitivity but different sensitivity on the support. A photosensitive unit layer may be provided. As a typical example, a blue-sensitive, green-sensitive, and red-sensitive photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity are provided on a support. A silver halide photographic material having at least one non-photosensitive layer. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer is composed of two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in German Patent 1,121,470 or British Patent 923,045. Are preferably arranged such that the photosensitivity decreases sequentially toward the support. In addition, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer on the side away from the support, A high-sensitivity emulsion layer may be provided on the side close to the body.

  As a specific example, from the side farthest from the support, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer (BH) / high sensitivity green photosensitive layer (GH) / low sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL) or BH / BL / GL / GH / RH / RL or BH / BL / GH / GL / RL / RH It can be installed in the order of.

  Further, as described in JP-B-55-34932, the light-sensitive layer can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. Further, as described in JP-A-56-25738 and JP-A-62-63936, they may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support. it can.

  In addition, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer having a low degree is arranged, and an arrangement composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even in the case of being composed of three layers having different sensitivities, as described in JP-A-59-202464, in the same color-sensitive layer, the medium-sensitive emulsion layer / high They may be arranged in the order of sensitive emulsion layer / low sensitive emulsion layer.

In addition, they may be arranged in the order of high sensitivity emulsion layer / low sensitivity emulsion layer / medium sensitivity emulsion layer, or low sensitivity emulsion layer / medium sensitivity emulsion layer / high sensitivity emulsion layer.
Further, the arrangement may be changed as described above even when there are four or more layers.

  In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different in grain size, grain size distribution, halogen composition, grain shape, and sensitivity of a photosensitive silver halide emulsion are mixed in the same layer. Can be used.

  Silver halide grains with fogged grain surfaces as described in US Pat. No. 4,082,553, silver halide grains with fogged grains as described in US Pat. No. 4,626,498 and JP-A-59-214852 Preferably, colloidal silver is applied to the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer. The silver halide grains fogged inside or on the surface of the grains are silver halide grains that can be developed uniformly (non-imagewise) regardless of the unexposed and exposed areas of the photosensitive material. The preparation method thereof is described in US Pat. No. 4,626,498 and JP-A-59-214852. The silver halide forming the inner core of the core / shell type silver halide grain in which the inside of the grain is fogged may have a different halogen composition. Any silver chloride, silver bromide, silver iodobromide, or silver chloroiodobromide can be used as the silver halide fogged inside or on the surface of the grain. The average grain size of these fogged silver halide grains is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The grain shape may be a regular grain or a polydisperse emulsion, but it is monodisperse (at least 95% of the silver halide grain mass or number of grains has a grain size within ± 40% of the average grain size). Are preferred).

  In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a silver halide fine grain which is not exposed during imagewise exposure for obtaining a dye image and is not substantially developed in the developing process, and is preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide. The fine grain silver halide preferably has an average particle size (average value of equivalent circle diameter of projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm.

The fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. Spectral sensitization or chemical sensitization may be performed on the surface of the silver halide grain, but it is not necessary to perform it. Prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole, azaindene, benzothiazolium, mercapto compound or zinc compound in advance. This fine grain silver halide grain-containing layer can contain colloidal silver.
Coated silver amount of the light-sensitive material of the present invention, such as for to improved sharpness, preferably 8.0 g / m ² or less, more preferably 5.0 g / m ² or less, 3.0 g / m ² or less is most preferred.

Photographic additives that can be used in the present invention are also described in the RD, and the description locations related to the following table are shown.
Type of additive RD17643 RD18716 RD307105
1. Chemical sensitizer, page 23, page 648, right column, page 8662. Sensitivity increasing agent, right column, page 648 Spectral sensitizer, pages 23 to 24, page 648, right column, pages 866 to 868, supersensitizer to page 649, right column 4. Brightener 24 pages 647 pages right column 868 pages 5. 5. Light absorber, 25-26 pages, 649, right column, page 873 Filters, -page, left page, 650 Dyes, ultraviolet absorbers Binder page 26 page 651 left column page 873-874 Plasticizer, page 27, page 650, right column, page 876 Lubricant 8. Coating aid, page 26-27, page 650, right column, page 875-876, surface active agent 9. Static page 27 page 650 right column pages 876-877 inhibitor
Ten. Matting agents 878-879.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable.
Yellow coupler:
Couplers represented by formulas (I) and (II) described in EP-A 502,424A;
A coupler represented by the formula (1), (2) described in EP 513,496A (particularly Y-28 on page 18);
A coupler represented by the formula (I) of claim 1 described in EP 568,037A;
A coupler represented by the general formula (I) described in US Pat. No. 5,066,576, column 45, lines 45-55;
A coupler represented by the general formula (I) described in paragraph 0008 of JP-A-4-74425;
Coupler according to claim 1 on page 40 of EP-A-498,381A1 (particularly D-35 on page 18);
A coupler represented by the formula (Y) described on page 4 of EP-A-447,969A1 (particularly Y-1 (page 17), Y-54 (page 41));
Couplers represented by formulas (II) to (IV) described in US Pat. No. 4,476,219 at columns 7 to 58 in column 7 (particularly II-17, 19 (column 17), II-24 (column 19)) .

