JP3639295B2 - Silver halide photographic material - Google Patents

Description

  The present invention relates to a silver halide photographic light-sensitive material. More specifically, the present invention relates to a silver halide photographic material having high sensitivity and low covering.

The silver halide photographic light-sensitive material mainly contains a dispersion medium containing photosensitive silver halide grains on a support. Enormous research has been conducted to increase the sensitivity of silver halide light-sensitive materials. In order to increase the sensitivity of silver halide photosensitive materials, it is very important to increase the sensitivity inherent to silver halide grains. Various methods are used to increase the sensitivity inherent to silver halide grains. It has been. For example, high sensitivity by chemical sensitizers such as sulfur, gold and group VIII metal compounds, chemical sensitizers such as sulfur, gold and group VIII metal compounds and additives that promote their sensitization effect Higher sensitivity is achieved by combination, and higher sensitivity is achieved by adding an additive having a sensitizing effect depending on the type of silver halide emulsion. These are described, for example, in Non-Patent Documents 1 and 2 and Patent Documents 1-8. Further, a method of increasing the reduction of silver halide grains is also used as a means for increasing sensitivity. The reduction sensitization of silver halide grains is described in, for example, Patent Documents 9 to 13, and the method of using a reducing agent is described in, for example, Patent Documents 14 to 16. Recently, a sensitization technique using an organic electron donating compound comprising an electron donating group and a leaving group as described in Patent Documents 17 to 22 has been reported. This method is an unprecedented new sensitization technique and is effective in increasing sensitivity. However, when this compound is used, the sensitivity is increased, but at the same time, there is a drawback that the covering (Dmin) becomes high, and there has been a strong demand for improvement.
Research Disclosure, Volume 120, April 1974, 12008 Research Disclosure, Volume 34, June 1975, 13452 US Pat. No. 2,642,361 U.S. Pat. No. 3,297,446 US Pat. No. 3,772,031 US Pat. No. 3,857,711 US Pat. No. 3,901,714 U.S. Pat. No. 4,266,018 U.S. Pat. No. 3,904,415 British Patent 1,315,755 US Pat. No. 2,518,698 US Pat. No. 3,201,254 US Pat. No. 3,411,917 U.S. Pat. No. 3,779,777 US Pat. No. 3,930,867 Japanese Patent Publication No.57-33572 Japanese Patent Publication No.58-1410 JP-A-57-179835 US Pat. No. 5,747,235 US Pat. No. 5,747,236 European Patent No. 786692A1 European Patent No. 893731A1 specification European Patent No. 893732A1 Specification International publication WO99 / 05570 pamphlet

  The present invention solves the above-mentioned problems of the prior art and provides a silver halide photographic light-sensitive material having high sensitivity and low covering.

The object of the present invention can be achieved by the following means.
(1) A silver halide color photographic material having at least one blue-sensitive layer, green-sensitive layer and red-sensitive layer on a support , wherein the blue-sensitive layer has the same critical micelle concentration in the same layer. An emulsified dispersion containing 0.01% by mass or more of all components contained in the blue-sensitive layer with a surfactant of 4.0 × 10 ⁻³ mol / L or less, and a compound of the following general formula (I): A silver halide color photographic light-sensitive material comprising:

Formula (I)
(X) k- (L) m- (AB) n
In the formula, X represents a silver halide adsorbing group or a light absorbing group having at least one atom selected from the group consisting of N, S, P, Se and Te. L represents a divalent linking group having at least one atom selected from the group consisting of C, N, S and O. A represents an electron donating group, B represents a leaving group or a hydrogen atom, and after oxidation, is eliminated or deprotonated to generate a radical A. k and m each independently represents an integer of 0 to 3, and n represents 1 or 2.

(2) The silver halide color photosensitive material as described in (1) above, wherein the emulsified dispersion contains a high-boiling organic solvent having a dielectric constant of 7.0 or less.

(3) The halogen according to (1) or (2), wherein 50% or more of the total projected area of the silver halide grains contained in the photosensitive layer satisfies the following (a) to (d): Silver halide color photographic material.

(A) Parallel main plane is (111) plane (b) Aspect ratio is 2 or more (c) At least 10 dislocation lines per grain (d) Silver chloride content is less than 10 mol% Tabular silver halide grains made of silver or silver chloroiodobromide

(4) 50% or more of the total projected area of silver halide grains contained in the photosensitive layer satisfies the following (a), (d) and (e): (1) or (2 Silver halide color photographic light-sensitive material as described in 1).

(A) tabular silver halide grains made of (111) plane parallel plane (d) silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol% (e) hexagonal halide At least one epitaxial junction per grain at the apex and / or side and / or main plane of the silver grain

(5) 50% or more of the total projected area of silver halide grains contained in the photosensitive layer satisfies the following (d), (f) and (g): (1) or (2) A silver halide color photographic light-sensitive material as described in 1.

(D) Tabular silver halide grains made of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol%. (F) Parallel main plane is (100) plane (g) Aspect ratio is 2. that's all

(6) In (1) or (2), 50% or more of the total projected area of silver halide grains contained in the photosensitive layer satisfies (g), (h) and (i) The silver halide color photographic light-sensitive material described.

(G) Tabular grains having an aspect ratio of 2 or more, (h) parallel main plane containing (111) plane or (100) plane (i) at least 80 mol% or more of silver chloride

(7) The silver halide color photographic light-sensitive material has the following general formulas (VI), (VII), (VIII-1), (VIII-2), (IX-1), (IX-2), ( The silver halide color photographic light-sensitive material as described in any one of (1) to (6), which contains at least one selected from the compounds represented by X) and (XI).

General formula (VI)

In the formula, Rb1, Rb2, Rb3 and Rb4 each independently represent a hydrogen atom, an aryl group, a chain or cyclic alkyl group, a chain or cyclic alkenyl group, or an alkynyl group, and Rb5 represents a chain or cyclic group. An alkyl group, a chain or cyclic alkenyl group, an alkynyl group, an aryl group or a heterocyclic group is represented.

Formula (VII)

In the formula, Het is an adsorbing group to silver halide. M represents a divalent linking group composed of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Hy represents a group having a hydrazine structure represented by Rb6Rb7N-NRb8Rb9. Rb6, Rb7, Rb8 and Rb9 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Rb6 and Rb7, Rb8 and Rb9, Rb6 and Rb8 or Rb7 and Rb9 are bonded to each other. A ring may be formed. However, at least one of Rb6, Rb7, Rb8 and Rb9 is an alkylene group, alkenylene group, alkynylene group, arylene group or divalent complex for substitution by-(M) k2 (Het) k1 in the general formula (VII). It is a ring residue. k1 and k3 each independently represent 1, 2, 3 or 4, and k2 represents 0 or 1.

General formula (VIII-1), (VIII-2)

In formula (VIII-1), Rb10, Rb11, Rb12 and Rb13 each independently represent a hydrogen atom or a substituent. However, when Rb10 and Rb13 or Rb11 and Rb12 are each an alkyl group, they do not take a substituent having exactly the same carbon number. In formula (VIII-2), Rb14, Rb15 and Rb16 each independently represent a hydrogen atom or a substituent. Z represents a nonmetallic atom group forming a 4-6 membered ring.

Formula (IX-1)

In formula (IX-1), Rc1 represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and Rc2 represents a hydrogen atom or a group represented by Rc1. Rc3 represents a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group having 1 to 10 carbon atoms. Rc1 and Rc2, Rc1 and Rc3, or Rc2 and Rc3 may be bonded to each other to form a 5- to 7-membered ring.

Formula (IX-2)

In the formula, G1 and G2 each represent a hydrogen atom or a monovalent substituent. Moreover, it may combine with each other to form a ring.

Formula (X)

In the formula, Rb17, Rb18 and Rb19 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and Rb20 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic ring. group or an NRb21Rb22,, J represents -CO- or -SO ₂ - represents, n represents 0 or 1. Rb21 represents a hydrogen atom, hydroxy group, amino group, alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, and Rb22 represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. Represent. Rb17 and Rb18, Rb17 and Rb19, Rb19 and Rb20, or Rb20 and Rb18 may be linked to form a ring.

Formula (XI)

一般式（３）および（４）において、Ｗ₅₁、Ｗ₅₂はスルホ基または水素原子を表す。但し、Ｗ₅₁、Ｗ₅₂の少なくとも１つはスルホ基を表す。
（１０）前記感光性層に含まれるハロゲン化銀粒子が、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およびＢｉからなる群から選択される金属のイオン少なくとも１種を粒子内部に含有することを特徴とする（１）ないし（９）のいずれか１項に記載のハロゲン化銀カラー写真感光材料。
（１１）前記乳化分散物の平均粒径が１０μｍ以下であることを特徴とする（１）〜（１０）のいずれかに記載のハロゲン化銀カラー写真感光材料。
（１２）前記高沸点有機溶媒のハロゲン化銀乳剤中の含有量が０．０５〜１０質量％であることを特徴とする（２）〜（１１）のいずれかに記載のハロゲン化銀カラー写真感光材料。
（１３）前記青感性層が高感度青感性層と低感度青感性層とを含み、前記乳化分散物と前記一般式（Ｉ）の化合物が含まれる層が高感度青感性層であることを特徴とする（１）〜（１２）のいずれかに記載のハロゲン化銀カラー写真感光材料。
（１４）前記ハロゲン化銀カラー写真感光材料がカラーネガ写真感光材料である（１）〜（１３）のいずれかに記載のハロゲン化銀カラー写真感光材料。 In the formula, X ² and Y ² each independently represent a hydroxyl group, —NRi23Ri24 or —NHSO ₂ Ri25. Ri21 and Ri22 each independently represent a hydrogen atom or an arbitrary substituent. Ri21 and Ri22 may be bonded to each other to form a carbocyclic or heterocyclic ring. Ri23 and Ri24 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Ri23 and Ri24 may be bonded to each other to form a heterocyclic ring. Ri25 represents an alkyl group, an aryl group, an amino group or a heterocyclic ring.
(8) The silver halide color as described in any one of (1) to (7), wherein the silver halide grains contained in the silver halide photographic light-sensitive material are subjected to reduction sensitization. Photosensitive material.
(9) A compound selected from a compound represented by the following general formula (3) and a compound represented by the following general formula (4) when the silver halide emulsion contained in the silver halide photographic light-sensitive material is prepared: The silver halide color photographic light-sensitive material as described in any one of (1) to (8), wherein at least one of them is added.

In the general formulas (3) and (4), 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.
(10) The silver halide grains contained in the photosensitive layer are Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, It contains at least one metal ion selected from the group consisting of Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb and Bi inside the particle. The silver halide color photographic material according to any one of (1) to (9).
(11) The silver halide color photographic light-sensitive material as described in any one of (1) to (10), wherein an average particle diameter of the emulsified dispersion is 10 μm or less.
(12) The silver halide color photograph as described in any one of (2) to (11) above, wherein the content of the high-boiling organic solvent in the silver halide emulsion is 0.05 to 10% by mass. Photosensitive material.
(13) The blue-sensitive layer includes a high-sensitivity blue-sensitive layer and a low-sensitivity blue-sensitive layer, and the layer containing the emulsified dispersion and the compound of the general formula (I) is a high-sensitivity blue-sensitive layer. The silver halide color photographic light-sensitive material according to any one of (1) to (12), which is characterized in that
(14) The silver halide color photographic light-sensitive material according to any one of (1) to (13), wherein the silver halide color photographic light-sensitive material is a color negative photographic light-sensitive material.

Hereinafter, the present invention will be described in more detail.
The silver halide emulsion in the present invention is preferably silver bromide, silver chloride, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloroiodobromide or the like. The form of the silver halide grains may be normal crystals such as octahedrons, cubes, and tetradecahedrons, but tabular grains are more preferred.

  First, a tabular shape made of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol%, wherein the silver halide grains as the first emulsion relating to the present invention are parallel (111) planes. The silver halide grains will be described.

This emulsion consists of opposing (111) main planes and side faces connecting the main planes. The tabular grain emulsion is composed of silver iodobromide or silver chloroiodobromide. Although silver chloride may be contained, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. The silver iodide content is 0.5 mol% or more and 40 mol% or less, preferably 1.0 mol% or more and 20 mol% or less.
Regardless of the silver iodide content, the variation coefficient of the distribution of silver iodide content among grains is preferably 20% or less, and particularly preferably 10% or less.

  The silver iodide distribution preferably has a structure within the grain. In this case, the structure of silver iodide distribution can be a double structure, a triple structure, a quadruple structure, or even more. Further, the silver iodide content may vary continuously within the grain.

  More than 50% of the total projected area is occupied by grains having an aspect ratio of 2 or more. Here, the projected area and aspect ratio of the tabular grains can be measured from electron micrographs obtained by the carbon replica method in which shadows are applied together with reference latex spheres. The tabular grains are usually hexagonal, triangular, or circular when viewed from above, and the aspect ratio is a value obtained by dividing the diameter of a circle having the same area as the projected area by the thickness. The shape of the tabular grains is preferably as the hexagonal ratio is high, and the ratio of the lengths of adjacent sides of the hexagon is preferably 1: 2 or less.

  The tabular grains preferably have a projected area diameter of 0.1 to 20.0 μm, more preferably 0.2 to 10.0 μm. The projected area diameter is the diameter of a circle having an area equal to the projected area of the silver halide grains. The thickness of the tabular grain is 0.01 μm or more and 0.5 μm or less, preferably 0.02 μm or more and 0.4 μm or less. The thickness of the tabular grain is the distance between the two main planes. The equivalent sphere diameter is preferably 0.1 μm or more and 5.0 μm or less, and more preferably 0.2 μm or more and 3 μm or less. The equivalent sphere diameter is the diameter of a sphere having a volume equal to the volume of each particle. The aspect ratio is preferably 1 or more and 100 or less, more preferably 2 or more and 50 or less. The aspect ratio is a value obtained by dividing the projected area diameter of a grain by the thickness of the grain.

  The silver halide grains contained in the first and second emulsions relating to the present invention are preferably monodispersed. The variation coefficient of the equivalent sphere diameter of all silver halide grains contained in the first and second emulsions relating to the present invention is 30% or less, preferably 25% or less. In the case of tabular grains, the variation coefficient of projected area diameter is also important, and the variation coefficient of projected area diameter of all silver halide grains of the present invention is preferably 30% or less, more preferably 25% or less. More preferably, it is 20% or less. Further, the variation coefficient of the thickness of the tabular grains is preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less. The coefficient of variation is a value obtained by dividing the standard deviation of the distribution of projected area diameters of individual silver halide grains by the average projected area diameter, or the standard deviation of thickness distribution of individual silver halide tabular grains by the average thickness. Divided value.

  The tabular grain spacing of the tabular grains contained in the first and second emulsions relating to the present invention is 0.012 μm or less as described in US Pat. No. 5,219,720, or described in JP-A-5-249585. (111) The distance between main planes / twin plane spacing may be 15 or more, and may be selected according to the purpose.

  The higher the aspect ratio, the more remarkable the effect is obtained. Therefore, the tabular grain emulsion preferably occupies 50% or more of the total projected area, preferably with grains having an aspect ratio of 5 or more. More preferably, the aspect ratio is 8 or more. If the aspect ratio is too large, the above-mentioned variation coefficient of the particle size distribution tends to increase. Therefore, the aspect ratio is usually preferably 100 or less.

  The dislocation lines of tabular grains are described in, for example, J. F. Hamilton, Photo. Sci. Eng. 11, 57, (1967) and T.W. Shiozawa, J. et al. Soc. Photo. Sci. It can be observed by a direct method using a transmission electron microscope at a low temperature described in Japan, 35, 213, (1972). In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation lines to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by a transmission method in a state where the tube is cooled. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, it is possible to observe more clearly by using an electron microscope of a high pressure type (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

  The number of dislocation lines is preferably an average of 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and clearly, it can be distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as the number average by counting the number of dislocation lines for 100 grains or more.

  Dislocation lines can be introduced, for example, in the vicinity of the side surfaces of the tabular grains. In this case, the dislocation is almost perpendicular to the side surface, and the dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (side surface) to the side surface. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the positions where the dislocation lines start is similar to the particle shape, but is not completely similar and may be distorted. This type of dislocation number is not found in the central region of the grain. The direction of dislocation lines is crystallographically approximately (211) but is often serpentine and sometimes intersects.

  Moreover, even if it has a dislocation line substantially uniformly over the whole region near the side surface of the tabular grain, it may have a dislocation line at a local position near the side surface. That is, taking hexagonal tabular silver halide grains as an example, the dislocation lines may be limited only to the vicinity of six vertices, or the dislocation lines may be limited to only one of the vertices. Conversely, it is possible that the dislocation line is limited to only the sides excluding the vicinity of the six vertices.

  Further, dislocation lines may be formed over a region including the centers of two parallel main planes of the tabular grains. When dislocation lines are formed over the entire main plane, the direction of the dislocation lines may be approximately (211) in terms of crystallography when viewed from the direction perpendicular to the main plane. It may be formed randomly, and the length of each dislocation line is also random, and it may be observed as a short line on the main plane, or it may be observed as reaching a side (periphery) as a long line. is there. Dislocation lines are often straight or meandering. They often cross each other.

  As described above, the position of the dislocation line may be limited to the outer periphery, the main plane, or a local position, or may be formed by combining them. That is, it may exist simultaneously on the outer periphery and the main plane.

  The silver iodide content on the surface of the tabular grain emulsion is preferably 10 mol% or less, particularly preferably 5 mol% or less. The silver iodide content on the surface of the grain of the present invention is measured using XPS (X-ray Photoelectron Spectroscopy). Regarding the principle of the XPS method used to analyze the silver iodide content near the surface of silver halide grains, refer to Aihara et al., “Electron Spectroscopy” (Kyoritsu Library-16, published by Kyoritsu Shuppan, Showa 53). can do. The standard XPS measurement method uses Mg-Kα as the excitation X-ray, and iodine (I) and silver (Ag) photoelectrons (usually I-3d5) emitted from silver halide in an appropriate sample form. / 2, Ag-3d5 / 2). To determine the iodine content, several standard samples with known iodine content are used, and a calibration curve of the intensity ratio (intensity (I) / intensity (Ag)) of the photoelectrons of iodine (I) and silver (Ag) is used. Can be obtained and obtained from this calibration curve. In a silver halide emulsion, the XPS measurement must be performed after degrading and removing gelatin adsorbed on the surface of the silver halide grains with a proteolytic enzyme or the like. A tabular grain emulsion having a silver iodide content of 10 mol% or less on the grain surface means an emulsion grain having a silver iodide content of 10 mol% or less when analyzed by XPS of the emulsion grains contained in one emulsion. . In this case, when two or more types of emulsions are clearly mixed, it is necessary to perform analysis on the same type of emulsion after appropriate pretreatment such as centrifugation and filtration.

  As the structure of the tabular grain emulsion of the present invention, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide and a higher order structure higher than that are preferable. The boundary of the silver iodide content between the structures may be clear, or may change continuously and gently. Usually, the measurement of silver iodide content using a powder X-ray diffraction method does not show two distinct peaks with different silver iodide contents, but lies in the direction of high silver iodide content. Such an X-ray diffraction profile is shown.

  The silver iodide content of the layer inside the surface is preferably high, and the silver iodide content of the layer inside the surface is preferably 3 mol% or more, more preferably 5 mol% or more.

  Next, the parallel main plane which is the second emulsion relating to the present invention is the (111) plane, and the ratio of the length of the side having the maximum length to the length of the side having the minimum length is 2 or less. The grains having at least one epitaxial junction per grain at the apex part and / or the side part and / or the main plane part of the hexagonal silver halide grains are described. An epitaxially bonded grain is a grain having a crystal part (that is, an epitaxial part) joined to the grain in addition to the silver halide grain body, and the joined crystal part usually protrudes from the silver halide grain body. The ratio of the bonded crystal part (epitaxial part) to the total silver amount of the grain is preferably 1% or more and 30% or less, and more preferably 2% or more and 15% or less. The epitaxial part may exist in any part of the grain body, but the grain main plane part, grain side part, and grain apex part are preferred. The number of epitaxials is preferably at least one. The composition of the epitaxial part is preferably AgBr, AgCl, AgBrCl, AgBrClI, AgBrI, AgI, AgSCN, or the like. When the epitaxial portion exists, dislocation lines may exist inside the grain, but it does not have to exist. Further, although dislocation lines may not exist in the epitaxial portion, the silver halide grain main body and the epitaxial junction portion, and the epitaxial portion, it is preferable that dislocation lines exist.

Next, a method for preparing the first emulsion and the second emulsion silver halide grains relating to the present invention will be described.
The preparation process of the present invention comprises (a) a base particle forming process and a subsequent particle forming process ((b) process). Basically, it is more preferable to perform the step (b) following the step (a), but only the step (a) may be performed. The step (b) may be any of (b1) dislocation introduction step, (b2) apex dislocation limited introduction step, or (b3) epitaxial junction step, and at least one or two or more may be combined. .

  First, (a) the base particle forming step will be described. The base portion is preferably at least 50% or more, more preferably 60% or more, based on the total silver amount used for grain formation. Moreover, the average content of iodine with respect to the amount of silver in the base portion is preferably 0 mol% or more and 30% mol or less, and more preferably 0 mol% or more and 15 mol% or less. The base portion may have a core-shell structure as necessary. At this time, the core part of the base part is preferably 50% or more and 70% or less with respect to the total silver amount of the base part, and the average iodine composition of the core part is preferably 0 mol% or more and 30 mol% or less, and 0 mol% or more and 15 mol or less. % Or less is more preferable. The iodine composition of the shell part is preferably 0 mol% or more and 3 mol% or less.

  As a method for preparing a silver halide emulsion, a method in which after forming silver halide nuclei and further growing silver halide grains to obtain grains of a desired size, the present invention is also the same. There is no change. Further, the formation of tabular grains includes at least nucleation, ripening, and growth steps. This process is described in detail in US Pat. No. 4,945,037. Hereinafter, nucleation, ripening, growth, and each process will be described.

1. Nucleation Step Tabular grain nucleation is generally performed by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding an aqueous solution of a protective colloid, or a protective colloid solution containing an alkali halide. A single jet method is used in which a silver salt aqueous solution is added. Moreover, the method of adding aqueous alkali halide solution to the protective colloid solution containing a silver salt as needed can also be used. Furthermore, if necessary, a protective colloid solution, a silver salt solution, and an alkali halide aqueous solution are added to a mixer disclosed in JP-A-2-44335, and immediately transferred to a reaction vessel, whereby the core of tabular grains is obtained. Formation can also be performed. Further, as disclosed in US Pat. No. 5,104,786, nucleation can be performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto. .

  Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. Examples of the gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide or the like (methionine content 40 μmol / g or less), amino group-modified gelatin of the present invention (for example, phthalated gelatin, Trimerized gelatin, succinated gelatin, maleated gelatin, esterified gelatin), and low molecular weight gelatin (molecular weight: 3000 to 40,000) are used. Japanese Patent Publication No. 5-12696 can be referred to for the oxidized gelatin, and Japanese Patent Application Laid-Open Nos. 8-82883 and 11-143002 can be referred to for the amino group-modified gelatin. In addition, a lime-processed bone gelatin containing 20% or more, preferably 30% or more of a component having a molecular weight of 280,000 or more is used in the molecular weight distribution measured by the paggy method described in JP-A-11-237704 as necessary. May be. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are described in Japanese Patent Publication No. 7-111550, Research Disclosure Magazine Vol. 176, No. 17643 (December 1978), section IX.

In the nucleation, the excess halogen salt is preferably Cl ⁻ , Br ⁻ , or I ⁻ , and these may be used alone or in plural. The total halogen salt concentration is 3 × 10 ⁻⁵ mol / L or more and 0.1 mol / L or less, preferably 3 × 10 ⁻⁴ mol / L or more and 0.01 mol / L or less.

The halogen composition in the halide solution added at the time of nucleation is preferably Br ⁻ , Cl ⁻ , or I ⁻ , and these may be used alone or in plural. May be used nucleation such that the chlorine content as described is 10 mol% or more of the amount of silver used in nucleation in JP-A-10-293372, this time Cl ^- concentrations The total halogen salt concentration is preferably 10 mol% or more and 100 mol% or less, more preferably 20 mol% or more and 80 mol% or less.
The protective colloid may be dissolved in the halide solution added at the time of nucleation, or the gelatin solution may be added at the same time as the nucleation separately from the halide solution.

The temperature during nucleation is preferably from 5 to 60 ° C, but more preferably from 5 to 48 ° C when producing fine tabular grains having an average particle size of 0.5 µm or less.
The pH of the dispersion medium is preferably 4 or more and 8 or less when amino group-modified gelatin is used, but preferably 2 or more and 8 or less when other gelatin is used.

2. Aging process In the nucleation, fine particles other than tabular grains (especially octahedral and single twin grains) are formed. Before entering the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and having good monodispersity. In order to make this possible, it is well known to perform Ostwald ripening following nucleation.

  Immediately after nucleation, pBr is adjusted, and then the temperature is increased and ripening is performed until the hexagonal tabular grain ratio reaches the maximum. At this time, a protective colloid solution may be additionally added. In this case, the concentration of the protective colloid with respect to the dispersion medium solution is preferably 10% by mass or less. As the additional protective colloid used at this time, the aforementioned alkali-treated gelatin, the amino group-modified gelatin of the present invention, oxidized gelatin, low molecular weight gelatin, natural polymer, or synthetic polymer is used. Moreover, you may use the lime processing bone gelatin which contains 30% or more of components of molecular weight 280,000 or more in the molecular weight distribution measured by the paggy method described in Unexamined-Japanese-Patent No. 11-237704 as needed. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used.