Magenta coupler;
L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13) described in JP-A-3-9737;
(A-4) -63 (page 134), (A-4) -73, -75 (page 139) described in EP 456,257;
M-4, -6 (page 26), M-7 (page 27) described in EP 486,965;
M-45 (page 19) as described in EP 571,959A;
(M-1) (page 6) described in JP-A-5-204106;
M-22 described in paragraph 0237 of JP-A-4-362631.

Usage of the present invention, cyan coupler other than the use layer:
CX-1,3,4,5,11,12,14,15 (pages 14-16) described in JP-A-4-204843;
C-7, 10 (page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42 to 43) described in JP-A-4-43345;
A coupler represented by the general formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385.
Polymer coupler: P-1, P-5 (page 11) described in JP-A-2-44345.

  As couplers in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,873B, and German Patent No. 3,234,533 are preferable.

  A coupler for correcting unwanted absorption of the coloring dye is a yellow colored compound represented by the formula (CI), (CII), (CIII), (CIV) described on page 5 of EP-A-456,257A1. Cyan couplers (especially YC-86 on page 84), yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251) described in the European Patent Application Publication, Magenta colored cyan coupler CC-9 (column 8), CC-13 (column 10) described in US Pat.No. 4,833,069, (2) (column 8) described in US Pat. Colorless masking couplers represented by the formula (A) of claim 1 described in the pamphlet of WO92 / 11575 (especially exemplified compounds on pages 36 to 45) are preferred.

  Examples of the compounds (including couplers) that release a photographically useful compound residue by reacting with oxidized developing agent include the following.

Development inhibitor releasing compounds: compounds represented by the formulas (I), (II), (III) and (IV) described on page 11 of EP-A-378,236A1 (especially T-101 (page 30)) ), T-104 (31 pages), T-113 (36 pages), T-131 (45 pages), T-144 (51 pages), T-158 (58 pages)), European Patent Application Publication No. 436, 938A2 Compounds represented by formula (I) described on page 7 of the specification (especially D-49 (page 51)), compounds represented by formula (1) of EP 568,037A (particularly ( 23) (page 11)), and compounds represented by formulas (I), (II), (III) described on pages 5 to 6 of European Patent Application Publication No. 440,195A2 (especially I- ( 1));
Bleach accelerator releasing compounds: compounds represented by formulas (I) and (I ') on page 5 of EP-A-310,125A2 (especially (60) and (61) on page 1) and JP-A-6 -59411 compound of the formula (I) of claim 1 (especially (7) (page 7);
Ligand-releasing compound: a compound represented by LIG-X described in claim 1 of US Pat. No. 4,555,478 (particularly the compound in columns 21 to 41 of column 12);
Leuco dye-releasing compound: compounds 1-6 of columns 3-8 of US Pat. No. 4,749,641;
Fluorescent dye releasing compounds: compounds represented by COUP-DYE of claim 1 of US Pat. No. 4,774,181 (especially compounds 1 to 11 in columns 7 to 10);
Development accelerator or fogging agent releasing compounds: compounds represented by formulas (1), (2), (3) in column 3 of US Pat. No. 4,656,123 (especially (I-22) of column 25) and European patents ExZK-2 on page 75, lines 36-38 of published application 450,637A2;
A compound that releases a group that becomes a dye only after leaving: a compound represented by the formula (I) in claim 1 of US Pat. No. 4,857,447 (particularly, Y-1 to Y-19 in columns 25 to 36).