  The aging temperature is 40 to 80 ° C., preferably 50 to 80 ° C., and the pBr is 1.2 to 3.0. The pH is preferably 4 or more and 8 or less when amino group-modified gelatin is present, but is preferably 2 or more and 8 or less for other gelatins.

At this time, a silver halide solvent may be added so that grains other than the tabular grains disappear quickly. In this case, the concentration of the silver halide solvent is preferably 0.3 mol / liter or less, more preferably 0.2 mol / liter or less (hereinafter, the liter is also expressed as “L”).
Aging in this way leaves almost 100% tabular grains only.
After the ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows.

(i) In the case of an alkaline silver halide solvent such as NH ₃ , an acid having a large solubility product with Ag ⁺ such as HNO ₃ is added to be invalidated.
(ii) In the case of a thioether-based silver halide solvent, it is invalidated by adding an oxidizing agent such as H ₂ O ₂ as described in JP-A-60-136736.

  In the method for producing an emulsion of the present invention, the end of the ripening step means grains other than tabular grains having a main plane of hexagon or triangle and having at least two twin planes (regular and single twin crystals). This refers to the point at which the particles have disappeared. The disappearance of grains other than tabular grains having a hexagonal or triangular main plane and having at least two twin planes can be confirmed by observing a TEM image of a replica of the grains.

  In the ripening step, an over-ripening step described in JP-A-11-174606 may be provided as necessary. The over-ripening step is a step of erasing tabular grains having a slow anisotropic growth speed by further aging the tabular grains themselves after ripening (ripening step) until the hexagonal tabular grain ratio reaches the maximum. . When the number of tabular grains obtained in the aging step is 100, the number of tabular grains is preferably reduced to 90 or less, more preferably 60 or more and 80 or less by the over-ripening step. .

  In the method for producing an emulsion of the present invention, conditions such as pBr and temperature in the overripening step can be set to be the same as those in the ripening step. In the overripening step, the silver halide solvent can be added in the same manner as in the ripening step, and the type, concentration, etc. can be set to be the same as those in the ripening step.

3. Growth Process It is preferable to keep pBr in the crystal growth period following the ripening process at 1.4 to 3.5. When the concentration of the protective colloid in the dispersion medium solution before entering the growth process is low (1% by mass or less), the protective colloid may be additionally added. In addition, protective colloids may be added during the growth process. The timing of additional addition may be any time during the growth process. The protective colloid concentration in the dispersion medium solution is preferably 1 to 10% by mass. As the protective colloid used at this time, the above-mentioned alkali-treated gelatin, the amino group-modified gelatin of the present invention, oxidized gelatin, natural polymer, or synthetic polymer is used. In addition, a lime-processed bone gelatin containing 20% or more, preferably 30% or more of a component having a molecular weight of 280,000 or more is used in the molecular weight distribution measured by the paggy method described in JP-A-11-237704 as necessary. May be. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. The pH during growth is preferably 4 to 8 or less when amino group-modified gelatin is present, and 2 to 8 is preferable otherwise. The addition rate of Ag ⁺ and halogen ions in the crystal growth period is preferably 20 to 100%, preferably 30 to 100% of the crystal critical growth rate. In this case, the addition rate of silver ions and halogen ions is increased with crystal growth. In this case, the addition rate of silver salt and halogen salt aqueous solution as described in Japanese Patent Publication Nos. 48-36890 and 52-16364. The concentration of the aqueous solution may be increased.

  When performing the double jet method in which a silver salt aqueous solution and a halogen salt aqueous solution are added simultaneously, in order to prevent the introduction of growth dislocation due to heterogeneous iodine, it is possible to improve the stirring of the reaction vessel and dilute the concentration of the added solution. preferable.

  A method of adding an AgI fine grain emulsion prepared outside the reaction vessel simultaneously with the addition of the silver salt aqueous solution and the halogen salt aqueous solution is further preferred. At this time, the growth temperature is preferably 50 ° C. or higher and 90 ° C. or lower, and more preferably 60 ° C. or higher and 85 ° C. or lower. The AgI fine grain emulsion to be added may be prepared in advance or may be added while continuously preparing. JP-A-10-43570 can be referred to for the preparation method in this case.

  The average grain size of the added AgI emulsion is 0.01 μm or more and 0.1 μm or less, preferably 0.02 μm or more and 0.08 μm or less. The iodine composition of the base grains can be changed depending on the amount of AgI emulsion to be added.

Further, silver iodobromide fine particles may be added in place of the addition of the silver salt aqueous solution and the halogen salt aqueous solution. At this time, the base particles having a desired iodine composition can be obtained by making the iodine amount of the fine particles equal to the iodine amount of the desired base particles. The silver iodobromide fine particles may be prepared in advance, but it is preferable to add them while preparing them continuously. The size of the silver iodobromide fine particles to be added is 0.005 μm or more and 0.05 μm or less, preferably 0.01 μm or more and 0.03 μm or less. The temperature during growth is 60 ° C. or higher and 90 ° C. or lower, preferably 70 ° C. or higher and 85 ° C. or lower.
Further, the above ion addition method, AgI fine particle addition method, and AgBrI fine particle addition method may be combined.

  In the present invention, the tabular grains preferably have dislocation lines, but it is preferable that no dislocation lines exist in the base portion in order to reduce pressure desensitization. Dislocation lines of tabular grains are described in, for example, JF Hamilton, Phot. Sci. Eng., 11, 57 (1967), T. Shiozawa, J. Soc. Phot. Sci. Japan, 35, 213 (1972). It can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out carefully so as not to apply a pressure that causes dislocation lines to the grains from the emulsion are placed on a mesh for electron microscope observation to prevent damage (printout, etc.) due to electron beams. Observation is performed by a transmission method in a state where the tube is cooled. At this time, the thicker the particle, the more difficult it is to transmit the electron beam. Therefore, it is possible to observe more clearly using a high-pressure type electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle when viewed from the direction perpendicular to the main plane can be obtained.

Next, step (b) will be described.
First, step (b1) will be described. The step (b1) includes a first shell step and a second shell step. A first shell is provided on the base described above. The ratio of the first shell is preferably 1% or more and 30% or less with respect to the total silver amount, and the average silver iodide content thereof is 20 mol% or more and 100 mol% or less. More preferably, the ratio of the first shell is 1% or more and 20% or less with respect to the total silver amount, and the average silver iodide content thereof is 25 mol% or more and 100 mol% or less. For the growth of the first shell on the substrate, a silver nitrate aqueous solution and a halogen aqueous solution containing iodide and bromide are basically added by the double jet method. Alternatively, an aqueous silver nitrate solution and an aqueous halogen solution containing iodide are added by the double jet method. Alternatively, an aqueous halogen solution containing iodide is added by the single jet method.

  Any of the above methods may be used in combination. As is apparent from the average silver iodide content of the first shell, silver iodide can be precipitated in addition to the silver iodobromide mixed crystal when the first shell is formed. In either case, normally, silver iodide disappears and all changes to a silver iodobromide mixed crystal when the next second shell is formed.

  As a preferred method for forming the first shell, there is a method in which a silver iodobromide or silver iodide fine grain emulsion is added, ripened and dissolved. Further, as a preferred method, there is a method of adding a silver iodide fine grain emulsion and then adding a silver nitrate aqueous solution or a silver nitrate aqueous solution and a halogen aqueous solution. In this case, dissolution of the silver iodide fine grain emulsion is promoted by the addition of an aqueous silver nitrate solution. The silver content of the added silver iodide fine grain emulsion is used as the first shell, and the silver iodide content is 100 mol%. . And it calculates as a 2nd shell using the silver amount of the added silver nitrate aqueous solution. The silver iodide fine grain emulsion is preferably added rapidly.

  The rapid addition of the silver iodide fine grain emulsion means that the silver iodide fine grain emulsion is preferably added within 10 minutes. More preferably, it means adding within 7 minutes. This condition may vary depending on the temperature of the system to be added, pBr, pH, type and concentration of protective colloid agent such as gelatin, presence / absence, type and concentration of silver halide solvent, but as described above, shorter one is preferable. When adding, it is preferable that substantially no silver salt aqueous solution such as silver nitrate is added. The temperature of the system at the time of addition is preferably 40 ° C. or higher and 90 ° C. or lower, and particularly preferably 50 ° C. or higher and 80 ° C. or lower.

The silver iodide fine grain emulsion may be substantially silver iodide, and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. 100% silver iodide is preferred. Silver iodide may have β-form, γ-form and α-form or α-form-like structure as described in US Pat. No. 4,672,026 in crystal structure. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form is used. The silver iodide fine grain emulsion may be formed immediately before the addition described in US Pat. No. 5,004,679 or the like, and may be any one subjected to a normal water washing step. What passed through the water washing process of this is used. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026. A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, in which the pI value at the time of grain formation is kept constant, is preferred. Where pI is the logarithm of the reciprocal of the I ⁻ ion concentration of the system. The type, concentration, presence / absence of silver halide solvent, type, concentration, etc. of the protective colloid agent such as temperature, pI, pH, and gelatin are not particularly limited, but the grain size is 0.1 μm or less, more preferably 0.07 μm. The following is convenient for the present invention. The particle shape cannot be completely specified because it is a fine particle, but the variation coefficient of the particle size distribution is preferably 25% or less. In particular, when it is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are obtained by placing the silver iodide fine grains on a mesh for observation with an electron microscope and directly observing them by a transmission method instead of the carbon replica method. This is because the measurement error becomes large in the observation by the carbon replica method because the particle size is small. The particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also obtained by using this equal projected area circle diameter. The silver iodide fine particles most effective in the present invention have a grain size of 0.06 μm or less and 0.02 μm or more, and a grain size distribution variation coefficient of 18% or less.

  The silver iodide fine grain emulsion is preferably prepared after the above-described grain formation, by usual water washing described in U.S. Pat. No. 2,614,929, etc., concentration adjustment of protective colloid agents such as pH, pI, gelatin and the like. Density adjustment is performed. The pH is preferably 5 or more and 7 or less. The pI value is preferably set to a pI value at which the solubility of silver iodide is minimized or a pI value higher than that value. As the protective colloid agent, ordinary gelatin having an average molecular weight of about 100,000 is preferably used. Low molecular weight gelatin having an average molecular weight of 20,000 or less is also preferably used. It may be convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The silver amount in terms of silver atom per kg of the emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The amount of gelatin and / or silver is preferably selected to be a value suitable for rapidly adding a silver iodide fine grain emulsion.

  The silver iodide fine grain emulsion is usually dissolved before being added, but it is necessary to sufficiently increase the stirring efficiency of the system at the time of addition. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of bubbles during stirring. Specifically, antifoaming agents described in Examples of US Pat. No. 5,275,929 are used.

  As a more preferable method for forming the first shell, an iodide ion releasing agent described in US Pat. No. 5,496,694 is used in place of the conventional iodide ion supply method (method of adding free iodide ions). Thus, a silver halide phase containing silver iodide can be formed while rapidly generating iodide ions.

  The iodide ion releasing agent releases iodide ions by reaction with an iodide ion release regulator (base and / or nucleophile). Preferred examples of the nucleophilic reagent used in this case include the following chemical species. It is done. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, metabisulfite ion, hydroxamic acids, oximes, dihydroxybenzenes, mercaptans, sulfinates, carboxylates, ammonia, amines, alcohols , Ureas, thioureas, phenols, hydrazines, hydrazides, semicarbazides, phosphines, sulfides.

  The release rate and timing of iodide ions can be controlled by controlling the concentration of the base and the nucleophilic reagent, the addition method, and the temperature of the reaction solution. The base is preferably an alkali hydroxide.

The preferred concentration range of the iodide ion releasing agent and the iodide ion release controlling agent used to rapidly generate iodide ions is 1 × 10 ^{−7 to} 20M, more preferably 1 × 10 ^{−5 to} 10M, Preferably it is 1 × 10 ^{−4 to} 5M, particularly preferably 1 × 10 ^{−3 to} 2M.
When the concentration exceeds 20M, the amount of the iodide ion releasing agent having a large molecular weight and the amount of the iodide ion releasing agent added is excessively large with respect to the capacity of the particle forming container.
On the other hand, if it is less than 1 × 10 ⁻⁷ M, the iodide ion releasing reaction rate becomes slow, and it becomes difficult to rapidly produce an iodide ion releasing agent, which is not preferable.

A preferable temperature range is 30 to 80 ° C, more preferably 35 to 75 ° C, and particularly preferably 35 to 60 ° C.
When the temperature is higher than 80 ° C., the iodide ion release reaction rate is generally extremely high, and when the temperature is lower than 30 ° C., the iodide ion release reaction rate is generally extremely low.

When a base is used in releasing iodide ions, a change in solution pH may be used. At this time, the pH range preferable for controlling the release rate and timing of iodide ions is 2 to 12, more preferably 3 to 11, particularly preferably 5 to 10, and most preferably adjusted pH is 7. .5 to 10.0. Even under neutral conditions at pH 7, hydroxide ions determined by the ionic product of water act as regulators.
Further, a nucleophile and a base may be used in combination, and at this time, the pH may be controlled within the above range to control the release rate and timing of iodide ions.

When iodine atoms are released from the iodide ion releasing agent in the form of iodide ions, all iodine atoms may be released or a part of them may remain without being decomposed.
The second shell is provided on the tabular grain having the base and the first shell described above. The ratio of the second shell is preferably 10 mol% or more and 40 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 5 mol% or less. More preferably, the ratio of the second shell is 15 mol% or more and 30 mol% or less with respect to the total silver amount, and the average silver iodide content thereof is 0 mol% or more and 3 mol% or less. The growth of the second shell on the tabular grains having the base and the first shell may be in the direction of increasing or decreasing the aspect ratio of the tabular grains. Basically, the second shell is grown by adding an aqueous silver nitrate solution and an aqueous halogen solution containing bromide by the double jet method. Alternatively, after adding an aqueous halogen solution containing bromide, an aqueous silver nitrate solution may be added by a single jet method. The system temperature, pH, type and concentration of protective colloid agent such as gelatin, presence or absence of silver halide solvent, type and concentration can vary widely. As for pBr, in the present invention, it is preferable that pBr at the end of formation of the layer is higher than pBr at the initial stage of formation of the layer. Preferably, pBr at the initial stage of formation of the layer is 2.9 or less, and pBr at the end of formation of the layer is 1.7 or more. More preferably, the pBr at the initial stage of formation of the layer is 2.5 or less, and the pBr at the end of the formation of the layer is 1.9 or more. Most preferably, the pBr at the initial stage of formation of the layer is 2.3 or less and 1 or more. Most preferably, the pBr at the end of the layer is from 2.1 to 4.5.

  It is preferable that a dislocation line exists in the part of (b1) process. The dislocation lines are preferably present in the vicinity of the side surface portion of the tabular grain. The vicinity of the side surface portion refers to the side surface portion on the six sides of the tabular grain and the inner portion thereof, that is, the portion grown in the step (b1). The average number of dislocation lines present on the side surface is preferably 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, it is preferred that silver halide grains containing 10 or more dislocation lines per grain account for 100 to 50%, more preferably 100 to 70%, particularly preferably 100 to 90%. Occupy.
If it is less than 50%, it is not preferable in terms of homogeneity between particles.

  In the present invention, when determining the ratio of dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 300 particles or more. Observe by observing.

Next, step (b2) will be described.
As a first aspect, a method of dissolving only the vicinity of the apex with iodide ions, as a second aspect, a method of simultaneously adding a silver salt solution and an iodide salt solution, as a third aspect, There is a method of substantially dissolving only the vicinity of the apex using a silver halide solvent, and a fourth embodiment is a method via halogen conversion.

A method of dissolving with iodide ions according to the first embodiment will be described.
By adding iodide ions to the base particles, the vicinity of each vertex of the base particles is dissolved and rounded. Subsequently, when a silver nitrate solution and a bromide solution, or a mixed solution of a silver nitrate solution, a bromide solution, and an iodide solution are added simultaneously, the grains further grow and dislocations are introduced near the apex. Regarding this method, JP-A-4-149541 and JP-A-9-189974 can be referred to.

The total amount of iodide ions added in this embodiment is calculated by multiplying the total number of moles of iodide ions by the total number of moles of silver in the base particles and multiplying the value by 100 as I ₂ (mol%). In order to obtain effective dissolution according to the present invention, it is preferable that (I ₂ -I ₁ ) satisfy 0 or more and 8 or less with respect to the silver iodide content I ₁ (mol%) of the base grain, more preferably 0 or more and 4 or less.

In this embodiment, the concentration of iodide ions added is preferably low, specifically, preferably 0.2 mol / L or less, and more preferably 0.1 mol / L.
Further, the pAg at the time of addition of iodide ions is preferably 8.0 or more, and more preferably 8.5 or more.

  Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution alone or a mixed solution of silver nitrate solution and bromide solution or silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.

  A method of simultaneous addition of a silver salt solution and an iodide salt solution, which is the second embodiment, will be described. By rapidly adding a silver salt solution and an iodide salt solution to the base grain, silver iodide or silver halide having a high silver iodide content can be epitaxially formed at the top of the grain. At this time, the preferable addition rate of the silver salt solution and the iodide salt solution is 0.2 to 0.5 minutes, and more preferably 0.5 to 2 minutes. Since this method is described in detail in JP-A-4-149541, it can be referred to.

  Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution alone or a mixed solution of silver nitrate solution and bromide solution or silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.

A method using a silver halide solvent which is the third embodiment will be described.
When a silver halide solvent is added to the dispersion medium containing the base grains and then a silver salt solution and an iodide salt solution are added at the same time, silver iodide or silver iodide is contained at the apex of the base grains dissolved by the silver halide solvent. High-rate silver halide will preferentially grow. At this time, the silver salt solution and the iodide salt solution do not need to be added rapidly. Since this method is described in detail in JP-A-4-149541, it can be referred to.

  Following dissolution of the apex of the base particles by addition of iodide ions to the base particles, a silver nitrate solution alone or a mixed solution of silver nitrate solution and bromide solution or silver nitrate solution, bromide solution and iodide solution is simultaneously added. Addition further grows the grains and introduces dislocations near the apex.

Next, a method through halogen conversion which is the fourth embodiment will be described.
By adding an epitaxial growth site indicator (hereinafter referred to as a site director), for example, a sensitizing dye described in JP-A-58-108526, or a water-soluble iodide to the base grain, silver chloride is added to the top part of the base grain. In this method, silver chloride is converted to silver iodide or silver halide having a high silver iodide content by adding iodide ions after the formation of the epitaxial layer. As the site director, sensitizing dyes, water-soluble thiocyanate ions, and water-soluble iodide ions can be used, but iodide ions are preferred. Iodide ion is 0.0005 to 1 mol%, preferably 0.001 to 0.5 mol%, based on the base particles. When an optimum amount of iodide ions is added and then a silver salt solution and a chloride salt solution are added simultaneously, a silver chloride epitaxial layer can be formed at the apex of the base grain.

  The halogen conversion by the iodide ion of silver chloride will be described. A silver halide having a high solubility is converted to a silver halide having a low solubility by adding a halogen ion capable of forming a silver halide having a low solubility. This process is called halogen conversion and is described, for example, in US Pat. No. 4,142,900. Silver chloride epitaxially grown on the top of the base is selectively halogen-converted with iodide ions to form a silver iodide phase on the top of the base grain. Details are described in JP-A-4-149541.

  Following the halogen conversion of silver chloride epitaxially grown on the top of the base grain to the silver iodide phase by addition of iodide ions, silver nitrate solution alone, or silver nitrate solution and bromide solution, or silver nitrate solution and bromide solution The mixed solution of iodide solution is simultaneously added to further grow the grains and introduce dislocations near the apex.

  It is preferable that dislocation lines exist in the step (b2). The dislocation line is preferably present in the vicinity of the apex of the tabular grain. The vicinity of the vertex is a three-dimensional area surrounded by the perpendicular and the side when a perpendicular is drawn from the point at the position of x% from the center of the straight line connecting the center of the particle to each vertex. It is a part of. The value of x is preferably 50 or more and less than 100, more preferably 75 or more and less than 100. The average number of dislocation lines present on the side surface is preferably 10 or more per particle. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, it is preferred that silver halide grains containing 10 or more dislocation lines per grain account for 100 to 50%, more preferably 100 to 70%, particularly preferably 100 to 90%. Occupy.
If it is less than 50%, it is not preferable in terms of homogeneity between particles.

  In the present invention, when determining the ratio of dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 300 particles or more. Observe by observing.

Next, the step (b3) will be described.
Regarding the epitaxial formation of silver halide on the base grain, as described in US Pat. No. 4,435,501, iodide ion, aminoazaindene, or spectral sensitizing dye adsorbed on the base grain surface, etc. It is shown that the silver salt epitaxial layer can be formed at a site selected by the site director, for example, at the apex portion or the side surface portion of the base particle. JP-A-8-69069 achieves high sensitization by forming silver salt epitaxials at selected sites of an ultrathin tabular grain base and optimally sensitizing this epitaxial phase.

  Also in the present invention, it is very preferable to enhance the sensitivity of the base particles of the present invention using these methods. As the site director, aminoazaindene or spectral sensitizing dyes may be used, iodide ions or thiocyanate ions may be used, and they may be used properly according to the purpose or may be combined.

  By changing the addition amount of sensitizing dye, iodide ion, and thiocyanate ion, the formation site of silver salt epitaxial can be limited to the main plane part, side part, or apex part of the base particle. A combination thereof is also possible. The addition amount of aminoazaindene, iodide ion, thiocyanate ion and spectral sensitizing dye used in the site director should be selected appropriately according to the silver content, surface area, and epitaxial limited site of the silver halide base grain used. Is preferred. The temperature for forming the silver salt epitaxial is preferably 40 to 70 ° C, more preferably 45 to 60 ° C. In this case, the pAg is preferably 9.0 or less, and more preferably 8.0 or less. Thus, by appropriately selecting the type of the site director, the amount added, and the epitaxial deposition conditions (temperature, pAg, etc.), the silver salt epitaxially is selectively applied to the main plane part, the side part, or the apex part of the base particle. Can be formed. The emulsion thus obtained may be sensitized by selectively chemically sensitizing the epitaxial phase as disclosed in JP-A-8-69069. However, following the silver salt epitaxial formation, a silver salt solution and a halogen salt solution are added. Further growth may be performed by simultaneous addition. The halogen salt aqueous solution added at this time is preferably a bromide salt solution or a mixed solution of a bromide salt solution and an iodide salt solution. Moreover, the temperature in this case is preferably 40 to 80 ° C, and more preferably 45 to 70 ° C. In this case, the pAg is preferably 5.5 or more and 9.5 or less, and more preferably 6.0 or more and 9.0 or less. Further, an epitaxial halogen conversion may be performed by adding a halogen solution different from the epitaxial composition. Epitaxial formation and subsequent growth or halogen conversion may be carried out subsequently after the formation of the silver halide base grains, or may be carried out after washing / redispersing once after the formation of the base grains, or before chemical sensitization. Epitaxial formation and subsequent growth or halogen conversion may be divided before and after water washing / redispersion.

  The epitaxial formed in the step (b3) is characterized in that it is formed to protrude outside the base particles formed in the step (a). The epitaxial composition is preferably AgBr, AgCl, AgBrCl, AgBrClI, AgBrI, AgI, AgSCN, or the like. It is further preferable to introduce a “dopant (metal complex)” as described in JP-A-8-69069 into the epitaxial layer. The position of the epitaxial growth may be at least a part of the top, side, and main plane portions of the base particle, and may extend over a plurality of locations. The apex portion refers to each apex of triangles and hexagonal tabular grains (6 for hexagons, 3 for triangles), and preferably, at least one of the apexes is epitaxial. In the case of hexagonal tabular grains, the side surface means the side on the six sides and the surface connecting the two main plane portions, that is, the side surface, and the epitaxial exists on the side of the six sides and on any part of the side surface. It does not matter as long as at least one is present. The same applies to triangular tabular grains. The main plane portion refers to two main planes referred to as tabular grains, and epitaxial may exist at any position on the main plane, and at least one or more may exist. As the epitaxial shape, a {100} plane, a {111} plane, and a {110} plane may appear independently, or a plurality may appear. Further, it may have an irregular shape in which a higher-order surface appears.

  (B3) Although dislocation lines do not have to exist in the part of the step, it is more preferable that dislocation lines exist. The dislocation lines are preferably present at the junction between the base particle and the epitaxial growth portion or at the epitaxial portion. The average number of dislocation lines present in the junction or epitaxial part is preferably 10 or more per grain. More preferably, the average number is 20 or more per particle. When dislocation lines are densely present, or when dislocation lines are observed crossing each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it can be counted to the order of approximately 10, 20, or 30, and it can be clearly distinguished from the case where there are only a few. The average number of dislocation lines per particle is obtained as a number average by counting the number of dislocation lines for 100 grains or more.

It is preferable that a 6-cyano metal complex is doped during the formation of the epitaxial portion. Among the 6 cyano metal complexes, those containing iron, ruthenium, osmium, cobalt, rhodium, iridium or chromium are preferred. The addition amount of the metal complex is preferably in the range of 10 ^{−9 to} 10 ⁻² mol per mol of silver halide, and more preferably in the range of 10 ^{−8 to} 10 ⁻⁴ mol per mol of silver halide. preferable. The metal complex can be added by dissolving in water or an organic solvent. The organic solvent is preferably miscible with water. Examples of the organic solvent include alcohols, ethers, glycols, ketones, esters, and amides.

The tabular grains of the present invention desirably have a uniform dislocation dose distribution between grains. In the emulsion of the present invention, silver halide grains containing 5 or more dislocation lines per grain preferably occupy 100 to 50%, more preferably 100 to 70%, particularly preferably 100 to 90%. Occupy.
If it is less than 50%, it is not preferable in terms of homogeneity between particles.

  In the present invention, when determining the ratio of dislocation lines and the number of dislocation lines, it is preferable to directly observe the dislocation lines for at least 100 particles, more preferably 200 particles or more, and particularly preferably 300 particles or more. Observe by observing.

  As the protective colloid used in the preparation of the emulsion of the present invention and as a binder for other hydrophilic colloid layers, gelatin is advantageously used, but other hydrophilic colloids can also be used.

  For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives Various synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinylpyrazole, or a single or copolymer Substances can be used.

  The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. Gelatin is used as the protective colloid, but natural polymers and synthetic polymers other than gelatin can be used as well. Examples of the gelatin include alkali-treated gelatin, oxidized gelatin obtained by oxidizing methionine groups in gelatin molecules with hydrogen peroxide or the like (methionine content 40 μmol / g or less), amino group-modified gelatin of the present invention (for example, phthalated gelatin, Trimellited gelatin, succinated gelatin, maleated gelatin, and esterified gelatin) are used. In addition, a lime-processed bone gelatin containing 20% or more, preferably 30% or more of a component having a molecular weight of 280,000 or more is used in the molecular weight distribution measured by the paggy method described in JP-A-11-237704 as necessary. May be. Further, for example, starches described in European Patent No. 758758 and US Pat. No. 5,733,718 may be used. In addition, natural polymers are described in Japanese Patent Publication No. 7-111550, Research Disclosure Magazine Vol. 176, No. 17643 (December 1978), section IX. The temperature for washing with water can be selected according to the purpose, but is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can be selected according to the purpose, but is preferably selected between 2 and 10. More preferably, it is the range of 3-8. The pAg at the time of washing can also be selected according to the purpose, but it is preferably selected from 5 to 10. The washing method can be selected from a noodle washing method, a dialysis method using a semipermeable membrane, a centrifugal separation method, a coagulation sedimentation method, an ion exchange method, and an ultrafiltration method. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like can be selected.

  At the time of grain formation of the present invention, it was described in, for example, JP-A-5-173268, JP-A-5-173269, JP-A-5-173270, JP-A-5-173271, JP-A-6-202258, and JP-A-7-175147. Polyalkylene oxide block copolymers or polyalkylene oxide copolymers described, for example, in Japanese Patent No. 3089578 may be present. The time when the compound is present may be any time during the preparation of the particles, but the effect is great when used at an early stage of particle formation.

  A tabular silver halide grain comprising silver iodobromide or silver chloroiodobromide having a (100) plane silver chloride content of less than 10 mol% on the main plane in which the silver halide grains of the third emulsion relating to the present invention are parallel Is described below.

  The {100} tabular grains of the present invention have an average aspect ratio of 2 or more, in which 50-100%, preferably 70-100%, more preferably 90-100% of the total projected area has a {100} plane as the main plane. It consists of tabular grains. The particle thickness is 0.01 to 0.10 μm, preferably 0.02 to 0.08 μm, more preferably 0.03 to 0.07 μm, and the aspect ratio is 2 to 100, preferably 3 to 50, more preferably 5 to 30. The variation coefficient of the particle thickness (100% of “standard deviation of distribution / average particle thickness”, hereinafter referred to as COV.) Is 30% or less, preferably 25% or less, more preferably 20% or less. The smaller the COV., The higher the monodispersity of the particle thickness.

  The projected area diameter and thickness of the tabular grains are determined by taking a transmission electron microscope (TEM) photograph by a replica method and calculating the projected area diameter and thickness of each grain. In this case, the thickness is calculated from the length of the shadow of the replica. The measurement of COV. In the present invention is the result of measuring at least 600 particles.

  The composition of {100} tabular grains of the present invention is silver chloroiodobromide or silver iodobromide having a silver chloride content of less than 10 mol%. Further, other silver salts such as rhodan silver, silver sulfide, silver selenide, silver telluride, silver carbonate, silver phosphate, organic acid silver, etc. are contained as separate grains or as a part of silver halide grains. Also good.

  As a method for examining the halogen composition in the AgX crystal, the X-ray diffraction method is known. The X-ray diffraction method is described in detail in Basic Analytical Chemistry Course 24 “X-ray diffraction” and the like. Typically, the diffraction angle of the AgX (420) plane is determined by a powder method using Cu Kβ rays as a radiation source.

When the diffraction nucleus 2θ is obtained, the lattice constant a is obtained from the Bragg equation as follows.
2 d sinθ = λ
d = a / (h ² + k ² + l ² ) ^1/2
Here, 2θ is the diffraction angle of the (hkl) plane, λ is the wavelength of the X-ray, and d is the surface spacing of the (hkl) plane. Since the relationship between the halogen composition of silver halide solid solutions and the lattice constant a is already known (for example, described in THJames “The Theory of Photographic Process. 4thEd” Macmillian New York) The composition can be determined.

  The halogen composition structure of the {100} tabular grains of the present invention may be any. For example, grains having a (core / shell) 2 structure in which the halogen composition of the core and the shell are different, and grains having a multiple structure having a core and two or more shells can be mentioned. The composition of the core is preferably silver bromide, but is not limited thereto. The shell composition preferably has a higher silver iodide content than the core.

  The {100} tabular grains of the present invention preferably have an average silver iodide content of 2.3 mol or more and a surface average silver iodide content of 8 mol% or more. Further, the coefficient of variation of silver iodide content between grains is more preferably less than 20%. The surface silver iodide content can be measured using the XPS described above.

  When the {100} tabular grains of the present invention are classified by shape, the following six can be listed. (1) Particles whose main plane is a right-angled parallelogram. (2) Particles in which one or more, preferably 1 to 4 of the four corners of the right-angled parallelogram are missing non-equivalently. That is, [(the area of the largest missing portion) / the area of the smallest missing portion = particles having K1 of 2 to ∞)], (3) particles in which the four corners are equivalently missing (particles having K1 smaller than 2) (4) Particles in which 5 to 100%, preferably 20 to 100%, of the area of the side surface of the missing portion is the {111} plane. (5) Particles in which at least two opposite sides of the four sides constituting the main plane are curved outwardly convex, (6) one or more of the four corners of the right-angled parallelogram, preferably Is a particle in which 1 to 4 particles are missing in a right-angled parallelogram shape. These can be confirmed by observation using an electron microscope.

  The {100} plane ratio in the crystal habit of the surface of the {100} tabular grains of the present invention is 80% or more, preferably 90% or more, and this is statistically determined using an electron micrograph of the grains. Can be estimated. When the {100} tabular ratio of AgX grains in the emulsion is almost 100%, the above estimation can be confirmed by the following method. The method is described in Japanese Chemical Society paper 1984, No. 6, 942p. The amount of the benzothiocyanine dye is changed to a certain amount of the {100} tabular grains at 40 ° C. for 17 hours. The total surface area of all grains per unit emulsion (S) and the total area of {100} planes (S1) are determined by light absorption at 625 nm. Based on these values, the formula: S1 / S This is a method of calculating the {100} plane ratio by × 100 (%).

  The average equivalent sphere diameter of the {100} tabular grains of the present invention is preferably less than 0.35 μm. The estimation of the particle size can be obtained by measuring the projected area and thickness by the replica method.

  In the fourth emulsion relating to the present invention, the main plane in which the silver halide grains are parallel is the (111) plane or the (100) plane, the aspect ratio is 2 or more, and the plate contains at least 80 mol% or more of silver chloride. The shaped particles will be described below.

  In order to produce (111) grains with high silver chloride, special measures are required. A method for producing high silver chloride tabular grains using ammonia in US Pat. No. 4,399,215 to Wey may be used. A method for producing high silver chloride tabular grains using thiocyanate in US Pat. No. 5,061,617 of Maskasky may be used. In order to form grains having the (111) face as the outer surface in the high silver chloride grains shown below, a method of adding an additive (crystal phase controlling agent) at the grain formation may be used. It is shown below.

Patent Number Crystal Phase Control Agent Inventor US Pat. No. 4,400,463 Azaindenes + Muscasky
Thioether peptizer
US Pat. No. 4,783,398 2-4-Dithiazolidinone Gyoto etc. US Pat. No. 4,713,323 Aminopyrazolopyrimidine Muscasky US Pat. No. 4,983,508 Bispyridinium salt Ishiguro et al. US Pat. No. 5 No. 5,185,239 Triaminopyrimidine Muscasky US Pat. No. 5,178,997 7-azaindole compounds Muscasky US Pat. No. 5,178,998 Xanthine Muscasky JP-A 64-70741 Dye Nishikawa et al. Special Kaihei 3-212439 Aminothioether Ishiguro JP 4-283742 Thiourea derivative Ishiguro JP 4-335632 Triazolium salt Ishiguro JP 2-32 Bispyridinium salt Ishiguro etc. JP 8-227117 Monopyridinium salt Ozeki etc.

  Regarding the formation of (111) tabular grains, methods using various crystal phase controlling agents are known as described in the above table, but the compounds described in JP-A-2-32 (Compound Example 1) are known. To 42) are preferred, and the crystal phase control agents 1 to 29 described in JP-A-8-227117 are particularly preferred. However, the present invention is not limited to these.

  (111) tabular grains are obtained by forming two parallel twin planes. Since the formation of twin planes depends on temperature, dispersion medium (gelatin), halogen concentration, etc., these appropriate conditions must be set. When the crystal phase controlling agent is present during nucleation, the gelatin concentration is preferably 0.1% to 10%. The chloride concentration is 0.01 mol / L or more, preferably 0.03 mol / L or more.

  In order to monodisperse the particles, it is disclosed in JP-A-8-184931 that it is preferable not to use a crystal phase controlling agent in nucleation. When the crystal phase controlling agent is not used during nucleation, the gelatin concentration is 0.03% to 10%, preferably 0.05% to 1.0%. The chloride concentration is 0.001 mol / L to 1 mol / L, preferably 0.003 mol / L to 0.1 mol / L. The nucleation temperature may be any temperature from 2 ° C. to 90 ° C., but is preferably 5 ° C. to 80 ° C., particularly preferably 5 ° C. to 40 ° C.

  Tabular grain nuclei are formed in the initial nucleation stage, but immediately after the nucleation, the reaction vessel contains many nuclei other than tabular grains. Therefore, a technique for aging after nucleation, leaving only tabular grains and extinguishing others is required. When normal Ostwald ripening is performed, tabular grain nuclei also dissolve and disappear, so that the number of tabular grain nuclei decreases and the resulting tabular grain size increases. In order to prevent this, a crystal phase controlling agent is added. In particular, by using phthalated gelatin in combination, the effect of the crystal phase controlling agent can be enhanced and dissolution of tabular grains can be prevented. The pAg during aging is particularly important, and is preferably 60 to 130 mV with respect to the silver-silver chloride electrode.

  Next, the formed nucleus is grown in the presence of a crystal phase control agent by physical ripening and addition of a silver salt and a halide. In this case, the chloride concentration is 5 mol / L or less, preferably 0.05 to 1 mol / L. The temperature during grain growth can be selected in the range of 10 ° C to 90 ° C, but the range of 30 ° C to 80 ° C is preferable.

The total amount of the crystal phase controlling agent used is preferably 6 × 10 ⁻⁵ mol or more, particularly 3 × 10 ⁻⁴ mol to 6 × 10 ⁻² mol, per mol of silver halide in the finished emulsion. The timing of adding the crystal phase controlling agent may be any time from the nucleation of silver halide grains to physical ripening and grain growth. Formation of the (111) plane starts after the addition. The crystal phase controlling agent may be added to the reaction vessel in advance, but when forming small-sized tabular grains, it is preferable to add the crystal phase controlling agent to the reaction vessel together with the grain growth to increase the concentration.

When the amount of the dispersion medium used at the time of nucleation is insufficient for growth, it is necessary to compensate by addition. Preferably 10 g / L to 100 g / L of gelatin is present for growth. As supplementary gelatin, phthalated gelatin or trimellit gelatin is preferable.
The pH at the time of particle formation is arbitrary, but a neutral to acidic region is preferable.

  Next, (100) tabular grains will be described. The (100) tabular grains are tabular grains having the (100) plane as the main plane. The shape of the main plane is a right-angled parallelogram shape, or a 3-5 pentagon shape where one corner of the right-angled parallelogram is missing (the missing shape is the side that forms the corner with the corner as the apex. Or a 4-8 octagonal shape in which two or more and four or less missing portions exist.

  When a right-angled parallelogram shape that compensates for the missing portion is a supplementary quadrilateral, the adjacent side ratio (long side length / short side length) of the right-angled parallelogram and the supplemental quadrilateral is 1 to 6. , Preferably 1 to 4, more preferably 1 to 2.

  (100) As a method of forming tabular silver halide emulsion grains having a main plane, an aqueous silver salt solution and an aqueous halide salt solution are added and mixed in a dispersion medium such as an aqueous gelatin solution while stirring. At this time, for example, in JP-A-6-301129, 6-347929, 9-34045 and 9-96881, silver iodide or iodide ion, or silver bromide or bromide ion is present. And a method of introducing a crystal defect that imparts anisotropic growth such as a screw dislocation by causing distortion in the nucleus due to the difference in the size of the crystal lattice from silver chloride. When the screw dislocation is introduced, the formation of two-dimensional nuclei on the surface is not rate-determining under low supersaturation conditions, so that crystallization proceeds on this surface, and tabular grains are formed by introducing the screw dislocation. Is done. Here, the low supersaturation condition is preferably 35% or less, more preferably 2 to 20% at the time of critical addition. Although the crystal defect is not determined to be a screw dislocation, it is considered that there is a high possibility that the crystal defect is a screw dislocation because the direction in which the dislocation is introduced or the anisotropic growth property is imparted to the particles. In order to make the tabular grains thinner, it is disclosed in Japanese Patent Application Laid-Open Nos. Hei 8-122954 and Hei 9-189777 that the introduced dislocations are preferably retained.

  In addition, in JP-A-6-347928, imidazoles and 3,5-diaminotriazoles are used, and in JP-A-8-339044, polyvinyl alcohols are used to add a (100) surface formation accelerator. A method of forming (100) tabular grains is disclosed. However, the present invention is not limited to these.

  High silver chloride grains mean grains having a silver chloride content of 80 mol% or more, and preferably 95 mol% or more is silver chloride. The particles of the present invention preferably have a so-called core / shell structure comprising a core part and a shell part surrounding the core part. It is preferable that 90 mol% or more of the core portion is silver chloride. The core part may further comprise two or more parts having different halogen compositions. The shell portion is preferably 50% or less, particularly preferably 20% or less of the total particle volume. The shell portion is preferably silver iodochloride or silver iodobromochloride. The shell part preferably contains 0.5 mol% to 13 mol% of iodine, particularly preferably 1 mol% to 13 mol%. The content of silver iodide in all grains is preferably 5 mol% or less, particularly preferably 1 mol% or less.

  The silver bromide content is preferably higher in the shell part than in the core part. The silver bromide content is preferably 20 mol% or less, particularly preferably 5 mol% or less.

  The average grain size (equivalent volume equivalent sphere diameter) of silver halide grains is not particularly limited, but is preferably 0.1 μm to 0.8 μm, particularly preferably 0.1 μm to 0.6 μm.

  The tabular grain of silver halide preferably has a projected area diameter of 0.2 to 1.0 μm. Here, the projected area diameter of silver halide grains refers to the diameter of a circle having an area equal to the projected area of grains in an electron micrograph. The thickness is 0.2 μm or less, preferably 0.1 μm or less, particularly preferably 0.06 μm or less. In the present invention, 50% or more of the projected area of all the silver halide grains is 2 or more in average aspect ratio (diameter / thickness ratio), preferably 5 or more and 20 or less.

  In general, a tabular grain has a tabular shape having two parallel planes. Therefore, the “thickness” in the present invention is represented by a distance between two parallel planes constituting the tabular grain.

  The grain size distribution of the silver halide grains of the present invention may be polydispersed or monodispersed, but is more preferably monodispersed. In particular, the variation coefficient of the projected area diameter of tabular grains occupying 50% or more of the total projected area is preferably 20% or less. Ideally 0%.

  If the crystal phase controlling agent is present on the particle surface even after the formation of the particles, the adsorption of the sensitizing dye and the development are affected. Therefore, it is preferable to remove the crystal phase controlling agent after forming the particles. However, when the crystal phase controlling agent is removed, it is difficult for the high silver chloride (111) tabular grains to maintain the (111) plane under normal conditions. Therefore, it is preferable to maintain the particle form by substituting with a photographically useful compound such as a sensitizing dye. About this method, JP-A-9-80656, JP-A-9-106026, US Pat. No. 5,221,602, US Pat. No. 5,286,452, US Pat. No. 5,298,387, US Pat. No. 5,298,388, No. 5,176,992, and the like.

  Although the crystal phase controlling agent is desorbed from the grains by the above method, it is preferable to remove the desorbed crystal phase controlling agent from the emulsion by washing with water. The washing temperature can be such that gelatin normally used as a protective colloid does not coagulate. As the water washing method, various known techniques such as a flocculation method and an ultrafiltration method can be used. The washing temperature is preferably 40 ° C. or higher.

  In addition, the crystal phase controlling agent is more desorbed than the particles at a low pH. Therefore, the pH of the water washing step is preferably a low pH as long as the particles do not aggregate excessively.

  The silver halide emulsion may be further characterized by the layer in which the emulsion is used. In particular, when used in a blue sensitive layer, the silver halide grains contained in the silver halide emulsion preferably have a silver iodide content of 3 mol% or more, more preferably 5 mol% or more. Moreover, when using for a highly sensitive layer, a projected area diameter is preferably 1 μm or more, and more preferably 2 μm or more.

  Further, the silver halide emulsion may have the following characteristics in order to impart pressure resistance to the light-sensitive material. The silver halide grains contained in the silver halide emulsion are all grains in which no dislocation line is present when observed with a transmission electron microscope in a portion within 50%, preferably within 80% in area from the center of the main plane. Of 80% or more, more preferably 90% or more. The center of the main plane is the position of the center of gravity in the area of the main plane.

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 (3) and (4) are also preferred reduction sensitizers.

In the general formulas (3) and (4), 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 and the like. 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 type of metal compound, but may be used in combination of two or more.

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 (eg, AgNO ₃ ) or an alkali halide aqueous solution (eg, 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 grain of the present invention has at least one of chalcogen sensitization such as sulfur sensitization, selenium sensitization and tellurium sensitization, noble metal sensitization such as gold sensitization and palladium sensitization, and reduction sensitization. Can be applied at any step in the production process of the silver halide emulsion. 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.

  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, and potassium aurithiocyanate, US Pat. Nos. 2,642,361 (gold sulfide, gold selenide, etc.), 3,503,749 (water-soluble) Thiolate gold having a group), 5,049,484 (bis (methylhydantoinato) gold complex, etc.), 5,049,485 (mesoionic thiolate gold complex such as 1,4,5- Trimethyl-1,2,4-triazolium-3-thiolate gold complex), macrocyclic heterocyclic gold complexes of 5,252,455 and 5,391,727, 5,620,841, 5,700,631, 5,759,760, 5,759,761, 5,912,111, 5,912,112, 5,939,245, JP-A-1 -147 37, 8-69074, 8-69075, 9-269554, JP-B 45-29274, German Patent DD-264524A, 264525A, 265474A, 298321A, JP-A-2001-75214, Gold compounds described in 2001-75215, 2001-75216, 2001-75217, and 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, hexathiocanthion), mercapto compounds (eg, cysteine), polythionate , 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, 6-51415, 6-180478, 6-180478, 6-208186, 6-208184, 6-317867, 7-92599, Selenium compounds described in 7-98483, 7-140539 and the like 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 the tellurium sensitization, an unstable tellurium compound is used, and JP-A-4-224595, JP-A-4-271341, JP-A-4-3333043, JP-A-5-303157, JP-A-6-27573, JP-A-6-180478, The unstable tellurium compounds described in JP-A-6-208186, JP-A-6-208184, JP-A-6-317867, and JP-A-7-140539 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 of 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 ), oxyacid salts such as chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine Perhalogenates (eg potassium periodate), high valent metal salts (eg potassium hexacyanoferric acid) and thio There is a sulfonate.
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. The method can be selected from a method of applying reduction sensitization after using an oxidizing agent, a reverse method thereof, or a method of simultaneously coexisting both. 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; , 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 of adding the sensitizing dye 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-58-113928, and silver halide grains can be precipitated. Spectral sensitization can also be started by adding before the completion of 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.

Next, compounds used in the light-sensitive material of the present invention will be described.
First, the compound represented by the general formula (I) of the present invention will be described.
The compound of the present invention represented by the general formula (I) may be used at any time during the preparation of the emulsion and during the photosensitive material production process. For example, at the time of particle formation, desalting step, chemical sensitization, and before coating. Moreover, it can also add in several steps in these processes. The compound of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is increased or decreased may be dissolved at a higher or lower pH and added.

The compound of the present invention represented by the general formula (I) is preferably used in the emulsion layer, but may be added together with the emulsion layer to a protective layer or an intermediate layer and diffused during coating. The timing of addition of the compound of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol, more preferably 1 × 10 ⁻⁸ to 2 mol per mol of silver halide, regardless of before and after the sensitizing dye. X10 ^-3 mol in a silver halide emulsion layer.

  In general formula (I), the silver halide adsorbing group represented by X has at least one selected from the group consisting of N, S, P, Se and Te, and preferably has a silver ion ligand structure. Is. When k is 2 or more, the plurality of X may be the same or different. Examples of the silver ion ligand structure include the following.

Formula (X-1)
-G ₁ -Z ₁ -R ₁
In the formula, G ₁ is a divalent linking group, a divalent heterocyclic group, or a substituted or unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group, SO ₂ group and a divalent heterocyclic group. It represents a divalent group bonded to any of them. Z ₁ represents an S, Se, or Te atom. R ₁ represents a hydrogen ion or a counter ion necessary when it becomes a dissociated form of Z ₁ , a sodium ion, a potassium ion, a lithium ion, and an ammonium ion.

Formula (X-2a), (X-2b)

The general formulas (X-2a) and (X-2b) are ring-formed, and their forms are a 5- to 7-membered heterosaturated ring, heterounsaturated ring, and unsaturated carbocycle. Z _a represents O, N, S, Se or Te atom, n1 represents an integer of 0 to 3. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. When n1 is 2 or more, a plurality of Z _a may be the same or different.

Formula (X-3)
_{-R 3 - (Z 2) n2} -R 4
In the formula, Z ₂ represents an S, Se or Te atom, and n 2 represents an integer of 1 to 3. R ₃ is a divalent linking group, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, an alkenylene group, an alkynylene group, an arylene group, This represents a divalent group bonded to any of the SO ₂ groups. R ₄ represents an alkyl group, an aryl group or a heterocyclic group. When n2 is 2 or more, a plurality of Z ₂ may be the same or different.

Formula (X-4)

In the formula, R ₅ and R ₆ each independently represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

General formula (X-5a), (X-5b)

In the formula, Z ₃ represents an S, Se or Te atom, and E ₁ represents a hydrogen atom, NH ₂ , NHR ₁₀ , N (R ₁₀ ) ₂ , NHN (R ₁₀ ) ₂ , OR ₁₀ or SR ₁₀ . E ₂ is a divalent linking group and represents NH, NR ₁₀ , NHNR ₁₀ , O or S. R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R ₈ and R ₉ may be bonded to each other to form a ring. R ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.

General formula (X-6a), (X-6b)

In the formula, R ₁₁ is a divalent linking group and represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group or a divalent heterocyclic group. G ₂ and J each independently represent COOR ₁₂ , SO ₂ R ₁₂ , COR ₁₂ , SOR ₁₂ , CN, CHO or NO ₂ . R ₁₂ represents an alkyl group, an alkenyl group or an aryl group.

General formula (X-1) is demonstrated in detail. In the formula, the linking group represented by G ₁ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, 3 -Oxapentylene, 2-hydroxytrimethylene), substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene, cyclopentylene, cyclohexylene), substituted or unsubstituted having 2 to 20 carbon atoms An alkenylene group (for example, ethene, 2-butenylene), an alkynylene group having 2 to 10 carbon atoms (for example, ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (for example, unsubstituted p-phenylene, unsubstituted 2, 5-naphthylene).

In the formula, as the SO ₂ group represented by G ₁ , in addition to the —SO ₂ — group, a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms, or a substitution having 3 to 6 carbon atoms or unsubstituted cycloalkylene group or -SO ₂ bound to an alkenylene group having 2 to 10 carbon atoms - group.