As additives other than couplers, the following are preferable.
Oil-soluble organic compound dispersion medium: P-3, 5, 16, 19, 25, 30, 42, 49, 54, 55, 66, 81, 85, 86, 93 described in JP-A-62-215272 (P. 140-144);
Latex for impregnation of oil-soluble organic compounds: Latex described in U.S. Pat.No. 4,199,363;
Oxidized developer scavenger: A compound represented by formula (I) described in column 2, lines 54 to 62 of U.S. Pat. No. 4,978,606 (especially I- (1), (2), (6), (12 (Columns 4-5), U.S. Pat. No. 4,923,787, column 2, lines 5-10 (particularly compound 1 (column 3);
Stain inhibitor: Formulas (I) to (III) described in European Patent Application No. 298321A, page 4, lines 30 to 33, particularly I-47, 72, III-1, 27 (pages 24 to 48) ;
Antifading agent: A-6,7,20,21,23,24,25,26,30,37,40,42,48,63,90,92, described in EP-A-298321A 94,164 (pages 69 to 118), II-1 to III-23 described in columns 25 to 38 of U.S. Pat.No. 5,122,444, in particular III-10, pages 8 to 12 of EP 471347A I-1 to III-4, in particular II-2, as described in U.S. Pat.No.5,139,931, columns 32 to 40, A-1 to 48, in particular A-39,42;
Material for reducing the amount of color-enhancing agent or color mixing inhibitor used: I-1 to II-15, particularly I-46, described on pages 5 to 24 of EP-A-411324A;
Formalin scavenger: SCV-1 to 28 described in pages 24 to 29 of EP-A-477932A, in particular SCV-8;
Hardener: H-1,4,6,8,14 described on page 17 of JP-A 1-214845, U.S. Pat.No. 4,618,573, columns 13-23, formulas (VII)-( XII) (H-1 to 54), JP-A-2-14852, page 8, lower right, compound (H-1 to 76) represented by formula (6), particularly H-14, A compound according to claim 1 of US Pat. No. 3,325,287;
Development inhibitor precursor: P-24,37,39 (pages 6 to 7) described in JP-A-62-168139; compounds described in claim 1 of US Pat. No. 5,019,492, in particular column 28 , 29;
Preservatives, antifungal agents: I-1 to III-43 described in columns 3 to 15 of U.S. Pat.No. 4,923,790, in particular II-1,9,10,18, III-25;
Stabilizer, antifoggant: I-1 to (14) described in columns 6 to 16 of U.S. Pat.No. 4,923,793, in particular I-1,60, (2), (13), U.S. Pat.No. 4,952,483 Compounds 1 to 65 described in columns 25 to 32 of the specification, especially 36: chemical sensitizer: triphenylphosphine selenide, compound 50 described in JP-A-5-40324;
Dye: a-1 to b-20 described in JP-A-3-156450, pages 15 to 18, especially a-1, 12, 18, 27, 35, 36, b-5, pages V to 27-29 -1 to 23, especially V-1, FI-1 to F-II-43, especially FI-11, F-II-8, European patents described on pages 33 to 55 of EP-A-445627A III-1 to 36 described on pages 17 to 28 of the specification of published application 457153A, particularly III-1,3, and dyes 1 to 124 described on pages 8 to 26 of pamphlet of WO 88/04794. Microcrystalline dispersions, compounds 1 to 22 described on pages 6 to 11 of EP 319999A, in particular compounds 1, in formulas (1) to (3) of EP 519306A Compound D-1 to 87 (pages 3 to 28), Compound 1 to 22 represented by formula (I) described in U.S. Application No. 4,268,622 (columns 3 to 10), U.S. Application No. 4,923,788 Compounds (1) to (31) (columns 2 to 9) represented by the formula (I) described in: UV absorber: a compound represented by the formula (1) described in JP-A-46-3335 (18b ) ~ (18r), 1 01-427 (pages 6-9), compounds (3)-(66) (pages 10-44) and formula (III) represented by formula (I) described in European Patent Application No. 520938A Compounds HBT-1 to 10 (page 14), compounds (1) to (31) represented by the formula (1) described in European Patent Application Publication No. 521823A (columns 2 to 9).

  Suitable supports that can be used in the present invention are described in, for example, RD. No. 17643, page 28, RD. No. 18716, page 647, right column to page 648, left column, and RD. No. 307105, page 879. ing.

In the light-sensitive material of the present invention, the thickness from the light-sensitive silver halide layer closest to the support to the surface of the photographic light-sensitive material is preferably 24 μm or less, more preferably 22 μm or less, and most preferably 20 μm or less. The membrane swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. T _1/2 is the time until the film thickness reaches 1/2 when 90% of the maximum swollen film thickness reached when processed at 30 ° C for 3 minutes and 15 seconds with a color developer is the saturated film thickness. It is defined as The film thickness means the film thickness measured at 25 ° C and 55% relative humidity (2 days), and T _1/2 is photographic science and engineering by A.Green et al. (Photogr. Sci. Eng.), 19 卷, 2, 124-129. T _1/2 can be adjusted by adding a hardener to gelatin as a binder or changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness) / film thickness.