Further, the divalent linking group represented by G ₁ includes a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, alkenylene group, alkynylene group, arylene group, or SO ₂ group. Bonded divalent groups, or those in which the heterocyclic part of these groups is benzo-fused or naphtho-fused (for example, 2,3-tetrazolediyl, 1,3-triazolediyl, 1,2-imidazolediyl, 3, 5-oxadiazolediyl, 2,4-thiazoldiyl, 1,5-benzimidazolediyl, 2,5-benzothiazolediyl, 2,5-benzoxazolediyl, 2,5-pyrimidinediyl, 3-phenyl-2 , 5-tetrazolediyl, 2,5-pyridinediyl, 2,4-furandyl, 1,3-piperidinediyl, 2,4-morpholinediyl). I can get lost.
In the above formula, G ₁ may have a substituent as much as possible. The substituents are shown below, and these substituents are referred to herein as substituent Y.

  Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (for example, methyl, ethyl, isopropyl, n-propyl, t-butyl), an alkenyl group (for example, allyl, 2-butenyl), Alkynyl groups (eg propargyl), aralkyl groups (eg benzyl), aryl groups (eg phenyl, naphthyl, 4-methylphenyl), heterocyclic groups (eg pyridyl, furyl, imidazolyl, piperidinyl, morpholyl), alkoxy groups (eg methoxy, Ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy), aryloxy groups (eg phenoxy, 2-naphthyloxy), amino groups (eg unsubstituted amino, dimethylamino, diethylamino, dipropylamino, dibutylamino) Ethylamino, anilino), acylamino groups (eg acetylamino, benzoylamino), ureido groups (eg unsubstituted ureido, N-methylureido), urethane groups (eg methoxycarbonylamino, phenoxycarbonylamino), sulfonylamino groups (eg methyl) Sulfonylamino, phenylsulfonylamino), sulfamoyl groups (eg unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), carbamoyl groups (eg unsubstituted carbamoyl, N, N-diethylcarbamoyl, N- Phenylcarbamoyl), sulfonyl groups (eg mesyl, tosyl), sulfinyl groups (eg methylsulfinyl, phenylsulfinyl), alkyloxycarbonyl groups (eg methoxycarbonyl, Toxicarbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl), acyl groups (eg acetyl, benzoyl, formyl, pivaloyl), acyloxy groups (eg acetoxy, benzoyloxy), phosphoramide groups (eg N, N-diethylphosphoric acid) Amide), cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, phosphono group, nitro group, ammonio group, phosphonio group, hydrazino group, and thiazolino group. Moreover, when there are two or more substituents, they may be the same or different, and the substituents may further have a substituent.

The preferable example of general formula (X-1) is shown.
In general formula (X-1), G ₁ is bonded to a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a substituted or unsubstituted alkylene group or an arylene group, or benzo-fused or naphtho-fused. And heterocyclic groups that form 5- to 7-membered rings. Examples of Z ₁ include S and Se, and examples of R ₁ include a hydrogen atom, a sodium ion, and a potassium ion.

More preferably, G ₁ is a heterocyclic group which forms a 5- or 6-membered ring bonded to or substituted with a substituted or unsubstituted arylene group having 6 to 8 carbon atoms, most preferably arylene. It is a heterocyclic group which forms a 5- or 6-membered ring bonded to a group or benzo-fused. More preferred Z ₁ is S, and R ₁ is a hydrogen atom or a sodium ion.

General formulas (X-2a) and (X-2b) will be described in detail.
In the formula, as the alkyl group, alkenyl group, and alkynyl group represented by R ₂ , a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, n-butoxypropyl, methoxymethyl), C3-C6 substituted or unsubstituted cyclic alkyl group (for example, cyclopropyl, cyclopentyl, cyclohexyl), C2-C10 alkenyl group (for example, allyl, 2-butenyl, 3-pentenyl), C2-C10 Alkynyl group (for example, propargyl, 3-pentynyl), aralkyl group having 6 to 12 carbon atoms For example, benzyl) and the like. Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 12 carbon atoms (for example, unsubstituted phenyl and 4-methylphenyl).
R ₂ may further have a substituent Y or the like.

Preferred examples of general formulas (X-2a) and (X-2b) are shown.
Wherein preferably R ₂ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, in Z _a is O, N or S N1 is an integer of 1 to 3.
More preferably, R ₂ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, Z _a is N or S, and n 1 is 2 or 3.

Next, general formula (X-3) will be described in detail.
In the formula, the linking group represented by R ₃ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, isopropylene, tetramethylene, hexamethylene, 3-oxapentylene, 2-hydroxytrimethylene), substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene, cyclopentynylene, cyclohexylene), substituted or unsubstituted having 2 to 20 carbon atoms A substituted alkenylene group (for example, ethene, 2-butenylene), an alkynylene group having 2 to 10 carbon atoms (for example, ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (for example, unsubstituted p-phenylene, unsubstituted 2) , 5-naphthylene), and examples of the heterocyclic group include substituted or unsubstituted heterocyclic groups, and And an alkylene group, alkenylene group, arylene group, or a heterocyclic group further bonded (for example, 2,5-pyridinediyl, 3-phenyl-2,5-pyridinediyl, 1,3-piperidinediyl, 2,4 -Morpholinediyl).

In the formula, the alkyl group represented by R ₄ is a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, t -Butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), carbon Examples thereof include substituted or unsubstituted cyclic alkyl groups having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl), and examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 12 carbon atoms (for example, unsubstituted phenyl, 2-methylphenyl).

Examples of the heterocyclic group include unsubstituted or alkyl groups, alkenyl groups, aryl groups, and those further substituted with a heterocyclic group (for example, pyridyl, 3-phenylpyridyl, piperidyl, morpholyl).
R ₄ may further have a substituent Y or the like.

The preferable example of general formula (X-3) is shown.
In the formula, R ₃ is preferably a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and R ₄ is a substituted or unsubstituted C 1-6 carbon atom or An unsubstituted alkyl group, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, Z ₂ is S or Se, and n 2 is 1 to 2.
More preferably, R ₃ is an alkylene group having 1 to ₄ carbon atoms, R ₄ is an alkyl group having 1 to ₄ carbon atoms, Z ₂ is S, and n 2 is 1.

Next, general formula (X-4) will be described in detail.
In the formula, the alkyl group and alkenyl group represented by R ₅ and R ₆ include a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl). N-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n -Butoxymethyl, n-butoxypropyl, methoxymethyl), substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl group having 2 to 10 carbon atoms (for example, allyl, 2 -Butenyl, 3-pentenyl). Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 12 carbon atoms (for example, unsubstituted phenyl and 4-methylphenyl), and examples of the heterocyclic group include unsubstituted or alkylene groups, alkenylene groups, arylene groups, Or what further substituted the heterocyclic group (for example, pyridyl, 3-phenylpyridyl, furyl, piperidyl, morpholyl) is mentioned.
In the above formula, R ₅ and R ₆ may further have a substituent Y or the like.

The preferable example of general formula (X-4) is shown.
In the formula, R ₅ and R ₆ are preferably a substituted or unsubstituted alkyl group having 1 to ₆ carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms.
More preferably, R ₅ and R ₆ are aryl groups having 6 to 8 carbon atoms.

Next, the general formulas (X-5a) and (X-5b) will be described in detail.
In the formula, groups represented by E ₁ include NH ₂ , NHCH ₃ , NHC ₂ H ₅ , NHPh, N (CH ₃ ) ₂ , N (Ph) ₂ , NHNHC ₃ H ₇ , NHNHPh, OC ₄ H ₉ , OPh, SCH ₃ , etc. can be mentioned, and E ₂ includes NH, NCH ₃ , NC ₂ H ₅ , NPh, NHNC ₃ H ₇ , NHNPh, etc. (where Ph = phenyl group (hereinafter the same). )).

In general formulas (X-5a) and (X-5b), the alkyl group and alkenyl group represented by R ₇ , R ₈ and R ₉ are substituted or unsubstituted straight chain having 1 to 10 carbon atoms, or Branched alkyl groups (eg, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, hydroxymethyl, 2- Hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl) Cyclohexyl), an alkenyl group having 2 to 10 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl) Le). Examples of the aryl group include substituted or unsubstituted aryl groups having 6 to 12 carbon atoms (for example, unsubstituted phenyl and 4-methylphenyl). Examples of the heterocyclic group include unsubstituted or alkylene groups, alkenylene groups, and arylene groups. Or further substituted with a heterocyclic group (for example, pyridyl, 3-phenylpyridyl, furyl, piperidyl, morpholyl).
R ₇ , R ₈ and R ₉ may further have a substituent Y and the like.

Preferable examples of the general formulas (X-5a) and (X-5b) are shown.
In the formula, preferably E ₁ is an alkyl-substituted or unsubstituted amino group or alkoxy group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R ₉ have 1 to A substituted or unsubstituted alkyl group having 6 or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, and Z ₃ is S or Se.

More preferably, E ₁ is an alkyl-substituted or unsubstituted amino group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R ₉ are substituted or substituted with 1 to 4 carbon atoms. An unsubstituted alkyl group, Z ₃ is S.

Next, general formulas (X-6a) and (X-6b) will be described in detail.
In the formula, groups represented by G ₂ and J include COOCH ₃ , COOC ₃ H ₇ , COOC ₆ H ₁₃ , COOPh, SO ₂ CH ₃ , SO ₂ C ₄ H ₉ , COC ₂ H ₅ , COPh, and SOCH _3. , SOPh, CN, CHO, NO _{2 and the} like.

In the formula, the linking group represented by R ₁₁ is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, 3 -Oxapentylene, 2-hydroxytrimethylene), substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (for example, cyclopropylene, cyclopentylene, cyclohexylene), substituted or unsubstituted having 2 to 20 carbon atoms An alkenylene group (for example, ethene, 2-butenylene), an alkynylene group having 2 to 10 carbon atoms (for example, ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (for example, unsubstituted p-phenylene, unsubstituted 2, 5-naphthylene).

Furthermore, the divalent linking group represented by R ₁₁ includes a divalent heterocyclic group, or a divalent heterocyclic group and any one of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and an SO ₂ group. And a bonded divalent group (for example, 2,5-pyridinediyl, 3-phenyl-2,5-pyridinediyl, 2,4-furandyl, 1,3-piperidinediyl, 2,4-morpholinediyl). .
In the formula, R ₁₁ may further have a substituent Y or the like.

Preferred examples of the general formulas (X-6a) and (X-6b) are shown.
In the formula, preferably G ₂ and J are carboxylic acid esters or carbonyls having 2 to 6 carbon atoms, and R ₁₁ is a substituted or unsubstituted alkylene group having 1 to 6 carbon atoms or a substitution having 6 to 10 carbon atoms. Or it is an unsubstituted arylene group.

More preferably, G ₂ and J are carboxylic acid esters having 2 to 4 carbon atoms, and R ₁₁ is a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms or a substituted or unsubstituted carbon group having 6 to 8 carbon atoms. An arylene group.

  The preferred general formula of the silver halide adsorbing group represented by X is (X-1)> (X-2a)> (X-2b)> (X-3)> (X-5a)> (X- 5b)> (X-4)> (X-6a)> (X-6b).

Next, the light absorbing group represented by X in the general formula (I) will be described in detail.
In the general formula (I), examples of the light absorbing group represented by X include the following.

Formula (X-7)

In the formula, Z ₄ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring, and L ₂ , L ₃ , L ₄ and L ₅ represent a methine group. p1 represents 0 or 1, and n3 represents an integer of 0 to 3. M ₁ represents a charge balanced counter ion, and m 2 represents an integer of 0 to 10 necessary for neutralizing the charge of the molecule. The nitrogen-containing heterocyclic ring formed by Z ₄ may be condensed with an unsaturated carbocyclic ring such as a benzene ring.

In the formula, the 5- or 6-membered nitrogen-containing heterocyclic ring represented by Z ₄ includes thiazolidine nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus, selenazole nucleus, benzoselenazole. Nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline Examples include a nucleus, a 1-isoquinoline nucleus, a 3-isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus, and a pyrimidine nucleus.
The 5- or 6-membered nitrogen-containing heterocycle represented by Z ₄ may have the aforementioned substituent Y.

In the formula, L ₂ , L ₃ , L ₄ and L ₅ each represent an independent methine group. The methine group represented by L ₂ , L ₃ , L ₄ and L ₅ may have a substituent. Examples of the substituent include a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms (for example, methyl , Ethyl, 2-carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (eg, phenyl, o-carboxyphenyl), a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms (eg, N, N-diethyl barbituric acid obtained by removing one hydrogen atom to form a monovalent group), halogen atom (eg, chlorine, bromine, fluorine, iodine), C 1-15 alkoxy group (eg, methoxy, ethoxy) , An alkylthio group having 1 to 15 carbon atoms (for example, methylthio, ethylthio), an arylthio group having 6 to 20 carbon atoms (for example, phenylthio), an amino group having 0 to 15 carbon atoms (for example, N, N -Diphenylamino, N-methyl-N-phenylamino, N-methylpiperazino) and the like.
Moreover, you may form a ring with another methine group. Alternatively, a ring can be formed with other moieties.

Where M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the light absorbing group. Typical cations include inorganic ions such as hydrogen ions (H ⁺ ) and alkali metal ions (eg, sodium ions, potassium ions, lithium ions), ammonium ions (eg, ammonium ions, tetraalkylammonium ions, pyridinium ions). Organic cation such as ethylpyridinium ion). The anion may be either an inorganic anion or an organic anion, such as a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p -Chlorobenzenesulfonic acid ion), aryl disulfonic acid ion (for example, 1,3-benzenedisulfonic acid ion, 1,5-naphthalenedisulfonic acid ion, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfuric acid ion) Ions), sulfate ions, thiocyanate ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, and trifluoromethanesulfonate ions. Further, an ionic polymer or a light absorbing group having a reverse charge may be used.

In the present invention, for example, the sulfo group is represented as SO ₃ ⁻ and the carboxy group is represented as CO ₂ ^— , but when the counter ion is a hydrogen ion, they can be represented as SO ₃ H and CO ₂ H, respectively.
In the formula, m2 represents a number necessary for balancing the electric charge, and is 0 when a salt is formed in the molecule.

The preferable example of general formula (X-7) is shown.
In general formula (X-7), Z ₄ is a benzoxazole nucleus, benzothiazole nucleus, benzimidazole nucleus or quinoline nucleus, and L ₂ , L ₃ , L ₄ and L ₅ are unsubstituted methine groups. , P1 is 0 and n3 is 1 or 2.
More preferably, Z ₄ is a benzoxazole nucleus or a benzothiazole nucleus, and n 3 is 1. Particularly preferred Z ₄ is a benzothiazole nucleus.
In general formula (I), k is preferably 0 or 1, more preferably 1.

Specific examples of the X group used in the present invention are shown below, but the compound used in the present invention is not limited to this.

Next, the linking group represented by L in the general formula (I) will be described in detail.
In the general formula (I), the linking group represented by L is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, Hexamethylene, 3-oxapentylene, 2-hydroxytrimethylene), a substituted or unsubstituted cyclic alkylene group having 3 to 18 carbon atoms (eg, cyclopropylene, cyclopentylene, cyclohexylene), 2 to 20 carbon atoms Substituted or unsubstituted alkenylene groups (for example, ethene, 2-butenylene), alkynylene groups having 2 to 10 carbon atoms (for example, ethyne), substituted or unsubstituted arylene groups having 6 to 20 carbon atoms (for example, unsubstituted) p-phenylene, unsubstituted 2,5-naphthylene), heterocyclic linking groups (for example, 2,6-pyridinediyl), Bonyl group, thiocarbonyl group, imide group, sulfonyl group, divalent sulfonic acid group, ester group, thioester group, divalent amide group, ether group, thioether group, divalent amino group, divalent ureido group, Examples thereof include a divalent thioureido group and a thiosulfonyl group. These linking groups may be linked to each other to form a new linking group. When m is 2 or more, the plurality of L may be the same or different.
L may further have the aforementioned substituent Y or the like.

  Preferred examples of the linking group L include an alkylene group having 1 to 10 carbon atoms linked to an unsubstituted alkylene group having 1 to 10 carbon atoms and an amino group, an amide group, a thioether group, a ureido group, or a sulfonyl group. Includes an alkylene group having 1 to 6 carbon atoms linked to an unsubstituted alkylene group having 1 to 6 carbon atoms and an amino group, an amide group or a thioether group.

  In general formula (I), m is preferably 0 or 1, more preferably 1.

Next, the electron donating group A will be described in detail.
A reaction process in which the AB part undergoes oxidation and fragmentation to generate electrons to generate radicals A., and radical A. to undergo oxidation to generate electrons to increase sensitivity is shown below.

  Since A is an electron donating group, the substituent on the aromatic group is preferably selected so that A has an excess of electrons in any structure. For example, when the aromatic ring has no electron excess, an electron donating group is introduced, and conversely, when it is extremely electron rich, such as anthracene, an electron withdrawing group is introduced to reduce the oxidation potential. It is preferable to adjust.

  Preferred A groups are those having the following general formula:

General formula (A-1), (A-2), (A-3)

In general formulas (A-1) and (A-2), R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkylene group, or an arylene group, and R ₁₄ represents Alkyl group, COOH, halogen, N (R ₁₅ ) ₂ , OR ₁₅ , SR ₁₅ , CHO, COR ₁₅ , COOR ₁₅ , CONHR ₁₅ , CON (R ₁₅ ) ₂ , SO ₃ R ₁₅ , SO ₂ NHR ₁₅ , SO ₂ NR ₁₅ , SO ₂ R ₁₅ , SOR ₁₅ , CSR ₁₅ are represented. Ar ₁ represents an arylene group or a heterocyclic linking group. R ₁₂ and R ₁₃ and R ₁₂ and Ar ₁ may be bonded to form a ring. Q ₂ represents O, S, Se or Te, m 3 and m 4 represent 0 or 1, and n 4 represents an integer of 1 to 3. L ₂ represents N—R (where R represents a substituted or unsubstituted alkyl group), N—Ar, O, S, Se. The cyclic form formed by combining R ₁₂ and R ₁₃ , R ₁₂ and Ar ₁ represents a 5- to 7-membered heterocyclic group or an unsaturated ring. R ₁₅ represents a hydrogen atom, an alkyl group or an aryl group. The cyclic form of the general formula (A-3) represents a substituted or unsubstituted 5- to 7-membered unsaturated ring or heterocyclic group.

General formulas (A-1), (A-2) and (A-3) will be described in detail.
In the formula, the alkyl group represented by R ₁₂ and R ₁₃ is a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n- Butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl ), A substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl), and the aryl group includes a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, Substituted phenyl, 2-methylphenyl).

  Examples of the alkylene group include a substituted or unsubstituted linear or branched alkylene group having 1 to 10 carbon atoms (for example, methylene, ethylene, trimethylene, tetramethylene, methoxyethylene), and an arylene group having 6 to 6 carbon atoms. And 12 substituted or unsubstituted arylene groups (for example, unsubstituted phenylene, 2-methylphenylene, naphthylene).

In general formulas (A-1) and (A-2), the group represented by R ₁₄ is an alkyl group (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, 2-pentyl, n-hexyl). , N-octyl, 2-ethylhexyl, 2-hydroxyethyl, n-butoxymethyl), COOH group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), OH, N (CH ₃ ) ₂ , NPh ₂ , OCH _{3, OPh, SCH 3, SPh} , CHO, COCH 3, COPh, COOC 4 H 9, COOCH 3, CONHC 2 H 5, CON (CH 3) 2, SO 3 CH 3, SO 3 C 3 H 7, SO 2 NHCH ₃ , SO ₂ N (CH ₃ ) ₂ , SO ₂ C ₂ H ₅ , SOCH ₃ , CSPh, CSCH ₃ may be mentioned.

Ar ₁ represented by the general formulas (A-1) and (A-2) is a substituted or unsubstituted arylene group having 6 to 12 carbon atoms (for example, phenylene, 2-methylphenylene, naphthylene), substituted or Examples thereof include a divalent or trivalent group obtained by removing one or two hydrogen atoms from an unsubstituted heterocyclic group (eg, pyridyl, 3-phenylpyridyl, piperidyl, morpholyl).

L ₂ represented by the general formula (A-1) includes NH, NCH ₃ , NC ₄ H ₉ , NC ₃ H ₇ (i), NPh, NPh-CH ₃ , O, S, Se, Te. It is done.

  Examples of the cyclic form of the general formula (A-3) include an unsaturated 5- to 7-membered carbocyclic ring and a saturated or unsaturated 5- to 7-membered heterocyclic ring (for example, furyl, piperidyl, morpholyl).

R ₁₂ , R ₁₃ , R ₁₄ , Ar ₁ , L _{2 in} the general formulas (A-1) and (A-2), and the substituent Y described above on the ring in the general formula (A-3) May further be included.

Preferred examples of general formulas (A-1), (A-2) and (A-3) are shown.
In general formulas (A-1) and (A-2), R ₁₂ and R ₁₃ are preferably a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an alkylene group, or a substituted or unsubstituted group having 6 to 10 carbon atoms. A substituted aryl group, wherein R ₁₄ is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, an amino group mono- or disubstituted with an alkyl group having 1 to 4 carbon atoms, a carboxylic acid, a halogen, or a carbon number 1 to 4 carboxylic acid ester, Ar ₁ is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, Q ₂ is O, S or Se, m 3 and m 4 are 0 or 1, n4 is 1 to 3, L ₂ is an alkyl substituted amino group of 0-3 carbon atoms.

In general formula (A-3), a preferable cyclic form is a 5- to 7-membered saturated or unsaturated heterocyclic ring.
In general formulas (A-1) and (A-2), R ₁₂ and R ₁₃ are more preferably a substituted or unsubstituted alkyl group or alkylene group having 1 to 4 carbon atoms, and R ₁₄ is 1 carbon atom. An unsubstituted alkyl group having ˜4, a monoamino-substituted or diamino-substituted alkyl group having 1 to 4 carbon atoms, Ar ₁ is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, and Q ₂ is O or a S, m3 and m4 are 0, n4 is 1, an amino group which L ₂ is alkyl substituted 0-3 carbon atoms.

In formula (A-3), a more preferable cyclic form is a 5- to 6-membered heterocyclic ring.
The portion where the A group is bonded to the L group (or the X group when m = 0) is Ar ₁ and R ₁₂ or R ₁₃ .

Specific examples of the A group used in the present invention are listed below, but the compound used in the present invention is not limited to this.

Next, the B group will be described in detail.
When B is a hydrogen atom, it is oxidized and then deprotonated by an intramolecular base to generate a radical A.

  Preferred B groups are those having a hydrogen atom and the following general formula:

General formula (B-1), (B-2), (B-3)

In the general formulas (B-1), (B-2) and (B-3), W represents Si, Sn or Ge, R ₁₆ each independently represents an alkyl group, and Ar ₂ each independently Represents an aryl group.
General formula (B-2) and (B-3) can be combined with the adsorption group X.

General formulas (B-1), (B-2), and (B-3) will be described in detail. In the formula, the alkyl group represented by R ₁₆ is a substituted or unsubstituted linear or branched alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, (t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, n-butoxyethyl, methoxymethyl), C 6-12 substitution Or an unsubstituted aryl group (for example, phenyl, 2-methylphenyl) is mentioned.

R ₁₆ and Ar ₂ in the general formulas (B-2) and (B-3) may further have the above-described substituent Y and the like.

Preferred examples of general formulas (B-1), (B-2) and (B-3) are shown below.
In general formulas (B-2) and (B-3), preferably, R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and Ar ₂ is a substituted or unsubstituted group having 6 to 10 carbon atoms. And W is Si or Sn.

In general formulas (B-2) and (B-3), more preferably, R ₁₆ is a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, and Ar ₂ is a substituted or unsubstituted group having 6 to 8 carbon atoms. A substituted aryl group, W is Si;
Of the general formulas (B-1), (B-2) and (B-3), the most preferable is COO ^{− in} the general formula (B-1) and Si— (R ₁₆ ) in the general formula (B-2). ₃ ).

In general formula (I), preferred n is 1.
In general formula (I), when n is 2, two (AB) may be the same or different.
Although the example of AB group used by this invention is given to the following, this invention is not limited to this.

  Examples of the counter ion necessary for the charge balance of the compound AB include sodium ion, potassium ion, triethylammonium ion, diisopropylammonium ion, tetrabutylammonium ion, and tetramethylguanidinium ion.

A preferable oxidation potential of AB is 0 to 1.5 V, more preferably 0 to 1.0 V, and still more preferably 0.3 to 1.0 V.
A preferable oxidation potential of the radical A · (E2) resulting from the bond cleavage reaction is −0.6 to −2.5 V, more preferably −0.9 to −2 V, and further preferably −0.9 to −−. The range is 1.6V.

The method for measuring the oxidation potential is as follows.
E1 can be performed by a cyclic voltammetry method. Electron donor A is dissolved in a solution of 80% / 20% water (volume%) containing acetonitrile / 0.1M or lithium chlorate. A glassy carbon disk is used for the working electrode, a platinum wire is used for the counter electrode, and a saturated calomel electrode (SCE) is used for the reference electrode. Measure at 25 ° C. with a potential scan rate of 0.1 V / sec. The oxidation potential versus SCE is taken at the peak potential of the cyclic voltammetry wave. The E1 values of these AB compounds are described in EP 93,731A1.

  Radical oxidation potential measurements are made by excessive electrochemical and pulse radiolysis methods. These are described in J. Am. Chem. Soc. 1988, 110, 132, 1974, 96, 1287, 1974, 96, 1295.

Specific examples of the compound represented by the general formula (I) are shown below, but the compound used in the present invention is not limited thereto.

Next, the photographic useful group releasing compound represented by the general formula (II) will be described in detail.
Formula (II)
COUP1-D1
(In the formula, COUP1 represents a coupler residue that releases D1 by a coupling reaction with an oxidized developer and forms a water-soluble or alkali-soluble compound. D1 is a photographic property linked at the coupling position of COUP1. Represents a useful group or a precursor thereof).