  In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150 to 500%.

  Next, the polyester support preferably used in the present invention will be described. For details including the photosensitive material, treatment, cartridge, and examples described later, the published technical report, public technical number 94-6023 (Invention Association; 1994.3.15). .)It is described in. The polyester used in the present invention is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic as aromatic dicarboxylic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.

Next, the polyester support is heat-treated at a heat treatment temperature of 40 ° C. or higher and lower than Tg, more preferably Tg−20 ° C. or higher and lower than Tg, in order to make it difficult to cause curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. This heat treatment time is 0.1 hours to 1500 hours, more preferably 0.5 hours to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while being conveyed in a web shape. The surface may be improved by providing irregularities on the surface (for example, applying conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ ). Further, it is desirable to devise measures such as preventing knurling of the core part by imparting knurling to the end part and slightly raising only the end part. These heat treatments may be carried out at any stage after forming the support, after the surface treatment, after applying the back layer (antistatic agent, slip agent, etc.) and after applying the undercoat. Preferred is after application of the antistatic agent.

  This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading commercially available dyes or pigments for polyester such as Mitsubishi Kasei's Diaresin and Nippon Kayaku's Kayaset.

  Next, in the present invention, it is preferable to perform a surface treatment in order to adhere the support and the light-sensitive material constituting layer. Examples of the surface activation treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the primer method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer, starting from a copolymer starting from a monomer selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc. Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Examples of compounds that swell the support include resorcin and p-chlorophenol. For the undercoat layer, as a gelatin hardener, chromium salts (such as chromium alum), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) Etc.), epichlorohydrin resins, active vinyl sulfone compounds and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

  In the present invention, an antistatic agent is preferably used. Examples of these antistatic agents include carboxylic acids, carboxylates, polymers containing sulfonates, cationic polymers, and ionic surfactant compounds.

The most preferable antistatic agent is at least one selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O _5. The volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less, and the particle size of 0.001 to 1.0 μm crystalline metal oxide or composite oxide thereof (Sb, P, B, In, S, Si, C, etc.), and also sol-like metal oxides or composite oxides thereof.

The addition amount to the photographic material, 5 to 500 mg / m ² is preferably particularly preferably 10 to 350 mg / m ^2. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

  The light-sensitive material of the present invention preferably has slipperiness. The slip agent-containing layer is preferably used for both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at 60 cm / min for a stainless steel ball having a diameter of 5 mm (25 ° C., 60% RH). In this evaluation, even if the counterpart material is replaced with the photosensitive layer surface, the value is almost the same.

  Examples of slip agents that can be used in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and examples of polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, Styrylmethylsiloxane, polymethylphenylsiloxane, and the like can be used. As the additive layer, the outermost layer of the emulsion layer or the back layer is preferable. In particular, polydimethylsiloxane and esters having a long chain alkyl group are preferred.

  The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be either the emulsion surface or the back surface, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and is preferably a combination of both. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, the particle size distribution is preferably narrow, and 90% or more of the total number of particles is preferably contained between 0.9 and 1.1 times the average particle size. It is also preferable to add fine particles of 0.8 μm or less at the same time in order to improve the matting property, for example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Examples thereof include polystyrene particles (0.25 μm) and colloidal silica (0.03 μm).

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
(Example 1)
(Preparation of emulsion Em-A)
An AgBrI monodisperse cubic emulsion was prepared according to the following. The following solutions were prepared.
<< Solution A >> Aqueous solution containing lime-treated ossein gelatin: 30 g, KBr: 0.4 g, and water: 1.3 L << Solution B >> 0.2 L of an aqueous solution containing 20 g of AgNO ₃
<< Solution C >> 0.2 L of aqueous solution containing KBr: 15 g and KI: 0.6 g
<< Solution D >> 0.65 L of aqueous solution containing 162.5 g of AgNO ₃
<< Solution E >> 0.7 L of an aqueous solution containing KBr: 124.8 g, KI: 5.4 g, and NaCl: 0.6 g.

Solution A was placed in a reaction vessel and kept at 60 ° C. and stirred. 150 mL of Solution B was added over 5 minutes. During this time, Solution C was added while controlling the amount of addition so that pBr in the reaction vessel was maintained at 3.5. After completion of the addition, the temperature of the solution in the reaction vessel was raised to 70 ° C. Subsequently, 540 mL of solution D was added over 15 minutes. During this time, solution E was added while controlling the amount added so that pBr in the reaction vessel was maintained at 3.5. During this addition, 0.005 g of thiourea dioxide: 0.005 g of sodium benzenesulfonate: 0.0003 g of K ₂ IrCl ₆ : 0.0003 g was added to the reaction vessel.

  After completion of the addition, a desalting step was performed by a flocculation method. After the desalting step, the following chemical sensitization treatment and spectral sensitization treatment were performed. The emulsion after desalting is kept at 60 ° C., and the sensitizing dye, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, 4-hydroxy-6-methyl-1,3,3a 7-tetrazaindene (TAI), Compound 1, Compound 2, and Compound 3 were added for optimal spectral sensitization and chemical sensitization. The sensitizing dye was added in an optimum amount by changing the ratio of the dyes shown in Table 1 as appropriate. The obtained particles were cubic particles having an average equivalent circle diameter of 0.18 μm and a coefficient of variation of 11%.

(Preparation of emulsions Em-B, D, G)
In the preparation of the emulsion Em-A, the temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to E, the addition rate of the solutions B to E, the pBr of the solution in the reaction vessel, thiourea dioxide, benzenesulfonic acid Emulsions Em-B, D, and G were prepared in the same manner as Emulsion A, except that sodium, K ₂ IrCl ₆ addition amount, sensitizing dye after completion of desalting, and chemical sensitization were appropriately changed.

(Preparation of emulsion Em-C)
An AgBrI monodisperse cubic emulsion was prepared according to the following. The following solutions were prepared.
"The solution A" lime-: 30 g, KBr: 0.4 g, and water: an aqueous solution containing 1.5 L "solution _B" AgNO 3: aqueous solution containing 162.5 g 0.65 L
<< Solution C >> 0.7 L of an aqueous solution containing KBr: 125.4 g, KI: 4.5 g, and NaCl: 0.3 g.

Solution A was placed in a reaction vessel and kept at 55 ° C. and stirred. 540 mL of Solution B was added over 10 minutes. During this time, Solution C was added while controlling the amount of addition so that pBr in the reaction vessel was maintained at 3.5. During this addition, 0.007 g of thiourea dioxide: 0.007 g of sodium benzenesulfonate and 0.0005 g of K ₂ IrCl ₆ were added to the reaction vessel.

  After completion of the addition, a desalting step was performed by a flocculation method. After the desalting step, the following chemical sensitization treatment and spectral sensitization treatment were performed. The emulsion after desalting is kept at 62 ° C., and the sensitizing dye, chloroauric acid, sodium thiosulfate, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI), Compound 1 Compound 2 and Compound 3 were added for optimal spectral sensitization and chemical sensitization. The sensitizing dye was added in an optimum amount by changing the ratio of the dyes shown in Table 1 as appropriate. The obtained particles were cubic particles having an average equivalent circle diameter of 0.10 μm and a coefficient of variation of 13%.

(Preparation of emulsions Em-E, F, H, I)
In the preparation of the emulsion C, the temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to C, the addition rate of the solutions B and C, the pBr of the solution in the reaction vessel, thiourea dioxide, sodium benzenesulfonate, Emulsions Em-E, F, H, and I were prepared in the same manner as Emulsion C, except that the addition amount of K ₂ IrCl ₆ , the sensitizing dye after completion of desalting, and chemical sensitization were appropriately changed.

(Preparation of multilayer color photosensitive material sample 101)
A support was produced by coating the cellulose triacetate film support on which an undercoat was applied with the back layer shown below.

(Back layer)
Methyl methacrylate-methacrylic acid copolymer (copolymerization molar ratio 1: 1) 1.5 parts by mass Cellulose acetate hexahydrophthalate (hydroxypropyl group 4%, methyl group 15%,
1.5% by weight Acetone 50 parts by weight Methanol 25 parts by weight Methyl Cellosolve 25 parts by weight Colloidal carbon 1.2 parts by weight The coating was applied so that the concentration was 1.0.

  On the opposite side of the support to which the back layer was applied, an undercoat was applied to prepare Sample 101, which is a multilayer color photosensitive material composed of layers having the compositions shown below.

(Sensitivity composition)
The amount of the silver coating amount for silver halide and colloidal silver, expressed in units of g / m ^2, also couplers, for additives and gelatin indicating the quantity, expressed in g / m ^2.