The photographically useful group releasing compound represented by the general formula (II) will be described.
Specifically, the photographic useful group releasing compound represented by the general formula (II) is represented by the following general formula (IIa) or (IIb).
Formula (IIa) COUP1- (TIME) _m -PUG
Formula (IIb) COUP1- (TIME) _i -RED-PUG
In the formula, COUP1 is a coupler residue that releases (TIME) _m -PUG or (TIME) _i -RED-PUG and generates a water-soluble or alkali-soluble compound by a coupling reaction with an oxidized form of a developing agent. TIME represents a timing group that cleaves PUG or RED-PUG after leaving from COUP1 by a coupling reaction, and RED represents a group that cleaves PUG by reacting with oxidized developer after leaving from COUP1 or TIME. PUG represents a photographically useful group, m represents an integer of 0 to 2, and i represents 0 or 1. When m is 2, two TIMEs are the same or different.

  When COUP1 represents a yellow coupler residue, for example, pivaloylacetanilide type, benzoylacetanilide type, malon diester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type, benzoxazolyl Examples thereof include coupler residues of lucacetamido type, benzimidazolyl acetamide type, quinazolin-4-one-2-ylacetanilide type or cycloalkanoyl acetamide type.

  When COUP1 represents a magenta coupler residue, for example, 5-pyrazolone type, pyrazolo [1,5-a] benzimidazole type, pyrazolo [1,5-b] [1,2,4] triazole type, pyrazolo [5, 1-c] [1,2,4] triazole type, imidazo [1,2-b] pyrazole type, pyrrolo [1,2-b] [1,2,4] triazole type, pyrazolo [1,5-b And pyrazole type or cyanoacetophenone type coupler residues.

  When COUP1 represents a cyan coupler residue, for example, phenol type, naphthol type, pyrrolo [1,2-b] [1,2,4] triazole type, pyrrolo [2,1-c] [1,2,4] Triazole type or 2,4-diphenylimidazole type may be mentioned.

  Further, COUP1 may be a coupler residue that does not substantially leave a color image. Examples of this type of coupler residue include coupler residues such as indanone type and acetophenone type.

Preferred examples of COUP1 include the following formulas (Cp-1), (Cp-2), (Cp-3), (Cp-4), (Cp-5), (Cp-6), (Cp-7), ( Cp-8), a coupler residue represented by (Cp-9), (Cp-10), (Cp-11) or (Cp-12). These couplers are preferable because of their high coupling speed.

In the above formula, the free bond derived from the coupling position represents the bonding position of the coupling-off group.
In the above formula, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ , R ₅₅ , R ₅₆ , R ₅₇ , R ₅₈ , R ₅₉ , R ₆₀ , R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ and R _The number of carbon atoms of ₆₆ is preferably 10 or less.

The coupler residue represented by COUP1 preferably has at least one R ₇₁ OCO— group, HOSO ₂ — group, HO— group, R ₇₂ NHCO— group or R ₇₂ NHSO ₂ — group as a substituent. That is, in formula (Cp-1), at least one of R ₅₁ or R ₅₂ is in formula (Cp-2), and at least one of R ₅₁ , R ₅₂ or R ₅₃ is in formula (Cp-3). In which at least one of R ₅₄ or R ₅₅ is at least one of R ₅₆ or R _{57 in} the formulas (Cp-4) and (Cp-5), and R ₅₈ or R _{59 in the} formula (Cp-6). At least one of R ₅₉ or R ₆₀ in formula (Cp-7), and at least one of R ₆₁ or R ₆₂ in formula (Cp-8) is represented by formula (Cp-9) And in (Cp-10) at least one R ₆₃ , in formulas (Cp-11) and (Cp-12) at least one of R ₆₄ , R ₆₅ or R ₆₆ is an R ₇₁ OCO— group, HOSO ₂ - group, HO- group, R ₇₂ NHCO- group, or R ₇₂ N SO ₂ - it is preferred to have at least one substituent group. R ₇₁ represents a hydrogen atom, an alkyl group having 6 or less carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, t-butyl) or a phenyl group, R ₇₂ represents a group represented by R ₇₁ , R ₇₄ CO -Group, R ₇₄ N (R ₇₅ ) CO- group, R ₇₃ SO ₂ -group or R ₇₄ N (R ₇₅ ) SO ₂ -group, wherein R ₇₃ is an alkyl group having 6 or less carbon atoms (for example, methyl, Ethyl, propyl, isopropyl, butyl, t-butyl) or a phenyl group, R ₇₄ and R ₇₅ each represent a group represented by R ₇₁ , and these may further have a substituent.

Hereinafter, R _{51 to} R ₆₆ , a, b, d, e, and f will be described in detail. In the following, R ₄₁ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, R ₄₂ represents an aryl group or a heterocyclic group, R ₄₃ , R ₄₄ and R ₄₅ represent a hydrogen atom, an aliphatic hydrocarbon group, Represents an aryl group or a heterocyclic group.

R ₅₁ represents the same meaning as R ₄₁ . a represents 0 or 1; R ₅₂ and R ₅₃ each have the same meaning as R ₄₃ . In the formula (Cp-2), when R ₅₂ is not a hydrogen atom, R ₅₂ and R ₅₁ may combine to form a 5- to 7-membered ring. b represents 0 or 1;

R ₅₄ represents a group having the same meaning as _{R 41, R 41 CON (R} 43) - _{group, R 41 SO 2 N (R} 43) - _{group, R 41 N (R 43)} - radical, R ₄₁ S- radical, R _{It represents a 43} O-group or a R ₄₅ N (R ₄₃ ) CON (R ₄₄ )-group. R ₅₅ represents a group having the same meaning as R ₄₁ .

R ₅₆ and R ₅₇ are each independently a group having the same meaning as the R ₄₃ group, R ₄₁ S-group, R ₄₃ O-group, R ₄₁ CON (R ₄₃ ) -group, R ₄₁ OCON (R ₄₃ ) -group Or represents an R ₄₁ SO ₂ N (R ₄₃ ) — group.

R ₅₈ represents a group having the same meaning as R ₄₃ . And R ₅₉ groups of the same meaning as _{R 41, R 41 CON (R} 43) - _{group, R 41 OCON (R 43)} - _{group, R 41 SO 2 N (R} 43) - group, R ₄₃ N (R ₄₄₎ CON (R ₄₅ ) — group, R ₄₁ O— group, R ₄₁ S— group, halogen atom or R ₄₁ N (R ₄₃ ) — group. d represents 0 to 3; When d is plural, plural R _59s represent the same substituent or different substituents.
R ₆₀ represents a group having the same meaning as R ₄₃ .

R ₆₁ represents a group having the same meaning as R _43, R ₄₃ OSO ₂ - _{group, R 43 N (R 44)} SO 2 - group, R ₄₃ OCO- _{group, R 43 N (R 44)} CO- group, a cyano group, R ₄₁ SO ₂ N (R ₄₃ ) CO— group, R ₄₃ CON (R ₄₄ ) CO— group, R ₄₃ N (R ₄₄ ) SO ₂ N (R ₄₅ ) CO— group, R ₄₃ N (R ₄₄ ) CON (R ₄₅ ) CO— group, R ₄₃ N (R ₄₄ ) SO ₂ N (R ₄₅ ) SO ₂ — group, R ₄₃ N (R ₄₄ ) CON (R ₄₅ ) SO ₂ — group.

R ₆₂ is a group of the same meaning as R _41, R ₄₁ CONH- group, R ₄₁ OCONH- group, R ₄₁ SO ₂ NH- _{group, R 43 N (R 44)} CONH- _{group, R 43 N (R 44)} SO _{2 represents an} NH— group, an R ₄₃ O— group, an R ₄₁ S— group, a halogen atom or an R ₄₁ N (R ₄₃ ) — group. In the formula (Cp-8), e represents an integer of 0 to 4, and when e is 2 or more, the plurality of R ₆₂ each represents the same or different.

R ₆₃ is a group having the same meaning as R ₄₁ , R ₄₃ CON (R ₄₄ ) — group, R ₄₃ N (R ₄₄ ) CO— group, R ₄₁ SO ₂ N (R ₄₃ ) — group, R ₄₁ N (R ₄₃ ) Represents an SO ₂ — group, an R ₄₁ SO ₂ — group, an R ₄₃ OCO— group, an R ₄₃ OSO ₂ — group, a halogen atom, a nitro group, a cyano group, or an R ₄₃ CO— group. In the formula (Cp-9), e represents an integer of 0 to 4, and when e is 2 or more, the plurality of R ₆₃ are the same or different. In the formula (Cp-10), f represents an integer of 0 to 3, and when f is 2 or more, the plurality of R ₆₃ are the same or different.

R ₆₄ , R ₆₅ and R ₆₆ are each independently a group having the same meaning as the R ₄₃ group, R ₄₁ S-group, R ₄₃ O-group, R ₄₁ CON (R ₄₃ ) -group, R ₄₁ SO ₂ N ( R ₄₃ ) — group, R ₄₁ OCO— group, R ₄₁ OSO ₂ — group, R ₄₁ SO ₂ — group, R ₄₁ N (R ₄₃ ) CO— group, R ₄₁ N (R ₄₃ ) SO ₂ — group, nitro Represents a group or a cyano group.

In the above, the aliphatic hydrocarbon group represented by R ₄₁ , R ₄₃ , R ₄₄ or R ₄₅ is a saturated or unsaturated group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, linear or branched, linear or branched, A substituted or unsubstituted aliphatic hydrocarbon group; Representative examples include methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3, Examples include 3-tetramethylbutyl, n-decyl, and allyl.

The aryl group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is an aryl group having 6 to 10 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl. .

The heterocyclic group represented by R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ or R ₄₅ is selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. A 3- to 8-membered substituted or unsubstituted heterocyclic group is preferred. Representative examples of the heterocyclic group include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazol-2-yl, 1,2, A 4-triazol-2-yl group or 1-indolinyl is mentioned.

When the aliphatic hydrocarbon group, aryl group and heterocyclic group have a substituent, typical substituents include halogen atom, R ₄₃ O— group, R ₄₁ S— group, R ₄₃ CON (R ₄₄ ) —. Group, R ₄₃ N (R ₄₄ ) CO— group, R ₄₁ OCON (R ₄₃ ) — group, R ₄₁ SO ₂ N (R ₄₃ ) — group, R ₄₃ N (R ₄₄ ) SO ₂ — group, R ₄₁ SO ₂ - group, R ₄₃ OCO- group, R ₄₁ SO ₂ O-group, group having the same meaning as _{R 41, R 43 N (R} 44) - group, R ₄₁ CO2 - group, R ₄₁ OSO ₂ - group, a cyano Group or nitro group.

Then _{R 51 ~R 66, a, b} , d, preferred range of e and f will be described.
R ₅₁ is preferably an aliphatic hydrocarbon group or an aryl group. a is particularly preferably 1. R ₅₂ and R ₅₅ are preferably aryl groups. R ₅₃ is preferably an aryl group when b is 1, and a heterocyclic group when b is 0. R ₅₄ is preferably an R ₄₁ CON (R ₄₃ ) — group or an R ₄₁ N (R ₄₃ ) — group. R ₅₆ and R ₅₇ are preferably an aliphatic hydrocarbon group, an aryl group, an R ₄₁ O— group or an R ₄₁ S— group. R ₅₈ is preferably an aliphatic hydrocarbon group or an aryl group.

In the formula (Cp-6), R ₅₉ is preferably a chlor atom, an aliphatic hydrocarbon group or an R ₄₁ CON (R ₄₃ ) — group, and d is preferably 1 or 2. R ₆₀ is preferably an aryl group. In the formula (Cp-7), R ₅₉ is preferably an R ₄₁ CON (R ₄₃ ) — group, and d is preferably 1.

R ₆₁ is R ₄₃ OSO ₂ — group, R ₄₃ N (R ₄₄ ) SO ₂ — group, R ₄₃ OCO— group, R ₄₃ N (R ₄₄ ) CO— group, cyano group, R ₄₁ SO ₂ N (R ₄₃ ) CO— group, R ₄₃ CON (R ₄₄ ) CO— group, R ₄₃ N (R ₄₄ ) SO ₂ N (R ₄₅ ) CO— group, R ₄₃ N (R ₄₄ ) CON (R ₄₅ ) CO— group preferable. In formula (Cp-8), e is preferably 0 or 1, and R ₆₂ is R ₄₁ OCON (R ₄₃ ) — group, R ₄₁ CON (R ₄₃ ) — group or R ₄₁ SO ₂ N (R ₄₃ ) — group. These substitution positions are preferably the 5-position of the naphthol ring.

In the formula (Cp-9), R ₆₃ is R ₄₁ CON (R ₄₃ ) — group, R ₄₁ SO ₂ N (R ₄₃ ) — group, R ₄₁ N (R ₄₃ ) SO ₂ — group, R ₄₁ SO ₂ —. Group, R ₄₁ N (R ₄₃ ) CO— group, nitro group or cyano group is preferred. e is preferably 1 or 2.

In the formula (Cp-10), R ₆₃ is preferably an R ₄₃ N (R ₄₄ ) CO— group, an R ₄₃ OCO— group or an R ₄₃ CO— group. f is preferably 1 or 2.

In the formulas (Cp-11) and (Cp-12), R ₆₄ and R ₆₅ are R ₄₁ OCO— group, R ₄₁ OSO ₂ — group, R ₄₁ SO ₂ — group, R ₄₄ N (R ₄₃ ) CO— group. , R ₄₄ N (R ₄₃ ) SO ₂ — group or cyano group is preferable, and R ₄₁ OCO— group, R ₄₄ N (R ₄₃ ) CO— group or cyano group is particularly preferable. R ₆₆ is preferably a group having the same meaning as R ₄₁ . R _{51 to} R ₆₆ each preferably have a total carbon number of 18 or less including substituents, and more preferably 10 or less.

Next, the photographically useful group represented by PUG will be described.
The photographically useful group represented by PUG may be any PUG known in the art.

  Examples include development inhibitors, bleach accelerators, development accelerators, dyes, bleach inhibitors, couplers, developing agents, development aids, reducing agents, silver halide solvents, silver complexing agents, fixing agents, images Contains toners, stabilizers, hardeners, tanning agents, fogging agents, UV absorbers, antifoggants, nucleating agents, chemical or spectral sensitizers, desensitizers, and optical brighteners However, it is not limited to these.

  Preferably, the PUG is a development inhibitor (eg, US Pat. Nos. 3,227,554, 3,384,657, 3,615,506, 3,617,291, 3,733,201, 5,200,306 and British Patent No. 1,450,479), bleach accelerators (for example, Research Disclosure 1973 Item No. 11449 and European Patent 193389). Bleach accelerators described in JP-A-61-2012247, JP-A-4-350848, JP-A-4-350849, JP-A-4-350853), development aids (for example, U.S. Pat. 48787), a development accelerator (for example, the development accelerator described in US Pat. No. 4,390,618 and JP-A-2-56543), a reducing agent (for example, JP-A-63-10). 439 and the reducing agent described in 63-128342), a fluorescent brightener (for example, the fluorescent brightener described in US Pat. Nos. 4,774,181 and 5,236,804), and the pKa of the PUG conjugate acid. Is preferably 13 or less, more preferably 11 or less.

PUG is more preferably a development inhibitor or bleach accelerator.
Preferred development inhibitors include mercaptotetrazole derivatives, mercaptotriazole derivatives, mercaptothiadiazole derivatives, mercaptooxadiazole derivatives, mercaptoimidazole derivatives, mercaptobenzimidazole derivatives, mercaptobenzthiazole derivatives, mercaptobenzoxazole derivatives, tetrazole derivatives, 1,2, Examples thereof include 3-triazole derivatives, 1,2,4-triazole derivatives, and benzotriazole derivatives.

More preferable development inhibitors are represented by the following general formulas DI-1 to DI-6.

In the formula, R ₃₁ is a halogen atom, R ₄₆ O— group, R ₄₆ S— group, R ₄₇ CON (R ₄₈ ) — group, R ₄₇ N (R ₄₈ ) CO— group, R ₄₆ OCON (R ₄₇ ) —. Group, R ₄₆ O ₂ (R ₄₇ ) — group, R ₄₇ N (R ₄₈ ) SO ₂ group, R ₄₆ SO ₂ — group, R ₄₇ OCO— group, R ₄₇ N (R ₄₈ ) CON (R ₄₉ ) — Group, R ₄₇ CON (R ₄₈ ) SO ₂ — group, R ₄₇ N (R ₄₈ ) CON (R ₄₉ ) SO ₂ — group, group having the same meaning as R ₄₆ , R ₄₇ N (R ₄₈ ) — group, R ₄₆ CO ₂ — group, R ₄₇ OSO ₂ — group, cyano group or nitro group.

R ₄₆ represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, and R ₄₇ , R ₄₈ and R ₄₉ each represent an aliphatic hydrocarbon group, an aryl group, a heterocyclic group or a hydrogen atom. The aliphatic hydrocarbon group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is saturated or unsaturated, linear or cyclic, linear or branched, substituted or substituted having 1 to 32 carbon atoms, preferably 1 to 20 carbon atoms. An unsubstituted aliphatic hydrocarbon group. Representative examples include methyl, cyclopropyl, isopropyl, n-butyl, t-butyl, i-butyl, t-amyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-octyl, 1,1,3, Examples include 3-tetramethylbutyl, n-decyl, allyl, and ethynyl.

The aryl group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is an aryl group having 6 to 32 carbon atoms, preferably substituted or unsubstituted phenyl, or substituted or unsubstituted naphthyl.

The heterocyclic group represented by R ₄₆ , R ₄₇ , R ₄₈ or R ₄₉ is selected from a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom having 1 to 32 carbon atoms, preferably 1 to 20, preferably 3 It is a substituted or unsubstituted heterocyclic group having a member or 8 members. Representative examples of the heterocyclic group include 2-pyridyl, 2-benzoxazolyl, 2-imidazolyl, 2-benzimidazolyl, 1-indolyl, 1,3,4-thiadiazol-2-yl, 1,2, A 4-triazol-2-yl group or 1-indolinyl is mentioned.

R ₃₂ represents a group having the same meaning as R ₄₆ .
k represents an integer of 1 to 4, g represents 0 or 1, and h represents 1 or 2.
V represents an oxygen atom, a sulfur atom or —N (R ₄₆ ) —.
R ₃₁ and R ₃₂ may further have a substituent.

Preferred bleach accelerators are shown below.

Next, the group represented by TIME will be described.
The group represented by TIME may be any linking group that can cleave PUG or RED-PUG after cleaving from COUP1 during development processing. For example, a group that utilizes the cleavage reaction of hemiacetal described in U.S. Pat.Nos. 4,146,396, 4,652,516, or 4,698,297; Timing group for causing cleavage reaction using substitution reaction, Timing group for causing cleavage reaction using electron transfer reaction described in U.S. Pat.Nos. 4,409,323 or 4,421,845, etc., as described in U.S. Pat.No. 4,546,073 Examples thereof include a group that causes a cleavage reaction using a hydrolysis reaction of an iminoketal, or a group that causes a cleavage reaction using a hydrolysis reaction of an ester described in West German Patent No. 2626317. TIME is bonded to COUP1 in the general formula (IIa) or (IIb) at a hetero atom contained therein, preferably an oxygen atom, a sulfur atom or a nitrogen atom. Preferable TIME includes the following general formula (T-1), (T-2) or (T-3).

Formula (T-1) * -W- ( X = Y) j-C (R 21) R 22 - **
General formula (T-2) * -W-CO-**
General formula (T-3) * -W-LINK-E1-**
In the formula, * represents the position of binding to COUP1 in the general formula (IIa) or (IIb), and ** binds to PUG, TIME (when m is plural) or RED (in the case of the general formula (IIa)). Represents a position, W represents an oxygen atom, a sulfur atom or> N—R ₂₃ , X and Y each represents a methine or nitrogen atom, j represents 0, 1 or 2, R ₂₁ , R ₂₂ and R ₂₃ Each represents a hydrogen atom or a substituent. Here, when X and Y represent substituted methine, any two substituents of the substituent, R ₂₁ , R ₂₂ and R ₂₃ are linked to form a cyclic structure (eg, benzene ring, pyrazole ring). Or in the case where it is not formed. In the general formula (T-3), E1 represents an electrophilic group, and LINK represents a linking group that is sterically related so that W and E1 can undergo an intramolecular nucleophilic substitution reaction.

Specific examples of TIME represented by the general formula (T-1) include the following.

Specific examples of TIME represented by the general formula (T-2) include the following.

Specific examples of TIME represented by the general formula (T-3) include the following.

Specific examples of (TIME) _m when m is 2 in the general formula (IIa) include the following.

  The group represented by RED in the formula (IIb) will be described below. RED is a group that can be cleaved from COUP1 or TIME to become RED-PUG, and can be cross-oxidized by an oxidizing substance present during development, for example, an oxidized developer. RED-PUG may be any one that can cleave PUG when oxidized. Examples of RED include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamidophenols, hydrazides, or sulfonamidonaphthols. Specifically, these groups include, for example, JP-A Nos. 61-230135, 62-251746, 61-278852, US Pat. Nos. 3,364,022, 3,379,529, 4, No. 618,571, No. 3,639,417, No. 4,684,604, or J. Org. Chem., 29, 588 (1964).

  Of these, preferred REDs are hydroquinones, 1,4-naphthohydroquinones, 2 (or 4) -sulfonamidophenols, pyrogallols or hydrazides. Among these, the redox group having a phenolic hydroxyl group is bonded to COUP1 or TIME at the oxygen atom of the phenol group.

  The photosensitive layer to which the compound represented by the general formula (IIa) or (IIb) is added until the silver halide photographic light-sensitive material containing the compound represented by the general formula (IIa) or (IIb) is developed. Alternatively, for the purpose of fixing to the non-photosensitive layer, the compound represented by formula (IIa) or (IIb) preferably has a diffusion-resistant group, and the diffusion-resistant group is included in TIME or RED. The case is particularly preferred. In this case, preferred diffusion-resistant groups are alkyl groups having 8 to 40 carbon atoms, preferably 12 to 32 alkyl groups or alkyl groups (3 to 20 carbon atoms), alkoxy groups (3 to 20 carbon atoms) or aryl groups (6 carbon atoms). And an aryl group having 8 to 40 carbon atoms, preferably 12 to 32 carbon atoms, having at least one of ˜20).

  As for the synthesis method of the compound represented by the general formula (IIa) or (IIb), known patents or documents cited for explanation of TIME, RED and PUG, JP-A Nos. 61-156127 and 58-160954 58-162949, 61-249052, 63-37350, US Pat. Nos. 5,026,628, European Patent Nos. 443530A2 and 444501A2, and the like.

Next, the photographic useful group releasing compound represented by the general formula (III) will be described.
General formula (III) COUP2-CE-D2
In the formula, COUP2 represents a coupler residue that can be coupled with an oxidized developer, E represents an electrophilic site, and C represents a coupling position derived from the developer in the coupling product of COUP2 and oxidized developer. Represents a divalent linking group or a single bond capable of releasing D2 with a 4- to 8-membered ring formation by an intramolecular nucleophilic substitution reaction between a nitrogen atom directly bonded to and an electrophilic site E, and COUP2 It may be bonded to COUP2 at the coupling position of COUP2, or may be bonded to COUP2 at a position other than the coupling position of COUP2. D2 represents a photographically useful group or a precursor thereof.

  The coupler residue represented by COUP2 is a yellow coupler residue generally known as a photographic coupler (for example, an open-chain ketomethine-type coupler residue such as acylacetanilide or malondianilide), a magenta coupler residue (for example, Coupler residues such as 5-pyrazolone type or pyrazolotriazole type), cyan coupler residues (for example, coupler residues such as phenol type, naphthol type or pyrrolotriazole type), US Pat. Yellow, magenta having a novel skeleton described in JP-A-7-12823, JP-A-62-222526, JP-A-9-258400, JP-A-9-258401, JP-A-9-269573, JP-A-6-27612, etc. Alternatively, it may be a coupler residue for forming a cyan dye, or other coupler residues (for example, aromatic amines described in U.S. Pat. Nos. 3,632,345 and 3,928,041). Coupler residues that react with oxidized oxidants to form colorless substances, or react with oxidized aromatic amine developers as described in U.S. Pat.Nos. 1,939,231, 2,181,944, etc. A coupler residue).

The coupler residue represented by COUP2 may be a monomer or part of a dimer coupler, oligomer or polymer coupler, in which case more than one PUG is contained in the coupler. Also good.
Although the preferable example of COUP2 of this invention is shown below, it is not limited to these.

In the formula, * represents a bonding position with C. X ′ is a hydrogen atom, a halogen atom (for example, fluorine atom, chloro atom, bromine atom, iodine atom), R ₁₃₁ −, R ₁₃₁ O—, R ₁₃₁ S—, R ₁₃₁ OCOO—, R ₁₃₂ COO—, R _{132 (R 133) NCOO-, R 132} CON (R 133) - represents a, Y 'represents an oxygen atom, a sulfur atom, an R ₁₃₂ N = or R ₁₃₂ ON =. Here, R ₁₃₁ represents an aliphatic hydrocarbon group (the aliphatic hydrocarbon group is a saturated or unsaturated, linear or cyclic, linear or branched, substituted or unsubstituted aliphatic hydrocarbon group, and hereinafter has the same meaning) An aliphatic hydrocarbon group), an aryl group or a heterocyclic group.

The aliphatic hydrocarbon group represented by R ₁₃₁ is preferably an aliphatic hydrocarbon group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms. Specific examples include methyl, ethyl, vinyl, ethynyl, propyl, Isopropyl, 2-propenyl, 2-propynyl, butyl, isobutyl, t-butyl, t-amyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, 1,1,3,3-tetramethylbutyl, decyl, dodecyl, hexadecyl and Octadecyl is mentioned. Here, the “carbon number” refers to the total number of carbon atoms including the carbon number of the substituent when the aliphatic hydrocarbon group is an substituted aliphatic hydrocarbon group. Similarly, the group other than the aliphatic hydrocarbon group means the total number of carbon atoms including the carbon number of the substituent.

The aryl group represented by R ₁₃₁ is preferably a substituted or unsubstituted aryl group having 6 to 32 carbon atoms, more preferably 6 to 22 carbon atoms, and specific examples thereof include phenyl, tolyl, and naphthyl.

The heterocyclic group represented by R ₁₃₁ is preferably a substituted or unsubstituted heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 22 carbon atoms. Specific examples include 2-furyl, 2-pyrrolyl, 2 -Thienyl, 3-tetrahydrofuranyl, 4-pyridyl, 2-pyrimidinyl, 2- (1,3,4-thiadiazolyl), 2-benzothiazolyl, 2-benzoxazolyl, 2-benzimidazolyl, 2-benzoselenazolyl, Examples include 2-quinolyl, 2-oxazolyl, 2-thiazolyl, 2-selenazolyl, 5-tetrazolyl and 2- (1,3,4 oxadiazolyl), 2-imidazolyl and the like.

R ₁₃₂ and R ₁₃₃ each independently represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R ₁₃₂ and R ₁₃₃ are as defined for R ₁₃₁ .

Preferably, X ′ represents a hydrogen atom, an aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aliphatic hydrocarbon thio group or R ₁₃₂ CON (R ₁₃₃ ) —, and Y ′ represents an oxygen atom.

Examples of the substituent suitable for the groups described above and below and the “substituent” described below include, for example, a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, carboxyl group, sulfo group , Cyano group, nitro group, alkyl group (for example, methyl, ethyl, hexyl), fluoroalkyl group (for example, trifluoromethyl), aryl group (for example, phenyl, tolyl, naphthyl), heterocyclic group (for example, R ₁₃₁ The heterocyclic group described above), alkoxy group (for example, methoxy, ethoxy, octyloxy), aryloxy group (for example, phenoxy, naphthyloxy), alkylthio group (for example, methylthio, butylthio), arylthio group (for example, phenylthio) Amino groups (eg amino, N-methylamino, N, N-dimethylamino) N-phenylamino), acyl group (eg acetyl, propionyl, benzoyl), alkyl or arylsulfonyl group (eg methylsulfonyl, phenylsulfonyl), acylamino group (eg acetylamino, benzoylamino), alkyl or arylsulfonyl Amino group (eg, methanesulfonylamino, benzenesulfonylamino), carbamoyl group (eg, carbamoyl, N-methylaminocarbonyl, N, N-dimethylaminocarbonyl, N-phenylaminocarbonyl), sulfamoyl group (eg, sulfamoyl, N -Methylaminosulfonyl, N, N-dimethylaminosulfonyl, N-phenylaminosulfonyl), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, octyloxycarbonyl) ), Aryloxycarbonyl group (for example, phenoxycarbonyl, naphthyloxycarbonyl), acyloxy group (for example, acetyloxy, benzoyloxy), alkoxycarbonyloxy group (for example, methoxycarbonyloxy, ethoxycarbonyloxy), aryloxycarbonyloxy group (For example, phenoxycarbonyloxy), alkoxycarbonylamino group (for example, methoxycarbonylamino, butoxycarbonylamino), aryloxycarbonylamino group (for example, phenoxycarbonylamino), aminocarbonyloxy group (for example, N-methylaminocarbonyloxy) N-phenylaminocarbonyloxy), aminocarbonylamino group (for example, N-methylaminocarbonylamino, N-phenylaminocarbo Arylamino), and the like.

R ₁₁₁ and R ₁₁₂ each independently represents R ₁₃₂ CO—, R ₁₃₁ OCO—, R ₁₃₂ (R ₁₃₃ ) NCO—, R ₁₃₁ SOn—, R ₁₃₂ (R ₁₃₃ ) NSO ₂ — or a cyano group. Here, R ₁₃₁ , R ₁₃₂ and R ₁₃₃ are as defined above, and n represents 1 or 2.
R ₁₁₃ represents a group having the same meaning as R ₁₃₁ described above.
R ₁₁₄ is R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₂ (R ₁₃₃ ) N-, R ₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₁ S-, R ₁₃₁ O-, R ₁₃₁ OCON ( R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R ₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NCO- or a cyano group. Here, R ₁₃₁ , R ₁₃₂ and R ₁₃₃ are as defined above, and R ₁₃₄ represents the same group as R ₁₃₂ .

R ₁₁₅ and R ₁₁₆ each independently represent a substituent, preferably R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₁ S-, R ₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R ₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NCO-, a halogen atom or a cyano group, more preferably R ₁₃₁ It is a group represented. Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above.

R ₁₁₇ represents a substituent, p represents an integer of 0 to 4, and q represents an integer of 0 to 3. Preferred substituents of _{R 117, R 131 -, R} 132 CON (R 133) -, R 131 OCON (R 132) -, R 131 SO 2 N (R 132) -, R 132 (R 133) NCON ( R ₁₃₄ ) —, R ₁₃₁ S—, R ₁₃₁ O—, and halogen atoms. Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. When p and q are 2 or more, each R ₁₁₇ may be the same or different, and adjacent R _117s may be bonded together to form a ring. In a preferred embodiment of the general formulas (III-1E) and (III-2E), at least one of the ortho positions of the hydroxyl group is substituted with R ₁₃₂ CONH-, R ₁₃₁ OCONH-, or R ₁₃₂ (R ₁₃₃ ) NCONH-. is there.

R ₁₁₈ represents a substituent, r represents an integer of 0 to 6, and s represents an integer of 0 to 5. Preferred substituents of _{R 118, R 132 CON (R} 133) -, R 131 OCON (R 132) -, R 131 SO 2 N (R 132) -, R 132 (R 133) NCON (R 134) - _{, R 131 S-, R 131 O-} , R 132 (R 133) NCO-, R 132 (R 133) NSO2-, R 131 OCO-, a cyano group or a halogen atom. Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. When r and s are 2 or more, each R ₁₁₈ may be the same or different, and may be bonded to each other adjacent R ₁₁₈ to form a ring. In a preferred embodiment of the general formulas (III-1F), (III-2F) and (III-3F), the ortho position of the hydroxyl group is R ₁₃₂ CONH-, R ₁₃₂ HNCONH-, R ₁₃₂ (R ₁₃₃ ) NSO ₂ -or R ₁₃₂ Replaced with NHCO-.

R ₁₁₉ represents a substituent, _{preferably, R 132 -, R 132 CON} (R 133) -, R 131 SO 2 N (R 132) -, R 131 S-, R 131 O-, R 131 OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R ₁₃₁ OCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₂ (R ₁₃₃ ) NCO-, a halogen atom or a cyano group, A group represented by R ₁₃₁ is preferred. Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above.

R ₁₂₀ and R ₁₂₁ each independently represent a substituent, preferably R _132- , R ₁₃₂ CON (R ₁₃₃ )-, R ₁₃₁ SO ₂ N (R ₁₃₂ )-, R ₁₃₁ S-, R ₁₃₁ O-, R ₁₃₁ OCON (R ₁₃₂ )-, R ₁₃₂ (R ₁₃₃ ) NCON (R ₁₃₄ )-, R ₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₁ OCO-, halogen atoms and cyano And more preferably R ₁₃₂ (R ₁₃₃ ) NCO—, R ₁₃₂ (R ₁₃₃ ) NSO ₂ —, a trifluoromethyl group, R ₁₃₁ OCO— and a cyano group. Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above.

E is -CO-, -CS-, -COCO-, -SO-, -SO _2- , -P (= O) (R ₁₅₁ )-, -P (= S) (R ₁₅₁ )-(R ₁₅₁ is An aliphatic hydrocarbon group, an aryl group, an aliphatic hydrocarbon oxy group, an aryloxy group, an aliphatic hydrocarbon thio group, and an arylthio group are represented. } Or the like or —C (R ₁₅₂ ) (R ₁₅₃ ) — {R ₁₅₂ , R ₁₅₃ each represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group. Each aliphatic hydrocarbon group, aryl group, and heterocyclic group has the same _meaning as described for R ₁₃₁ . }, Preferably —CO—.

  C is obtained by an intramolecular nucleophilic substitution reaction between the nitrogen atom directly bonded to the coupling position derived from the developing agent in the coupling product of COUP2 and the oxidized developing agent and the electrophilic site E (preferably 4 to 8 members). Represents a divalent linking group or a single bond capable of releasing D2 with a ring formation of (more preferably 5 to 7 members, more preferably 6 members).

Examples of the linking group represented by C include the following.
× − (CO) _n1 − (Y ′) _n2 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − ××
× − (CO) _n1 − {N (R ₁₄₃ )} _n3 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − ××
× − (Y ′) _n2 − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − ××
× − {N (R ₁₄₃ )} _n3 − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − ××
× − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − (Y ′) _n2 − ××
× − (CO) _n1 − {C (R ₁₄₁ ) (R ₁₄₂ )} _n4 − {N (R ₁₄₃ )} _n3 − ××
× − (Y ′) _n2 − ××, × − {N (R ₁₄₃ )} _n3 − ××

In the formula, x represents a site bonded to COUP2, xx represents a site bonded to E, Y ′ represents an oxygen atom or a sulfur atom, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ represent a hydrogen atom, Represents an aromatic hydrocarbon group, an aryl group, or a heterocyclic group (the respective aliphatic hydrocarbon group, aryl group, or heterocyclic group has the same _meaning as described for R ₁₃₁ ), and each of R ₁₄₁ , R _142, and R ₁₄₃ may combine with each other or with COUP2 to form a ring.

R ₁₄₁ and R ₁₄₂ are preferably a hydrogen atom or an aliphatic hydrocarbon group, and more preferably a hydrogen atom.
R ₁₄₃ is preferably a hydrogen atom or an aliphatic hydrocarbon group.

n1 and n3 represent an integer of 0 to 2, n2 represents 0 or 1, n4 represents an integer of 1 to 5 (when n3 and n4 represent an integer of 2 or more, each N (R ₁₄₃ ) and C (R ₁₄₁ ) (R ₁₄₂ ) may be the same or different.) And nitrogen directly bonded to the coupling position derived from the developing agent in the coupling product of COUP2 and oxidized developing agent N1 + n2 + n4, n1 + n3 + n4, n2 and n3 are selected so that a 4- to 8-membered ring is formed by an intramolecular nucleophilic substitution reaction between the atom and the electrophilic site E. However, when -N (R ₁₄₃ )-is directly bonded to E, R ₁₄₃ is preferably not a hydrogen atom. Further, when the linking group C is linked at the coupling position of COUP2, the portion directly linked to COUP2 is not -Y'-.

  The coupling position of COUP2 and linking group C is determined by intramolecular nucleophilic substitution reaction between the developing agent-derived nitrogen atom and electrophilic site E in the coupling product after the coupling reaction between the coupler and oxidized developer. Any of those capable of releasing D2 with ring formation (preferably 4- to 8-membered, more preferably 5- to 7-membered, more preferably 6-membered), but preferably a cup of COUP2 The ring position or its vicinity (the atom adjacent to the coupling position or the atom adjacent thereto).

The coupler according to the invention when the linking group C is bonded to 1) the coupling position of the coupler residue represented by COUP2, 2) the atom next to the coupling position and 3) the atom next to the coupling position; The reaction of the coupler of the present invention with an oxidized aromatic amine developing agent (Ar ′ = NH) represented by ArNH ₂ can be represented by the following formula.

General formula (III-1) {where COUP2 is preferably (III-1A), (III-1B), (III-1C), (III-1D), (III-1E), (III-1F ) Or (III-1G). }, For example, the following may be mentioned as preferred C for
× -CO-C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) (R ₁₄₂ ) -XXX,
X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -xxx,
X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -XXX,
× -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R ₁₄₃ ) -XX,
X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -O-xx,
X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -S-XX,
X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -N ( _R143 ) -XX,
More preferably,
× -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R ₁₄₃ ) -XX,
X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -O-xx,
× -C (R ₁₄₁ ) (R ₁₄₂ ) -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R ₁₄₃ ) -XX
It is.

In the formula, x, xx, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ have the same _meanings as above (each having two or more —C (R ₁₄₁ ) (R ₁₄₂ ) — in one linking group). R ₁₄₁ and R ₁₄₂ may be the same or different.)

General formula (III-2) {where COUP2 is preferably (III-2A), (III-2B), (III-2C), (III-2D), (III-2E), (III- 2F) or (III-2G). }, For example, the following are preferable as C:
× −C (R ₁₄₁ ) (R ₁₄₂ ) − ××,
X-C ( _R141 ) ( _R142 ) -C ( _R141 ) ( _R142 ) -xxx,
X-O-xxx, x-S-xxx, x-N ( _R143 ) -xxx,
X-C ( _R141 ) ( _R142 ) -O-xx,
X-C ( _R141 ) ( _R142 ) -S-xx,
× -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R ₁₄₃ ) -XX
More preferably,
X-O-xxx, x-N ( _R143 ) -xxx,
X-C ( _R141 ) ( _R142 ) -O-xx,
× -C (R ₁₄₁ ) (R ₁₄₂ ) -N (R ₁₄₃ ) -XX
It is.

In the formula, x, xx, R ₁₄₁ , R ₁₄₂ and R ₁₄₃ have the same _meanings as above (each having two or more —C (R ₁₄₁ ) (R ₁₄₂ ) — in one linking group). R ₁₄₁ and R ₁₄₂ may be the same or different.)

General formula (III-3) {where COUP2 is preferably represented by (III-3F). }, The preferred C is
X-C ( _R141 ) ( _R142 ) -xxx, x-O-xxx, x-S-xxx,
X-N (R ₁₄₃ ) -xx, more preferably x-O-xxx,
X-N ( _R143 ) -xxx, with x-N ( _R143 ) -xxx being particularly preferred.

In the formula, x, xx, R ₁₄₁ , R ₁₄₂ , and R ₁₄₃ are as defined above.

D2 represents a photographically useful group or a precursor thereof. A preferred embodiment of D2 is represented by the following general formula (III-B).
#-(T) _k -PUG (III-B)
In the formula, # represents a site linked to E, T represents a timing group capable of releasing PUG after being released from E, k represents an integer of 0 to 2, preferably 0 or 1, PUG represents a photographically useful group.

  As a timing group represented by T, for example, a group that releases PUG using a cleavage reaction of hemiacetal described in US Pat. Nos. 4,146,396, 4,652,516, or 4,698,297, No. 4,248,962, No. 5,719,017 or No. 5,709,987, etc., a group that releases PUG using an intramolecular ring closure reaction, JP-B-54-39727, JP-A-57-136640, JP-A-57-154234, PUG is emitted by electron transfer via π-electrons described in JP-A-4-61530, 4-212246, 6-324439, 9-114058, US Pat. No. 4,409,323 or 4,421,845, etc. Group, a group that generates carbon dioxide as described in JP-A-57-179842, JP-A-4-61530, 5-313322, etc. to release PUG, hydrolysis reaction of iminoketal as described in US Pat. No. 4,546,073 A group that releases PUG by the ester hydrolysis reaction described in West German Patent No. 2626317. Thus, a group that releases PUG or a group that releases PUG using a reaction with sulfite ion described in European Patent No. 572084 can be used.

Preferred examples of the timing group represented by T of the present invention include, but are not limited to, the following timing groups.

In the formula, # represents a site that binds to the electrophilic site E or ##, and ## represents a position that binds to PUG or #. Z represents an oxygen atom or a sulfur atom, preferably an oxygen atom. R ₁₆₁ represents a substituent, preferably _{R 131 -, R 132 CON (} R 133) -, R 131 SO 2 N (R 132) -, R 131 S-, R 131 O-, R 131 OCON (R 132 _{) -, R 132 (R 133} ) NCON (R 134) -, R 132 (R 133) NCO-, R 132 (R 133) NSO 2 -, represents a R ₁₃₁ OCO-, halogen atom, nitro group and cyano group . Here, R ₁₃₁ , R ₁₃₂ , R ₁₃₃ and R ₁₃₄ are as defined above. R ₁₆₁ may combine with any of R ₁₆₂ , R ₁₆₃ , and R ₁₆₄ to form a ring. n1 represents an integer of 0 to 4. When n1 represents an integer of 2 or more, each R ₁₆₁ may be the same or different, and R ₁₆₁ may be bonded to each other to form a ring.

R ₁₆₂ , R ₁₆₃ and R ₁₆₄ represent the same group as R _132, and n2 represents 0 or 1. R ₁₆₂ and R ₁₆₃ may combine to form a spiro ring. R ₁₆₂ and R ₁₆₃ are preferably a hydrogen atom or an aliphatic hydrocarbon group (having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms), more preferably a hydrogen atom. R ₁₆₄ is preferably an aliphatic hydrocarbon group (having 1 to 20 carbon atoms, preferably 1 to 10) or an aryl group (having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms). R ₁₆₅ represents R _132- , R ₁₃₂ (R ₁₃₃ ) NCO-, R ₁₃₂ (R ₁₃₃ ) NSO _2- , R ₁₃₁ OCO-, R ₁₃₂ CO-. Here, R ₁₃₁ , R ₁₃₂ and R ₁₃₃ are as defined above. R ₁₆₅ preferably represents R ₁₃₂ , more preferably an aryl group having 6 to 20 carbon atoms.
The photographically useful group represented by PUG is as defined above.

  Preferred embodiments of the coupler of the present invention are those represented by the above general formula (III-2) or (III-3), and (III-3) is more preferred (general formulas (III-2), (III- In 3), C, E, D2 and preferred ranges thereof are as defined above.

A more preferred embodiment of the general formula (III-3) is represented by the following general formula (III-3a), more preferably represented by the following general formula (III-3b), and particularly preferably represented by the general formula (III-3c). expressed. In addition, the structure of the cyclized product obtained by the reaction of the general formula (III-3c) with the oxidized developer (Ar ′ = NH) represented by ArNH _{2 can} be represented by the general formula (III-C). it can.

In the formula, Q ₁ and Q ₂ each form a 5- or 6-membered ring and are a group of nonmetallic atoms necessary to cause a coupling reaction with an oxidized developer at the root of X ′, ', T, k, PUG, R ₁₁₈ , s, and R ₁₃₂ are as defined above. R ₁₄₄ represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, preferably an aliphatic hydrocarbon group, an aryl group or a heterocyclic group, more preferably an aliphatic hydrocarbon group (respectively The aliphatic hydrocarbon group, aryl group, and heterocyclic group of the above are as defined for R _131. )

In the present invention, at least the following groups are not D1 and D2.

In the formula, *** represents an electrophilic site represented by E or a site linked to a timing group represented by T, R ₇₁ represents a substituted or unsubstituted aliphatic hydrocarbon group, R ₇₂ represents an unsubstituted aliphatic hydrocarbon group.

Specific examples of couplers used in the light-sensitive material of the present invention are shown below, but are not limited thereto.

  Methods for synthesizing the compound represented by the general formula (II) are described in, for example, JP-A-58-162949, JP-A-63-37350, JP-A-4-356042, JP-A-5-61160, JP-A-6-130594, and US5234800. Has been.

Synthesis examples of the compound represented by the general formula (III) are shown below.

  N of N, N-dimethylacetamide (250 ml (hereinafter referred to as “mL”) in a solution of Compound 62a (50 g) and o-tetradecyloxyaniline (51.1 g) at 30 ° C. with N of dicyclohexylcarbodiimide (41.3 g) , N-dimethylacetamide (60 mL) was added dropwise, and the reaction mixture was stirred at 50 ° C. for 1 hour, and then ethyl acetate (250 mL) was added and cooled to 20 ° C. The reaction mixture was filtered with suction, and the filtrate was filtered. 1N Hydrochloric acid (250 mL) was added for liquid separation, hexane (100 mL) was added to the organic layer, and the precipitated crystals were filtered, washed with acetonitrile, and dried to give compound 62b (71 g).

Synthesis of Compound 62c To a solution of Compound 62b (71 g) in methanol (350 mL) / tetrahydrofuran (70 mL) was added dropwise an aqueous solution of sodium hydroxide (30 g) (150 mL), and the mixture was stirred at 60 ° C. for 1 hour in a nitrogen atmosphere. After cooling the reaction solution to 20 ° C., concentrated hydrochloric acid was added dropwise until the system became acidic. The precipitated crystals were filtered, washed with water, washed with acetonitrile, and then dried to obtain Compound 62c (63 g).

Synthesis of Compound 62d Compound 62c (20 g), succinimide (5.25 g), and 37% aqueous formalin solution 4.3 mL in ethanol (150 mL) were stirred and refluxed for 5 hours. After cooling to 20 ° C., the precipitated crystals were filtered and dried to obtain Compound 62d (16 g).

Synthesis of Compound 62e Sodium borohydride (1.32 g) was slowly added to a solution of Compound 62d (7 g) in dimethyl sulfoxide (70 mL) at 60 ° C. so as not to exceed 70 ° C., and the mixture was stirred at that temperature for 15 minutes. The reaction mixture was slowly added to 1N aqueous hydrochloric acid (100 mL), and extracted with ethyl acetate (100 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. The origin component was removed with a short pass column (developing solvent: ethyl acetate / hexane = 2/1), and then recrystallized from an ethyl acetate / hexane system to obtain Compound 62e (3.3 g).

Synthesis of Compound (62) Bis (trichloromethyl) carbonate (1.98g) in dichloromethane (80mL) in phenoxycarbonylbenzotriazole (4.78g) and N, N-dimethylaniline (2.42g) in dichloromethane (100mL) / ethyl acetate (200 mL) solution was added dropwise and stirred at 20 ° C. for 2 hours (Solution S).

  120 mL of the above solution S was added dropwise at 10 ° C. to a solution of compound 62e (2.0 g) and dimethylaniline (0.60 g) in tetrahydrofuran (20 mL) / ethyl acetate (20 mL), and the mixture was stirred at 20 ° C. for 2 hours. The reaction mixture was slowly added to 1N aqueous hydrochloric acid (200 mL), and extracted with ethyl acetate (200 mL). The organic layer was washed with water, dried over magnesium sulfate, and concentrated under reduced pressure. After purification by column (developing solvent: ethyl acetate / hexane = 1/5), recrystallization from an ethyl acetate / hexane system gave 1.3 g (mp = 138-140 ° C.) of Exemplified Compound (62) (compound Identification was performed by elemental analysis, NMR and Mass spectrum.)

The surfactant that can be used in the present invention may be any surfactant as long as the critical micelle concentration is 4.0 × 10 ⁻³ mol / L or less, but preferably functions as a dispersant for a high-boiling organic solvent. More preferred surfactants for use in the present invention are anionic surfactants such as sulfoalkyl or sulfoaryl, nonionic surfactants such as alkyl polyethylene oxide, and betaine surfactants such as sulfoalkylammonium. A polymer surfactant having a functional group bonded to a polymer can also be used. Here, the critical micelle concentration refers to the value of the surface tension at each concentration measured using SURFACE TENSIOMETER A3 prepared by Kyowa Kagaku Co., Ltd. A concentration-surface tension curve was obtained by plotting on the axis, and the concentration reaching the minimum surface tension of this curve was defined as the critical micelle concentration. The critical micelle concentration is the lowest concentration at which the surfactant forms micelles, and the lower this value, the better the surface activity.

In the present invention, the content of the surfactant in the light-sensitive material is preferably 0.01% by mass or more, and more preferably 0%, based on all components contained in the emulsion layer containing the surfactant. 0.02% by mass or more. The content of the surfactant in the light-sensitive material is preferably 5% by mass or less.
Only specific examples of the surfactant used in the present invention are shown below. Of course, the present invention is not limited to these.

  The high-boiling organic solvent that can be used in the present invention is preferably a high-boiling organic solvent having a dielectric constant of 7.0 or less, and a high-boiling organic solvent having a boiling point of about 175 ° C. or higher at normal pressure, such as phthalates and phosphates. , Phosphonic acid esters, benzoic acid esters, fatty acid esters, amides, phenols, alcohols, ethers, carboxylic acids, N, N-dialkylanilines, trialkylamines, hydrocarbons, oligomers or You can choose from polymers. However, when two or more kinds of high-boiling organic solvents are used as a mixture, if the dielectric constant after mixing is 7.0 or less, it corresponds to the high-boiling organic solvent having a dielectric constant of 7.0 or less.

  It is also possible to use these high boiling point organic solvents having a dielectric constant of 7.0 or less in combination with a high boiling point organic solvent having a dielectric constant of greater than 7.0. If it is 7.0 or less, it corresponds to the high boiling point organic solvent having a dielectric constant of 7.0 or less. Here, the dielectric constant is a relative dielectric constant with respect to vacuum, measured by a transformer bridge method at a measurement temperature of 25 ° C. and a measurement frequency of 10 kHz using a Ando Electric TRS-10T type dielectric constant measurement device. The dielectric constant of the organic solvent correlates with the square of the dipole moment of the organic solvent molecule, that is, represents the magnitude of the polarity of the molecule. In general, molecules with a high dielectric constant are highly polar.