First layer (Anti-halation layer)
Black colloidal silver Silver coating amount 0.090
Silver iodobromide emulsion grains Silver coating amount 0.020
(Average grain size 0.07 μm, silver iodide content 2 mol%)
Gelatin 0.910.

Second layer (intermediate layer)
Gelatin 2.160
ExF-4 0.694.

Third layer: low-sensitivity red-sensitive emulsion layer EM-I silver coating amount 0.260
Gelatin 1.900
ExC-1 0.141
ExC-2 0.194
ExC-3 0.019
ExC-4 0.034
ExC-5 0.029
Cpd-2 0.105
Solv-1 0.440.

Fourth layer: Intermediate red-sensitive emulsion layer Em-H Silver coating amount 0.238
Gelatin 1.067
ExC-1 0.091
ExC-2 0.125
ExC-3 0.019
ExC-4 0.028
ExC-5 0.008
Cpd-2 0.069
Solv-1 0.293.

5th layer; high sensitivity red-sensitive emulsion layer Em-G silver coating amount 0.231
Gelatin 0.757
ExC-1 0.057
ExC-2 0.079
ExC-3 0.019
ExC-5 0.005
Cpd-2 0.044
Solv-1 0.165.

Layer 6: Intermediate layer Gelatin 1.489
Cpd-1 0.069
ExF-5 0.074
ExF-7 0.062
ExF-8 0.028
Solv-1 0.223.

Seventh layer; low-sensitivity green-sensitive emulsion layer Em-F silver coating amount 0.312
Gelatin 1.614
ExM-1 0.164
ExM-3 0.095
ExM-4 0.148
Solv-1 0.473
Solv-2 0.050.

Eighth layer: Medium sensitivity green-sensitive emulsion layer Em-E Silver coating amount 0.184
Gelatin 0.525
ExM-1 0.048
ExM-2 0.037
ExM-3 0.021
ExM-4 0.043
Solv-1 0.171
Solv-2 0.020.

Ninth layer: High-sensitivity green-sensitive emulsion layer Em-D Silver coating amount 0.251
Gelatin 0.447
ExM-1 0.040
ExM-2 0.031
ExM-3 0.018
ExM-4 0.036
Solv-1 0.150
Solv-2 0.010.

10th layer: Yellow filter layer Yellow colloidal silver Silver coating amount 0.064
Gelatin 0.950
Cpd-1 0.105
ExF-8 0.028
Solid disperse dye ExF-9 0.125
Solv-1 0.121.

Eleventh layer; low-sensitivity blue-sensitive emulsion layer Em-C silver coating amount 0.130
Gelatin 1.514
ExY-1 0.056
ExY-2 0.561
ExC-2 0.008
Solv-1 0.234.

12th layer: Medium sensitivity blue-sensitive emulsion layer Em-B Silver coating amount 0.154
Gelatin 0.859
ExY-1 0.039
ExY-2 0.391
ExC-3 0.009
Solv-1 0.163.

13th layer: High-sensitivity blue-sensitive emulsion layer Em-A Silver coating amount 0.285
Gelatin 0.371
ExY-1 0.010
ExY-2 0.101
ExC-3 0.003
Solv-1 0.042.

14th layer; 1st protective layer Silver iodobromide emulsion grains Silver coating amount 0.211
(Average grain size 0.07 μm, silver iodide content 2 mol%)
Gelatin 0.683
Solid disperse dye ExF-9 0.054
ExF-1 0.073
H-1 0.160.

15th layer; 2nd protective layer Gelatin 0.727
B-1 (diameter 2.0 μm) 0.007
B-2 (diameter 2.0 μm) 0.005
B-3 0.047
H-1 0.170.

(Preparation of dispersion of organic solid disperse dye)
ExF-9 of the 10th layer and the 14th layer was dispersed by the following method.
ExF-9 wet cake (containing 17.6 wt% water) 2.800 kg
Sodium octylphenyldiethoxymethanesulfonate (31 mass% aqueous solution) 0.376 kg
F-15 (7% aqueous solution) 0.011 kg
4.020 kg of water
Total 7.210kg
(Adjusted to pH = 7.2 with NaOH)
After the slurry having the above composition is stirred and roughly dispersed by a dissolver, it is dispersed using an agitator mill LMK-4 at a peripheral speed of 10 m / s, a discharge rate of 0.6 kg / min, and a filling rate of zirconia beads having a diameter of 0.3 mm of 80%. Dispersion was performed until the absorbance ratio of the liquid reached 0.29 to obtain a solid fine particle dispersion. The average particle size of the dye fine particles was 0.29 μm.