The high boiling point organic solvent preferably used in the present invention is a high boiling point organic solvent having a dielectric constant of 7.0 or less and represented by the following general formulas [S-1] to [S-8].

In the formula [S-1], R ₁ , R ₂ and R ₃ each independently represents an aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group or an aryl group. In the formula [S-2], R ₄ and R ₅ each independently represents an aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or an aryl group, and R ₆ represents a halogen atom (F, Cl, Br, I and so on) ), An aliphatic hydrocarbon group, an aliphatic hydrocarbon oxy group, an aryloxy group or an aliphatic hydrocarbon oxycarbonyl group, and a represents an integer of 0 to 3. When a is a plurality, a plurality of R ₆ may be the same or different.

In the formula [S-3], Ar represents an aryl group, b represents an integer of 1 to 6, and R ₇ represents a b-valent hydrocarbon group or a hydrocarbon group bonded to each other through an ether bond. In the formula [S-4], R ₈ represents an aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon group, c represents an integer of 1 to 6, and R ₉ represents a c-valent hydrocarbon group or an ether bond, Represents a bonded hydrocarbon group. In the formula [S-5], d represents an integer of 2 to 6, R ₁₀ represents a d-valent hydrocarbon group (excluding an aryl group), and R ₁₁ represents an aliphatic hydrocarbon group or a cyclic aliphatic hydrocarbon. Represents a group or an aryl group. In the formula [S-6], R ₁₂ , R ₁₃ and R ₁₄ each independently represents an aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group or an aryl group. R ₁₂ and R ₁₃ or R ₁₃ and R ₁₄ may be bonded to each other to form a ring.

In the formula [S-7], R ₁₅ represents an aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aliphatic hydrocarbon oxycarbonyl group, an aliphatic hydrocarbon sulfonyl group, an arylsulfonyl group, an aryl group, or a cyano group. R ₁₆ represents a halogen atom, an aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, an aryl group, an alkoxy group, or an aryloxy group, and e represents an integer of 0 to 3. When e is plural, plural R ₁₆ may be the same or different.

In the formula [S-8], R ₁₇ and R ₁₈ each independently represents an aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group or an aryl group, and R ₁₉ represents a halogen atom, an aliphatic hydrocarbon group or a cyclic aliphatic carbonization. Represents a hydrogen group, an aryloxy group, or an aliphatic hydrocarbon oxy group, and f represents an integer of 0 to 4. When f is plural, plural R ₁₉ may be the same or different. In the formulas [S-1] to [S-8], when R ₁ to R ₆ , R ₈ , R _{11 to} R ₁₉ are an aliphatic hydrocarbon group or a group containing an aliphatic hydrocarbon group, the alkyl group is straight Either a chain or a branched chain may be used, and an unsaturated bond may be included or a substituent may be included. Examples of the substituent include a halogen atom, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, and an epoxy group.

In the formulas [S-1] to [S-8], when R ₁ to R ₆ , R ₈ and R _{11 to} R ₁₉ are a cyclic aliphatic hydrocarbon group or a group containing a cyclic aliphatic hydrocarbon group, The group hydrocarbon group may contain an unsaturated bond in a 3- to 8-membered ring, and may have a substituent or a bridging group. Examples of the substituent include a halogen atom, a hydroxyl group, an acyl group, an aryl group, an alkoxy group, an epoxy group, and an alkyl group. Examples of the cross-linking group include methylene, ethylene, isopropylidene, and the like.

In the formulas [S-1] to [S-8], when R ₁ to R ₆ , R ₈ and R _{11 to} R ₁₉ are an aryl group or a group containing an aryl group, the aryl group is a halogen atom, an alkyl group, an aryl It may be substituted with a substituent such as a group, an alkoxy group, an aryloxy group, or an alkoxycarbonyl group.

In the formulas [S-3], [S-4], and [S-5], when R ₇ , R _9, or R ₁₀ is a hydrocarbon group, the hydrocarbon group is a cyclic structure (eg, benzene ring, cyclopentane ring, cyclohexane Ring), an unsaturated bond, and may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an acyloxy group, an aryl group, an alkoxy group, an aryloxy group, and an epoxy group.

Examples of R ₁ , R ₂ and R _{3 in} the formula [S-1] include aliphatic hydrocarbon groups having 1 to 24 (preferably 4 to 18) total carbon atoms (hereinafter abbreviated as C number) (for example, n -Butyl, 2-ethylhexyl, 3,3,5-trimethylhexyl, n-dodecyl, n-octadecyl, benzyl, 2-chloroethyl, 2,3-dichloropropyl, 2-butoxyethyl, 2-phenoxyethyl), C number 5-24 (preferably 6-18) cycloaliphatic hydrocarbon group (eg cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 4-methylcyclohexyl) or aryl having 6 to 24 carbon atoms (preferably 6-18) Groups such as phenyl, cresyl, p-nonylphenyl, xylyl, cumenyl, p-methoxyphenyl, p-methoxycarbonylphenyl are included.

In the formula [S-2], examples of R ₄ and R ₅ include aliphatic hydrocarbon groups having 1 to 24 carbon atoms (preferably 4 to 18) (for example, the same groups as the aliphatic hydrocarbon groups mentioned for R ₁ above). , Ethoxycarbonylmethyl, 1,1-diethylpropyl group, 2-ethyl-1-methylhexyl, cyclohexylmethyl, 1-ethyl-1,5-dimethylhexyl), C 5-24 (preferably 6-18) A cyclic aliphatic hydrocarbon group (for example, the cyclic aliphatic hydrocarbon group mentioned for R ₁ , 3,3,5-trimethylcyclohexyl, menthyl, bornyl, 1-methylcyclohexyl) or C 6-24 (preferably 6-6 18) aryl groups (for example, the aryl groups mentioned above for R ₁ , 4-t-butylphenyl, 4-t-octylphenyl, 1,3,5-trimethylphenyl, 2, 4-di-t-butylphenyl, 2,4-di-t-pentylphenyl), and examples of R ₆ include halogen atoms (preferably Cl), C 1-18 aliphatic hydrocarbon groups ( For example, methyl, isopropyl, t-butyl, n-dodecyl), C 1-18 aliphatic hydrocarbon oxy group (for example, methoxy, n-butoxy, n-octyloxy, methoxyethoxy, benzyloxy), C 6-6 18 aryloxy groups (eg phenoxy, p-tolyloxy, 4-methoxyphenoxy 4-t-butylphenoxy) or C 2-19 aliphatic hydrocarbon oxycarbonyl groups (eg methoxycarbonyl, n-butoxycarbonyl, 2 -Ethylhexyloxycarbonyl) and a is 0 to 3 (preferably 0 or 1).

In the formula [S-3], examples of Ar include aryl groups having 6 to 24 carbon atoms (preferably 6 to 18) such as phenyl, 4-chlorophenyl, 4-methoxyphenyl, 1-naphthyl, and 4-n-butoxyphenyl. 1,3,5-trimethylphenyl), b is an integer of 1 to 6 (preferably 1 to 3), and examples of R ₇ include b-valent C number of 2 to 24 (preferably 2 to 2). hydrocarbon group [for example the aliphatic hydrocarbon group mentioned for R ₄ of 18), a cyclic aliphatic hydrocarbon group, an aryl _{group, - (CH 2) 2 -} ,

Or a hydrocarbon group bonded to each other by a b-valent C 4-24 (preferably 4-18) ether bond [for example, —CH ₂ CH ₂ OCH ₂ CH ₂ —, —CH ₂ CH ₂ (OCH _{2 CH 2) 3 -, -} CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -,

] Is included.

In the formula [S-4], examples of R ₈ include an aliphatic hydrocarbon group having 1 to 24 carbon atoms (preferably 1 to 17) (for example, methyl, n-propyl, 1-hydroxyethyl, 1-ethylpentyl, n-undecyl, pentadecyl, 8,9-epoxyheptadecyl) or a C3-C24 (preferably 6-18) cyclic aliphatic hydrocarbon group (for example, cyclopropyl, cyclohexyl, 4-methylcyclohexyl), c is an integer of 1 to 6 (preferably 1 to 3), and examples of R ₉ include c-valent C 2-24 (preferably 2-18) hydrocarbon group or c-valent 4 carbon atoms. -24 (preferably 4 to 18) hydrocarbon groups bonded to each other by ether bonds (for example, the groups mentioned for R ₇ above) are included.

In the formula [S-5], d is 2 to 6 (preferably 2 or 3), and examples of R ₁₀ include d-valent hydrocarbon groups [for example,

In the examples of R ₁₁ , C 1-24 (preferably 4-18) aliphatic hydrocarbon group, C 5-24 (preferably 6-18) cyclic aliphatic hydrocarbon group or An aryl group having 6 to 24 carbon atoms (preferably 6 to 18) (for example, an alkyl group, a cycloalkyl group, or an aryl group mentioned above for R ₄ ) is included.

In the formula [S-6], examples of R ₁₂ include an aliphatic hydrocarbon group having 1 to 24 carbon atoms (preferably 3 to 20) [for example, n-propyl, 1-ethylpentyl, n-undecyl, n-pentadecyl, 2,4-di-t-pentylphenoxymethyl, 4-t-octylphenoxymethyl, 3- (2,4-di-t-butylphenoxy) propyl, 1- (2,4-di-t-butylphenoxy) Propyl], a C5-C24 (preferably 6-18) cyclic aliphatic hydrocarbon group (for example, cyclohexyl, 4-methylcyclohexyl) or a C6-C24 (preferably 6-18) aryl group (for example, the above-mentioned) include aryl groups) mentioned for Ar, aliphatic hydrocarbon group (such as methyl R ₁₃ and C number in the example of R ₁₄ 1 to 24 (preferably 1 to 18), ethyl, isopropyl, n- Bed , N-hexyl, 2-ethylhexyl, n-dodecyl), C 5-18 (preferably 6-15) cyclic aliphatic hydrocarbon group (eg cyclopentyl, cyclopropyl) or C 6-18 (preferably 6-15) aryl groups (eg phenyl, 1-naphthyl, p-tolyl). R ₁₃ and R ₁₄ may be bonded to each other to form a pyrrolidine ring, piperidine ring or morpholine ring together with N, or R ₁₂ and R ₁₃ may be bonded to each other to form a pyrrolidone ring.

In the formula [S-7], examples of R ₁₅ include aliphatic hydrocarbon groups having 1 to 24 carbon atoms (preferably 1 to 18) (for example, methyl, isopropyl, t-butyl, t-pentyl, t-hexyl, t -Octyl, 2-butyl, 2-hexyl, 2-octyl, 2-dodecyl, 2-hexadecyl, t-pentadecyl), C 3-18 (preferably 5 to 12) cyclic aliphatic hydrocarbon group (for example, cyclopentyl) Cyclohexyl), an aliphatic hydrocarbon oxycarbonyl group having 2 to 24 carbon atoms (preferably 5 to 17) (for example, n-butoxycarbonyl, 2-ethylhexyloxycarbonyl, n-dodecyloxycarbonyl), 1 to 24 carbon atoms ( Preferably 1-18) aliphatic hydrocarbon sulfonyl groups (eg methylsulfonyl, n-butylsulfonyl, n-dodecylsulfonyl) C 6-30 (preferably 6-24) arylsulfonyl group (for example, p-tolylsulfonyl, p-dodecylphenylsulfonyl, p-hexadecyloxyphenylsulfonyl), C 6-32 (preferably 6-24) Aryl group (for example, phenyl, p-tolyl) or cyano group, R ₁₆ is a halogen atom (preferably Cl), C 1-24 (preferably 1-18) aliphatic hydrocarbon group (for example, the above-mentioned) R ₁₅ aliphatic hydrocarbon groups mentioned above, C 3-18 (preferably 5 to 17) cyclic aliphatic hydrocarbon groups (eg cyclopentyl, cyclohexyl), C 6-32 (preferably 6-24) Aryl group (for example, phenyl, p-tolyl), C 1-24 (preferably 1-18) aliphatic hydrocarbon oxy group (for example, methoxy, n-butene) C, 2-ethylhexyloxy, benzyloxy, n-dodecyloxy, n-hexadecyloxy) or an aryloxy group having 6 to 32 carbon atoms (preferably 6 to 24) (for example, phenoxy, pt-butylphenoxy, p -T-octylphenoxy, m-pentadecylphenoxy, p-dodecyloxyphenoxy), and e is an integer of 0 to 3 (preferably 1 or 2).

In the formula [S-8], R ₁₇ and R ₁₈ are the same as R ₁₃ and R ₁₄ , and R ₁₉ is the same as R ₁₆ . f is an integer of 0 to 4 (preferably 0 to 2).

Among the high-boiling organic solvents represented by the general formulas [S-1] to [S-8], the general formula [S-1] (R ₁ , R ₂ and R ₃ are preferably alkyl groups), [S-2 ], [S-3] (b is preferably 1), [S-4], [S-5] and [S-7] are particularly preferred high-boiling organic solvents represented by the general formula [S-1] , [S-2], [S-4] and [S-5] are most preferable. Specific examples of the high boiling point organic solvent used in the present invention are shown below.

  These high-boiling organic solvents may be used alone or in combination of two or more [for example, di (2-ethylhexyl) phthalate and trioctyl phosphate, di (2-ethylhexyl) sebacate and triisononyl phosphate, dibutyl phthalate and di (2-Ethylhexyl) adipate]. Here, when two or more kinds of high-boiling organic solvents are mixed and used, the dielectric constant after mixing is preferably 7.0 or less.

  Examples of other high boiling point organic solvents used in the present invention and / or methods for synthesizing these high boiling point organic solvents are disclosed in, for example, US Pat. Nos. 2,322,027, 2,533,514, and 2 772,163, 2,835,579, 3,594,171, 3,676,137, 3,689,271, 3,700,454 3,748,141, 3,764,336, 3,765,897, 3,912,515, 3,936,303, 4, No. 004,929, No. 4,080,209, No. 4,127,413, No. 4,193,802, No. 4,207,393, No. 4,220,711, No. 4,239,851, No. 4,278,757, No. , 353,979, 4,363,873, 4,430,421, 4,464,464, 4,483,918, 4,540,657 No. 4,684,606, No. 4,728,599, No. 4,745,049, European Patent Nos. 276,319A, No. 286,253A, No. 289,820A, 309,158A, 309,159A, 309,160A, JP-A-48-47335, 50-26530, 51-25133, 51-26036, 51- 277211, 51-27922, 51-149028, 52-46816, 53-1520, 53-1521, 53-15127, 53-146622, 54-1062 No. 8, No. 56-64333, No. 56-81836, No. 59-204401, No. 61-84641, No. 62-118345, No. 62-247364, No. 63-167357, No. 63-214744 63-301941 and 64-68745, JP-A-1-101543, and JP-A-1-102454.

  In the present invention, the high boiling point organic solvent is preferably contained as an emulsion (microdispersion). The average particle size of the emulsion is preferably 50 μm or less, more preferably 10 μm or less, particularly preferably 2 μm or less, and most preferably 0.5 μm or less. In preparing the emulsion, it can be dispersed only by mechanical stirring, but it is also preferable to use a surfactant. It is also preferable to prepare the emulsion by adding a polymer such as gelatin.

  The content of the high boiling point organic solvent in the emulsion is preferably 0.05% to 10% by mass% (the mass of the organic solvent contained in 100 g of the emulsion), more preferably 0.1% to 10%. More preferably, it is 0.2% to 10%.

  General formula (IV) and general formula (V) will be described in detail. In general formula (IV), Q represents an N or P atom. Ra1, Ra2, Ra3, Ra4 are each preferably substituted or unsubstituted alkyl having 1 to 20 carbon atoms (for example, methyl, butyl, hexyl, dodecyl, hydroxyethyl and trimethylammonioethyl, and benzyl, phenethyl and p An aryl-substituted alkyl having 7 to 20 carbon atoms such as chlorobenzyl), preferably a substituted or unsubstituted aryl having 6 to 20 carbon atoms (eg, phenyl, p-chlorophenyl), a substituted or unsubstituted heterocycle ( For example, thienyl, furyl, pyrrolyl, imidazolyl, pyridyl), and Ra1, Ra2, Ra3, and Ra4 are connected to form a saturated ring (eg, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring). Ra1, Ra2, Ra3, and Ra4 may be formed by combining three of these unsaturated rings (for example, pyridine ring, Imidazole ring, quinoline ring, may form a isoquinoline ring). Examples of substituted alkyl of Ra1, Ra2, Ra3, and Ra4 may have a quaternary ammonium salt, a quaternary pyridinium salt, or a quaternary phosphonium salt as a substituent.

  Y represents an anionic group, but Y does not exist in the case of an inner salt. Examples of Y are chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate ion, and oxalate.

  In general formula (V), each of Ra5, Ra6 and Ra7 is preferably a substituted or unsubstituted alkyl having 1 to 20 carbon atoms (for example, methyl, butyl, hexyl, dodecyl and hydroxyethyl, and benzyl, phenethyl and p -Aryl substituted alkyl having 7 to 20 carbon atoms such as chlorobenzyl), substituted or unsubstituted aryl having 6 to 20 carbon atoms (eg, phenyl, p-chlorophenyl), substituted or unsubstituted heterocyclic ring (eg, thienyl) , Furyl, pyrrolyl, imidazolyl, and pyridyl), Ra5, Ra6, and Ra7 may be linked together to form a saturated ring (eg, pyrrolidine ring, piperidine ring, piperazine ring, morpholine ring). Or Ra5, Ra6 and Ra7 are jointly unsaturated rings (eg pyridine ring, imidazole ring, quinoline ring, isoquinoline ring) It may be formed.

Ra8 represents an alkylene, arylene, —O—, —S—, or —CO ₂ — alone or in combination. However, -O -, - S -, - CO 2 - is linked adjacent to an alkylene or arylene respectively. A substituent such as a hydroxy group may be substituted as an alkylene substituent. The number of carbon atoms in the alkylene group is 1 to 10 preferably Ku, e.g., trimethylene, pentamethylene, heptamethylene, _{nonamethylene, -CH 2 CH 2 OCH 2 CH} 2 -, - (CH 2 CH 2 O) 2 -CH 2 CH _{2 -, - (CH 2 CH} 2 O) 3 -CH 2 CH 2 -, - (CH 2 CH 2 S) 3 -CH 2 CH 2 -, - CH 2 CH 2 COOCH 2 CH 2 OCOCH 2 CH 2 - and Can be mentioned.
Ra9, Ra10, and Ra11 are synonymous with Ra5, Ra6, and Ra7.

The compound of the general formula (IV) of the present invention is preferably a compound of the general formula (V).
The compounds represented by general formula (IV) and general formula (V) of the present invention are preferably added after being dissolved in water, a water-soluble solvent such as methanol, ethanol or a mixed solvent thereof.

  The addition time of the compound represented by the general formula (IV) or general formula (V) of the present invention is not limited to before or after the addition time of the sensitizing dye, and the preferable addition amount is 1 mol% to 50 mol% of the sensitizing dye. More preferably, it is contained in the silver halide emulsion at a ratio of 2 mol% to 25 mol%. When the amount of the compound represented by the general formula (IV) or general formula (V) used in the present invention is excessively large, the amount of the sensitizing dye that can be adsorbed to the emulsion grains may be decreased. .

The compounds represented by general formula (IV) and general formula (V) of the present invention can be easily synthesized by a method similar to the synthesis method described in Quart. Rev., 16, 163 (1962).
Representative examples of the compounds represented by formulas (IV) and (V) used in the present invention are shown below, but the present invention is not limited to these.

Next, general formulas (VI) to (XI) will be described in detail.
The compounds represented by the general formulas (VI) to (XI) of the present invention are all reducing compounds, and their oxidation potentials are measured by Akira Fujishima “Electrochemical measurement method” (pages 150 to 208, published by Gihodo) It can be measured using the measurement method described in “Chemical Experiment Course” 4th edition (Vol. 9, pp. 282 to 344, Maruzen) edited by the Chemical Society of Japan. For example, by a rotating disk voltammetry technique, specifically, a sample is dissolved in a solution of methanol: pH 6.5 Briton-Robinson buffer = 10%: 90% (volume%), and nitrogen gas is used for 10 minutes. , A glassy rotating disk electrode (RDE) is used as a working electrode, a platinum wire is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, 25 ° C., 1000 rev / min, 20 mV / sec. Can be measured at sweep speed. A half-wave potential (E _1/2 ) can be obtained from the obtained voltammogram.
The reducing compound of the present invention preferably has an oxidation potential in the range of about −0.3 V to about 1.0 V when measured by the above measurement method. More preferably, it is in the range of about -0.1V to about 0.8V, and particularly preferably in the range of about 0 to about 0.6V.

  In general formula (VI), the alkyl group, alkenyl group, and alkynyl group represented by Rb1 and Rb2 are substituted or unsubstituted linear or branched alkyl groups having 1 to 10 carbon atoms (eg, methyl, ethyl, isopropyl). N-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutyl Aminoethyl, n-butoxypropyl, methoxymethyl), substituted or unsubstituted cyclic alkyl groups having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl groups having 2 to 10 carbon atoms (for example, allyl, 2 -Butenyl, 3-pentenyl, 2-cyclohexenyl), having 2 to 10 carbon atoms Examples include a alkynyl group (for example, propargyl, 3-pentynyl), an aralkyl group having 7 to 12 carbon atoms (for example, benzyl), and the aryl group includes a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms (for example, Unsubstituted phenyl, 4-methylphenyl) and the like.

In general formula (VI), the alkyl group, alkenyl group, and alkynyl group represented by Rb3 and Rb4 are substituted or unsubstituted linear or branched alkyl groups having 1 to 10 carbon atoms (for example, methyl, ethyl, isopropyl). , N-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, methoxyethyl, ethoxyethoxy Ethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group having 2 to 10 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl, 2- Cyclohexenyl), an alkynyl group having 2 to 10 carbon atoms (for example, propargyl, 3 Pentynyl), an aralkyl group having 7 to 12 carbon atoms (for example, benzyl) and the like. As the aryl group, a substituted or unsubstituted phenyl group having 6 to 12 carbon atoms (for example, unsubstituted phenyl, 4-methylphenyl) And substituted or unsubstituted naphthyl having 10 to 16 carbon atoms (for example, unsubstituted naphthyl).
Rb1 or Rb2 and Rb3 or Rb4 may be linked to form a ring.

  In general formula (VI), as the alkyl group, alkenyl group, and alkynyl group represented by Rb5, a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, n -Propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl, 2-ethylhexyl, 2-hydroxyethyl, diethylaminoethyl), substituted or unsubstituted 3 to 6 carbon atoms Cyclic alkyl groups (for example, cyclopropyl, cyclopentyl, cyclohexyl), alkenyl groups having 2 to 10 carbon atoms (for example, allyl, 2-butenyl, 3-pentenyl, 2-cyclohexenyl), alkynyl groups having 2 to 10 carbon atoms ( For example, propargyl, 3-pentynyl), an aralkyl group having 7 to 12 carbon atoms (for example, benzyl) and the like. As the aryl group, a substituted or unsubstituted phenyl group having 6 to 16 carbon atoms (for example, unsubstituted phenyl, 4-methylphenyl, 4- (2-hydroxyethyl) -phenyl, 4-sulfophenyl, 4- Chlorophenyl, 4-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-carboxyphenyl, 2,5-dimethylphenyl, 4-dimethylaminophenyl, 4- (3-carboxypropionylamino) -phenyl, 4-methoxyphenyl , 2-methoxyphenyl, 2,5-dimethoxyphenyl, 2,4,6-trimethylphenyl), and naphthyl having 10 to 16 carbon atoms (for example, unsubstituted naphthyl group, 4-methylnaphthyl), and heterocyclic groups Examples include pyridyl, furyl, imidazolyl, piperidyl, and morpholyl. It is done.

  Further, in the general formula (VI), Rb1, Rb2, Rb3, Rb4 and Rb5 may further have a substituent Yy shown below. Examples of the substituent Yy include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkyl group (eg, methyl, ethyl, isopropyl, n-propyl, t-butyl), an alkenyl group (eg, allyl, 2 -Butenyl), alkynyl groups (eg propargyl), aralkyl groups (eg benzyl), aryl groups (eg phenyl, naphthyl, 4-methylphenyl), heterocyclic groups (eg pyridyl, furyl, imidazolyl, piperidinyl, morpholyl) ), Alkoxy groups (for example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy), aryloxy groups (for example, phenoxy, 2-naphthyloxy), amino groups (for example, unsubstituted amino, dimethylamino) , Diethylamino, dipropi Amino, dibutylamino, ethylamino, anilino), acylamino group (eg, acetylamino, benzoylamino), ureido group (eg, unsubstituted ureido, N-methylureido), urethane group (eg, methoxycarbonylamino, phenoxycarbonylamino) ), Sulfonylamino groups (eg, methylsulfonylamino, phenylsulfonylamino), sulfamoyl groups (eg, unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), carbamoyl groups (eg, unsubstituted) Carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl), sulfonyl group (eg, mesyl, tosyl), sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), alkyloxy Rubonyl group (eg methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl), acyl group (eg acetyl, benzoyl, formyl, pivaloyl), acyloxy group (eg acetoxy, benzoyloxy), phosphoric acid Amide group (for example, N, N-diethylphosphoric acid amide), cyano group, sulfo group, thiosulfonic acid group, sulfinic acid group, carboxy group, hydroxy group, phosphono group, nitro group, ammonio group, phosphonio group, hydrazino group, A thiazolino group is mentioned. Moreover, when there are two or more substituents, they may be the same or different, and the substituents may further have a substituent.