  In addition to the above, Sample 101 prepared in this manner included 1,2-benzisothiazolin-3-one (average 200 ppm relative to gelatin), n-butyl-p-hydroxybenzoate (about 1000 rpm), and 2-phenoxyethanol ( About 10000 rpm) was added.

Furthermore, Cpd-3 to Cpd-7, B-4, B-5, W-1 to W-13, F-1 to F-21, ExF-2, ExF-3, ExF-6, UV-1 to UV -5 was added.
The structural formulas of the substances used in the photosensitive material are shown below.

In the preparation of Em-D used for the ninth layer in the obtained sample 101, the temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to E, the addition rate of the solutions B to E, the solution in the reaction solution Em-I and B were prepared by appropriately changing the amount of pBr, thiourea dioxide, sodium benzenesulfonate, K ₂ IrCl ₆ , the amount of sensitizing dye after completion of desalting, and the amount of chemical sensitizer. . However, no chemical sensitizer was added to Em-Ro. For Em-D to F and Em-i and b, the order of emulsion sensitivity was the same as the order of grain size. It shows in Table 2.

  For the obtained sample 101, the Em-D of the ninth layer was reduced by 10%, and it was changed to add Em-I, Em-E, Em-F, and Em-B by the silver amount equal to the reduced amount. Materials 102, 103, 104 and 105 were made.

  For the obtained sample 101, Em-E, Em-F and Em-B are added to the ninth layer by 10% by silver amount, and the amount of Em-D applied is adjusted so that the sensitivity of sample 101 and G is the same. Photosensitive materials 106, 107 and 108 were produced by changing the number of the photosensitive materials.

  The obtained sample 101 was changed so that Em-i was added by an equal amount of silver instead of Em-D of the ninth layer, and a photosensitive material 109 was produced.

  In the obtained sample 109, the Em-a of the ninth layer was reduced by 10%, and the silver materials equal to the reduced amount were changed to add Em-E, Em-F and Em-ro, and the photosensitive materials 110, 111 were changed. And 112 were produced.

  For the obtained sample 109, Em-F and Em-B were added to the ninth layer by 10% in terms of silver amount, and the coating amount of Em-i was changed so that the sensitivity of sample 109 and G would be the same. Photosensitive materials 113 and 114 were produced.

  The sensitivity of the green sensitive layer is indicated by the logarithm of the reciprocal of the exposure amount at which the magenta color image density gives the lowest density +0.35. About experiment No9-14, it showed by the difference of the absolute value when experiment No9 was made into the reference | standard.

試料１０１〜１１４を現像処理したカラー現像処理の内容は以下の通りである。 Bleeding and color purity were evaluated using a G laser, developed after exposure, evaluated by the method described in the text, and the results are shown in Table A.

The contents of the color development processing performed on the samples 101 to 114 are as follows.

Processing step Temperature (° C) Time (1) Pre-bath 27 ± 1 10 seconds (2) Backing removal and spray water washing 27-385 5 seconds (3) Color development 41.1 ± 0.1 3 minutes (4) Stop 27- 38 30 seconds (5) Washing 27-38 30 seconds (6) Bleaching 27 ± 13 3 minutes (7) Washing 27-38 1 minute (8) Fixing 38 ± 12 minutes (9) Washing 27-38 2 minutes (10 ) Stable 27-38 10 seconds.

  The prescription of the treatment liquid used in each treatment step is as follows.

Prescription of each treatment solution (1) Pre-bath Prescription value Water of 27-38 ° C 800ml
Borax (10 hydrate) 20.0g
Sodium sulfate (anhydrous) 100g
Sodium hydroxide 1.0g
Add water 1.00 liter pH (27 ° C.) 9.25.

(2) Color development 850 ml of water at 21-38 ° C
Kodak Anti-Calcium No. 4 2.0ml
Sodium sulfite (anhydrous) 2.0g
Eastman Anti-Fog No. 9 0.22g
Sodium bromide (anhydrous) 1.20 g
Sodium carbonate (anhydrous) 25.6g
Sodium bicarbonate 2.7g
Color developing agent;
4-Amino-3-methyl-N-ethyl-
N- (β-Methanesulfonamidoethyl) -aniline
4.0g
Add water 1.00 liter pH (27 ° C.) 10.20.

(3) Stop 900-ml water at 21-38 ° C
7.0N sulfuric acid 50ml
Add water 1.00 liter pH (27 ° C) 0.9.

(4) Bleaching solution 700-ml water at 24-38 ° C
Proxel GXL 0.07ml
Kodak Killing Agent No. 1 24.2g
28% ammonium hydroxide 30.0ml
Ammonium bromide 32.5g
Glacial acetic acid 10.0ml
Ferric nitrate (9 salt) 28.8g
Add water 1.0 liter pH (27 ° C.) 5.0 ± 0.2.

(5) Fixing 700 ml of water at 20 to 38 ° C
Kodak Anti-Calcium No. 4 2.0ml
185 ml of 58% ammonium thiosulfate solution
Sodium sulfite (anhydrous) 10.0 g
Sodium bisulfite (anhydrous) 8.4g
Add water 1.0 liter pH (27 ° C.) 6.5.

(6) Stable 21-27 ° C water 1.00 liter Kodak Stabilizer Additive 0.14 ml
Formalin (37.5% solution) 1.5 ml.

Sensory evaluation of the image quality of samples 101 to 114 was performed by the following method.
A landscape image with digital information of the number of pixels (2048 x 1556) is exposed to samples 101 to 114 with a B, G, R laser with a size of 0.8 x 0.6 inches, and the resulting negative image is projected to 20 people Of the inspector. The evaluation was carried out by a relative evaluation method with the evaluation value when using the sample 101 being 3 (standard). Further, this negative image was further exposed to a Fuji color positive film F-CP, and then developed by the method described in the section “FUJIFILM PROCESSING MANUAL Motion Picture Films”, to obtain a positive image. This was projected and the same evaluation was performed.

  Sharpness was evaluated for the negative image, and sharpness and color saturation were evaluated for the positive image in the following seven stages, and the average of the evaluation values of the 20 inspectors was calculated. The results are shown in Table A.

0: very inferior 1: inferior 2: slightly inferior 3: (standard)
4: Somewhat excellent 5: Excellent 6: Very good

  From Table A, it can be seen that if the image recording method of the present invention is employed, a projected image with high sensitivity, sharpness and color saturation can be obtained.

The figure which shows the relationship between the color development density D of a silver halide photographic light-sensitive material, and the blur k.

Explanation of symbols

D: Color density of silver halide photographic material k: Bleeding at color density D

Claims (9)

  A silver halide photograph having a blue-sensitive photosensitive unit layer, a green-sensitive photosensitive unit layer, and a red-sensitive photosensitive unit layer each including a plurality of layers having the same color sensitivity but different sensitivity on a transparent support. In the photosensitive material, the silver halide grains contained in the silver halide emulsion of at least one of the plurality of layers having different sensitivities have two or more grain sizes, so that in the grain size distribution curve thereof. The sensitivity of the silver halide grains having two or more maximums and having the maximum particle size (D1) having the largest particle size among the two or more maximums is the maximum particle size (D2) having the smallest particle size. ) And a silver halide grain having a maximum particle size (D1) having the largest particle size and a silver halide particle having a maximum particle size (D2) having the smallest particle size. Feel when mixing But silver halide photographic material comprising a higher sensitivity of the silver halide grains having a particle size of the largest maxima particle diameter (D1). The silver halide according to claim 1, wherein the maximum particle size (D1) having the largest particle size and the maximum particle size (D2) having the smallest particle size satisfy the following formula (I): Photosensitive material.
Formula (I)
D2 / D1 <0.7 The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the maximum particle size (D2) having the smallest particle size satisfies the following formula (II).
Formula (II)
D2 <0.1 μm The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the maximum particle size (D2) having the smallest particle size satisfies the following formula (III).
Formula (III)
D2 <0.05 μm   5. The silver halide photographic light-sensitive material according to claim 1, wherein the image information is recorded with little deterioration during image formation in which digital image information is recorded at a resolution of 2000 dpi or more.   5. The silver halide photographic light-sensitive material according to claim 1, which records digital image information of 3 million pixels or more with little deterioration. 7. The silver halide photographic light-sensitive material according to claim 1, wherein the blur k during image recording satisfies the following formula (A).
k <4.5 × (D−0.2) ² (A)
In formula (A),
D: Color density blur of silver halide photographic material k: Bleeding at color density D (μm)   8. The silver halide photographic light-sensitive material according to claim 1, wherein the color purity ratio is 80% or more in color reproduction at the time of image recording.   9. An image forming method for recording the silver halide photographic light-sensitive material according to claim 1 on the silver halide photographic light-sensitive material in an analog manner.

Images