  In general formula (VI), Rb1 and Rb2 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms. Rb3 and Rb4 are each independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted phenyl group having 6 to 10 carbon atoms, and Rb5 is It is preferable that it is a C6-C12 substituted or unsubstituted phenyl group, and the molecular weight of the compound represented by general formula (VI) is 350 or less.

Furthermore, in general formula (VI), Rb1 and Rb2 are substituted or unsubstituted linear alkyl groups having 1 to 3 carbon atoms, Rb3 and Rb4 are hydrogen atoms, and Rb5 is a substituted 6 to 10 carbon atoms. Or it is more preferable that it is an unsubstituted phenyl group and the molecular weight of the compound represented by general formula (VI) is 300 or less. Further, in the general formula (VI), it is most preferable that the total number of carbon atoms of Rb1 to Rb5 is 11 or less.
Although the specific example of a compound represented by general formula (VI) below is given, this invention is not limited to these.

  The compound represented by the general formula (VI) is easily available as a commercially available chemical or as a compound synthesized from a commercially available chemical by a known method. As a synthesis method of the general formula (VI), Journal of Chemical Society (J. Chem. Soc.), Page 408 (1954), US Pat. No. 2,743,279 (1953), US Pat. No. 2,772 , 282 (1953), etc., or a method analogous thereto.

  The compound represented by the general formula (VI) is preferably added to the adjacent layer of the emulsion layer or other layers before or during coating of the coating solution and diffused in the emulsion layer. It can also be added before chemical sensitization, during chemical sensitization, or after completion of chemical sensitization during emulsion preparation. The compound represented by the general formula (VI) can be added to the sensitive layer or can be added to the non-photosensitive layer.

The preferred addition amount largely depends on the above-mentioned addition method and the kind of compound to be added, but generally 5 × 10 ⁻⁶ mol to 0.05 mol, more preferably 1 × 10 ⁻⁵ mol per mol of photosensitive silver halide. To 0.005 mol is used. When the amount is more than the above-mentioned amount, an adverse effect such as an increase in fog occurs and is not preferable.

  The compound represented by the general formula (VI) is preferably added after being dissolved in a water-soluble solvent. The pH may be lowered or raised with an acid or a base, or a surfactant may coexist. Moreover, it can also be dissolved in a high boiling point organic solvent and added as an emulsified dispersion, or may be added as a microcrystalline dispersion by a known dispersion method.

  The compound represented by formula (VII) will be described in further detail. First, the hydrazine structure represented by Rb6Rb7N-NRb8Rb9, which is preferably used as Hy, will be described in detail.

  Rb6, Rb7, Rb8 and Rb9 each represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb6 and Rb7, Rb8 and Rb9, Rb6 and Rb8, and Rb7 and Rb9 may be bonded to each other to form a ring, but they do not form an aromatic heterocycle (for example, pyridazine or pyrazole). However, at least one of Rb6, Rb7, Rb8 and Rb9 is an alkylene group, alkenylene group, alkynylene group, arylene group or divalent group for substitution by-(M) k2- (Het) k1 in the general formula (VII). It is a heterocyclic residue.

  Rb6, Rb7, Rb8 and Rb9 include, for example, an unsubstituted alkyl group, an alkenyl group, an alkynyl group having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, Hexyl, octyl, dodecyl, octadecyl, cyclopentyl, cyclopropyl, cyclohexyl, allyl, 2-butenyl), substituted alkyl groups having 1 to 18 carbon atoms, more preferably 1 to 8 carbon atoms, alkenyl groups, and alkynyl groups.

  Rb6 and Rb7, Rb8 and Rb9, Rb6 and Rb8, and Rb7 and Rb9 may be bonded to each other to form a ring. However, it does not form an aromatic heterocycle. These rings may be substituted with the above-mentioned substituent Yy, for example.

  More preferably, Rb6, Rb7, Rb8 and Rb9 are unsubstituted alkyl groups, alkenyl groups, alkynyl groups, substituted alkyl groups, alkenyl groups, alkynyl groups, and Rb6 and Rb7, Rb8, Rb9, Rb6 and Rb8, and Rb7 and Rb9. Are bonded to each other, and the atoms constituting the ring do not contain carbon atoms other than carbon atoms (for example, oxygen atoms, sulfur atoms, nitrogen atoms) {the alkylene group may be substituted (for example, the above-described substituent Yy). } Is formed.

  More preferably, Rb6, Rb7, Rb8 and Rb9 are when the carbon atom directly bonded to the nitrogen atom of hydrazine is an unsubstituted methylene group. Rb6, Rb7, Rb8 and Rb9 are particularly preferably an unsubstituted alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, butyl), a substituted alkyl group having 1 to 8 carbon atoms {for example, a sulfoalkyl group ( For example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl, 3-sulfobutyl), a carboxyalkyl group (eg, carboxymethyl, 2-carboxyethyl), a hydroxyalkyl group (eg, 2-hydroxyethyl)} and Rb6 and Rb7, Rb8 And Rb9, Rb6 and Rb8, and Rb7 and Rb9 are bonded to each other by an alkylene chain to form a 5-membered ring, 6-membered ring and 7-membered ring.

  The hydrazine group represented by Rb6Rb7N-NRb8Rb9 is substituted with at least one-(M) k2- (Het) k1. The substitution position may be any of Rb6, Rb7, Rb8 and Rb9.

Furthermore, the compound represented by Rb6Rb7N-NRb8Rb9 used in the present invention is particularly preferred when it is a compound selected from the following general formulas (Hy-1), (Hy-2) and (Hy-3).

  In the formula, Rb39, Rb40, Rb41 and Rb42 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb39 and Rb40, and Rb41 and Rb42 may be bonded to each other to form a ring.

Z ₄ represents an alkylene group having 4, 5 or 6 carbon atoms. Z ₅ represents an alkylene group having 2 carbon atoms. Z ₆ represents an alkylene group having 1 or 2 carbon atoms. Z ₇ and Z ₈ represent an alkylene group having 3 carbon atoms. L ₃ and L ₄ represent a methine group.

  In the general formulas (Hy-1), (Hy-2), and (Hy-3), at least one-(M) k2- (Het) k1 is substituted. More preferred is a compound selected from general formulas (Hy-1) and (Hy-2), and particularly preferred is a compound selected from general formula (Hy-1).

  The general formula (Hy-1) will be described in detail below. Rb39 and Rb40 have the same meanings as Rb6, Rb7, Rb8 and Rb9, and preferred ranges are also the same. Particularly preferred is the case where an alkyl group and Rb39 and Rb40 are bonded to each other to form an unsubstituted tetramethylene group or a pentamethylene group.

Z ₄ represents an alkylene group having 4, 5 or 6 carbon atoms, preferably an alkylene group having 4 or 5 carbon atoms. However, the oxo group is not substituted on the carbon atom directly bonded to the nitrogen atom of hydrazine. The alkylene group may be unsubstituted or substituted. Examples of the substituent include the aforementioned substituent Yy, and the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene group. Z4 is particularly preferably an unsubstituted tetramethylene group or an unsubstituted pentamethylene group. The hydrazine group represented by the general formula (Hy-1) is substituted with at least one-(M) k2- (Het) k1. The substitution position may be any of Rb39, Rb40 and Z4. Rb39 and Rb40 are preferable.

The general formula (Hy-2) will be described in detail below. Rb41 and Rb42 are synonymous with Rb6, Rb7, Rb8 and Rb9, and the preferred ranges are also the same. Particularly preferred is the case where an alkyl group and Rb41 and Rb42 are bonded to each other to form a trimethylene group. Z ₅ represents an alkylene group having 2 carbon atoms. Z ₆ represents an alkylene group having 1 or 2 carbon atoms. These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the aforementioned substituent Yy. More preferably, Z5 is an unsubstituted ethylene group. Z ₆ is more preferably an unsubstituted methylene group or an ethylene group. L ₃ and L ₄ represent substituted and unsubstituted methine groups. Examples of the substituent include the aforementioned substituent Yy, and an unsubstituted alkyl group (for example, a methyl group or a t-butyl group) is preferable. More preferred is an unsubstituted methine group. The hydrazine group represented by formula (Hy-2) is substituted with at least one-(M) k2- (Het) k1. The substitution position may be any of Rb41, Rb42, Z ₅ , Z ₆ , L ₃ and L ₄ . Rb41 and Rb42 are preferred.

The general formula (Hy-3) will be described in detail. Z ₇ and Z ₈ each independently represents an alkylene group having 3 carbon atoms. However, the oxo group is not substituted on the carbon atom directly bonded to the nitrogen atom of hydrazine. These alkylene groups may be unsubstituted or substituted. Examples of the substituent include the aforementioned substituent Yy, and the carbon atom directly bonded to the nitrogen atom of hydrazine is preferably an unsubstituted methylene group. Z ₇ and Z ₈ are particularly preferably an unsubstituted trimethylene and a trimethylene group substituted with an unsubstituted alkyl group (for example, 2,2-dimethyltrimethylene). The hydrazine group represented by the general formula (Hy-3) is substituted with at least one-(M) k2- (Het) k1. The substitution position may be either Z ₇ or Z ₈ .

  In the general formula (VII), the group represented by Het preferably has any of the following structures (i) to (v).

(i) 5-, 6- or 7-membered heterocycle having 2 or more heteroatoms
(ii) a 5-, 6- or 7-membered nitrogen-containing heterocycle represented by the following A having a quaternary nitrogen atom
(iii) a 5-, 6- or 7-membered nitrogen-containing heterocycle represented by the following B having a thioxo group
(iv) 5-, 6- or 7-membered nitrogen-containing heterocycle represented by C
(v) 5-, 6- or 7-membered nitrogen-containing heterocycle represented by D and E below

  Ra is preferably exemplified by the alkyl groups, alkenyl groups and alkynyl groups of Rb6, Rb7, Rb8 and Rb9 described above.

The nitrogen-containing heterocyclic ring containing Zc as a ring constituent atom contains at least one nitrogen atom, and may contain a hetero atom other than the nitrogen atom (for example, an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom). Good 5-membered, 6-membered or 7-membered heterocycles, preferably azole rings (eg imidazole, triazole, tetrazole, oxazole, thiazole, selenazole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, thiadiazole, oxadiazole Benzoselenazole, pyrazole, naphthothiazole, naphthimidazole, naphthoxazole, azabenzimidazole, purine), pyrimidine ring, triazine ring, azaindene ring (eg, triazaindene, tetrazaindene, pentaazaindene) And the like.
However, at least one-(M) k2- (Hy) is substituted on the group represented by Het.

Further preferred as Het are compounds represented by the following general formulas (Het-a), (Het-b), (Het-c), (Het-d) and (Het-e).

In the formula, Rb43, Rb44, Rb45, Rb46, Rb47 and Rb48 each independently represent a hydrogen atom or a monovalent substituent. Rb49 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X ₁ represents a hydrogen atom, an alkali metal atom, an ammonium group or a blocking group. Y ₁ is an oxygen atom, a sulfur atom,>NH,> N- (L 4) p 3 -R b 53, L ₃ and L ₄ represent a divalent linking group, and R b 50 and R b 53 represent a hydrogen atom, an alkyl group, and an alkenyl group. Represents an alkynyl group, an aryl group or a heterocyclic group. X ₂ has the same meaning as X ₁ . p2 and p3 are each independently an integer of 0 to 3. Preferably, p2 and p3 are 1.

Z ₉ represents an atomic group necessary for forming a 5-membered or 6-membered nitrogen-containing heterocyclic ring. Rb51 represents an alkyl group, an alkenyl group, or an alkynyl group. Rb52 represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. However, in the general formulas (Het-a) to (Het-e), at least one-(M) k2- (Hy) is substituted. However, X ₁ and X ₂ in the general formulas (Het-c) and (Het-d) are not substituted. Of the general formulas (Het-a) to (Het-e), the general formulas (Het-a), (Het-c) and (Het-d) are preferable, and the general formula (Het-c) is more preferable. It is.

Next, the general formulas (Het-a) to (Het-e) will be described in more detail.
Rb43, Rb44, Rb45, Rb46, Rb47 and Rb48 each independently represents a hydrogen atom or a monovalent substituent. Examples of the monovalent substituent include Rb6, Rb7, Rb8, Rb9 and the substituent Yy described above. More preferably, a lower alkyl group (preferably a substituted or unsubstituted one having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, methoxyethyl, hydroxyethyl, hydroxy Methyl, vinyl, allyl), carboxy group, alkoxy group (preferably substituted or unsubstituted having 1 to 5 carbon atoms, such as methoxy, ethoxy, methoxyethoxy, hydroxyethoxy), aralkyl group (preferably substituted or unsubstituted) Those having 7 to 12 carbon atoms, such as benzyl, phenethyl, phenylpropyl), aryl groups (preferably substituted or unsubstituted having 6 to 12 carbon atoms, such as phenyl, 4-methylphenyl, 4-methoxyphenyl) , Heterocyclic groups (eg 2-pyridyl), alkylthio groups (preferably A substituted or unsubstituted one having 1 to 10 carbon atoms, such as methylthio, ethylthio), an arylthio group (preferably a substituted or unsubstituted one having 6 to 12 carbon atoms such as phenylthio), an aryloxy group (preferably a substituted or unsubstituted one). A substituted one having 6 to 12 carbon atoms (for example, phenoxy), an alkylamino group having 3 or more carbon atoms (for example, propylamino, butylamino), an arylamino group (for example, anilino), a halogen atom (for example, a chlorine atom, Bromine atom, fluorine atom), or the following substituents.

Here, L ₅ , L ₆ and L ₇ each represent a linking group represented by an alkylene group (preferably having 1 to 5 carbon atoms, such as methylene, propylene, 2-hydroxypropylene). Rb54 and Rb55 may be the same or different and are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group (preferably a substituted or unsubstituted one having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl , N-butyl, t-butyl, n-octyl, methoxyethyl, hydroxyethyl, allyl, propargyl), aralkyl group (preferably substituted or unsubstituted having 7 to 12 carbon atoms, such as benzyl, phenethyl, vinylbenzyl ), An aryl group (preferably a substituted or unsubstituted one having 6 to 12 carbon atoms, such as phenyl, 4-methylphenyl), or a heterocyclic group (for example, 2-pyridyl).

  The alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group of Rb49 may be unsubstituted or substituted. Preferred examples include the substituents mentioned as Rb6, Rb7, Rb8, Rb9 and Yy.

  More preferably, a halogen atom (for example, chlorine atom, bromine atom, fluorine atom), nitro group, cyano group, hydroxy group, alkoxy group (for example, methoxy), aryl group (for example, phenyl), acylamino group (for example, propionylamino), alkoxy Carbonylamino group (eg methoxycarbonylamino), ureido group, amino group, heterocyclic group (eg 2-pyridyl), acyl group (eg acetyl), sulfamoyl group, sulfonamido group, thioureido group, carbamoyl group, alkylthio group (eg Methylthio), arylthio groups (for example, phenylthio, heterocyclic thio groups (for example, 2-benzothiazolylthio), carboxylic acid groups, sulfo groups, or salts thereof) The above ureido groups, thioureido groups, sulfamoyl groups , Cal A moyl group and an amino group each include an unsubstituted group, an N-alkyl-substituted group, and an N-aryl-substituted group, and examples of the aryl group include a phenyl group and a substituted phenyl group. Examples thereof include Rb6, Rb7, Rb8, Rb9, and a substituent Yy.

The alkali metal atom represented by X ₁ and X ₂ is, for example, a sodium atom or a potassium atom, and the ammonium group is, for example, tetramethylammonium or trimethylbenzylammonium. The blocking group is a group that can be cleaved under alkaline conditions, and represents, for example, acetyl, cyanoethyl, or methanesulfonylethyl.

Specific examples of the divalent linking group represented by L ₃ and L ₄ include the following linking groups. These linking groups are preferably used alone, but may be combined. When combined, the total carbon number is preferably 0-20.

Rb56, Rb57, Rb58, Rb59, Rb60, Rb61, Rb62, Rb63, Rb64 and Rb65 each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group (preferably a substituted or unsubstituted C1-4 carbon atom. Represents, for example, methyl, ethyl, n-butyl, methoxyethyl, hydroxyethyl, allyl) or an aralkyl group (preferably substituted or unsubstituted having 7 to 12 carbon atoms, such as benzyl, phenethyl, phenylpropyl) .
Rb50 and Rb53 are preferably the same as those described above for Rb49.

As the heterocyclic group having Z ₉ as a ring constituent atom, thiazoliums {for example, thiazolium, 4-methylthiazolium, benzothiazolium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5 -Methoxybenzothiazolium, 6-methylbenzothiazolium, 6-methoxybenzothiazolium, naphtho [1,2-d] thiazolium, naphtho [2,1-d] thiazolium}, oxazoliums {eg oxazolium, 4-methyloxazolium, benzoxazolium, 5-chlorobenzoxazolium, 5-phenylbenzoxazolium, 5-methylbenzoxazolium, naphtho [1,2-d] oxazolium}, imidazoliums {Eg 1-methylbenzimidazolium, 1-propyl-5-chloroben Imidazolium, 1-ethyl-5,6-cyclobenzoimidazolium, 1-allyl-5-trifluoromethyl-6-chloro-benzimidazolium), selenazoliums {eg benzoselenazolium, 5-chlorobenzoselena Zorium, 5-methylbenzoselenazolium, 5-methoxybenzoselenazolium, naphtho [1,2-d] selenazolium} and the like. Particularly preferred are thiazoliums (for example, benzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, naphtho [1,2-d] thiazolium).

  Rb51 and Rb52 are preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 18 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl), or a substitution having 2 to 18 carbon atoms Alkyl group {for example, vinyl group, carboxy group, sulfo group, cyano group, halogen atom (for example, fluorine, chlorine, bromine), hydroxy group, C1-C8 alkoxycarbonyl group (for example, methoxycarbonyl as a substituent) , Ethoxycarbonyl, phenoxycarbonyl, benzyloxycarbonyl), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, benzyloxy, phenethyloxy), a monocyclic aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, p-tolyloxy), C1-C3 acylo A xyl group (for example, acetyloxy, propionyloxy), an acyl group having 1 to 8 carbon atoms (for example, acetyl, propionyl, benzoyl, mesyl), a carbamoyl group (for example, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl) ), Sulfamoyl groups (for example, sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), aryl groups having 6 to 10 carbon atoms (for example, phenyl, 4-chlorophenyl, 4-methylphenyl, α- Naphthyl) -substituted alkyl group having 1 to 18 carbon atoms}. However, Rb51 is not a hydrogen atom. More preferably, Rb51 is an unsubstituted alkyl group (eg, methyl, ethyl) or an alkenyl group (eg, allyl group), and Rb52 is a hydrogen atom or an unsubstituted lower alkyl group (eg, methyl, ethyl).

  M1 and m1 are included in the formula to indicate the presence or absence of a cation or anion when necessary to neutralize the ionic charge of the compound represented by the general formula (Het-e). It has been. Whether a certain dye is a cation, an anion, or has a net ionic charge depends on its auxiliary color groups and substituents. Typical cations are inorganic or organic ammonium ions and alkali metal ions, while the anions may specifically be either inorganic or organic anions, such as halogen anions (eg, fluorine ions, Chlorine ion, bromine ion, iodine ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene disulfonate ion), 1 , 5-naphthalenedisulfonic acid imide, 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (for example, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, Acetate ion, trifluoromethane Sulfonic acid ions. Ammonium ion, iodine ion, bromine ion, and p-toluenesulfonic acid ion are preferable.

Each of the nitrogen-containing heterocycles represented by the general formulas (Het-a) to (Het-e) is substituted with at least one-(M) k2- (Hy). The substitution positions are Rb43, Rb44, Rb45, Rb46, Rb47, Rb48, Rb49, Rb50, Rb51, Y ₁ , L ₃ and Z ₉ .

  In the general formula (VII), M represents a divalent linking group composed of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom, and an oxygen atom. Preferably, an alkylene group having 1 to 8 carbon atoms (for example, methylene, ethylene, propylene, butylene, pentylene), an arylene group having 6 to 12 carbon atoms (for example, phenylene, naphthylene), an alkenylene group having 2 to 8 carbon atoms ( For example, ethynylene, propenylene), amide group, ester group, sulfoamide group, sulfonic acid ester group, ureido group, sulfonyl group, sulfinyl group, thioether group, ether group, carbonyl group, -N (R0)-(R0 is a hydrogen atom) Represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group), a divalent heterocyclic residue (for example, 6-chloro-1,3,5-triazine-2,4-diyl, pyrimidine) -2,4-diyl, quinoxaline-2,3-diyl) in combination with one or more carbon atoms having 4 to 4 carbon atoms It represents a divalent linking group 0. More preferred are a ureido group, an ester group and an amide group.

  In the general formula (VII), k1 and k3 are preferably 1 or 2. More preferably, k1, k2 and k3 are all 1. When k1 or k3 is 2 or more, Hy and Het may be the same or different.

Among the compounds represented by the general formula (VII) of the present invention, more preferable compounds are the following general formulas (VII-A), (VII-B), (VII-C), (VII-D) and (VII-E). ).

Furthermore, a particularly preferable compound in the present invention is represented by the following general formula (VII-F).

In the formula, Ma has the same meaning as M in formula (VII). Zd has the same meaning as Z ₄ in the general formula (Hy-1). Rb69 represents a monovalent substituent. Rb66 represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Rb67 and Rb68 each independently represents a hydrogen atom or a monovalent substituent. n1 represents an integer of 0 to 4. n2 represents 0 or 1. n3 represents an integer of 1-6. X ₁ has the same meaning as X ₁ in the general formula (Het-c). Y _1, L _3, p2 is Y ₁ in formula _{(Het-d), L 3} , p2 and respectively the same. Rb51 is synonymous with Rb51 in the general formula (Het-e). When n1 and n3 are 2 or more, Rb69 and C (Rb67) (Rb68) are repeated, but need not be the same.

More specifically, Ma is preferably the same as M in formula (VII), and more preferably a ureido group, an ester group or an amide group. Zd is of the general formula similar to Z ₄ of (Hy-1) is preferably used, more preferably an unsubstituted tetramethylene group, pentamethylene group. Rb69 is preferably the same as Rb43. Rb66 is preferably the same as Rb6, Rb7, Rb8 and Rb9, and particularly preferably an unsubstituted alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl). Rb67 and Rb68 are preferably the same as Rb43, and particularly preferably a hydrogen atom. n1 is preferably 0 or 1. n2 is preferably 1. n3 is preferably 2-4.
Next, typical examples of the compound used in the present invention will be given, but the present invention is not limited thereto.

  Het of the general formula (VII) used in the present invention is described in U.S. Pat. No. 3,266,897, Belgian Patent No. 671,402, JP-A-60-138548, JP-A-59-68732, JP JP 59-123838, JP-B 58-9939, JP 59-137951, JP 57-202531, JP 57-164734, JP 57-14836, JP 57- 116340, U.S. Pat. No. 4,418,140, JP 58-95728, JP 55-79436, OLS 2,205,029, OLS 1,962,605, JP 55-59463 JP-B-48-18257, JP-B-53-28084, JP-A-53-48723, JP-B-59-52414, JP-A-58-217929, JP-B-49-8334 U.S. Pat. No. 3,598,602, U.S. Pat. No. 887,009, British Patent 965,047, Belgian Patent 737809, U.S. Pat. No. 3,622,340, JP-A-60-87322. JP 57-211112, JP 58-158631, JP 59-15240, US Pat. No. 3,671,255, JP 48-34166, JP 48-322112, JP 58-221839, JP-B 48-32367, JP-A 60-130731, JP-A 60-122936, JP-A 60-117240, US Pat. No. 3,228,770, JP-B 43- No. 13496, JP-B 43-10256, JP-B 47-8725, JP-B 47-30206, JP-B 47-4417, JP-B 51-25340, UK National Patent 1,165,075, U.S. Patent 3,512,982, U.S. Patent 1,472,845, Japanese Patent Publication No. 39-22067, Japanese Patent Publication No. 39-22068, US Patent No. 3,148,067, US Pat. No. 3,759,901, US Pat. No. 3,909,268, JP-B-50-40665, JP-B-39-2829, US Pat. No. 3,148,066, JP-B-45-22190, US patent 1,399,449, British Patent 1,287,284, US Patent 3,900,321, US Patent 3,655,391, US Patent 3,910,792, British Patent 1,064,805 US Patent 3,544,336, US Patent 4,003,746, British Patent 1,344,525, British Patent 972,211, Japanese Patent Publication No. 43-4136, US Patent 3 140,178, French Patent 2,015,456, US Patent 3,114,637, Belgian Patent 681,359, US Patent 3,220,839, British Patent 1,290,868, US Patent 3,137,578, US 3,420,670, US 2,759,908, US 3,622,340, OLS 2,501,261, DAS 1,772,424, US Patent 3,157,509, French Patent 1,351,234, US Patent 3,630,745, French Patent 2,005,204, German Patent 1,447,796, US Patent 3 915,710, JP 49-8334, British Patent 1,021,199, British Patent 919,061, JP 46-17513, US Pat. No. 3,202,512, OL No. 2,553,127, JP-A-50-104927, French Patent 1,467,510, US Patent 3,449,126, US Patent 3,503,936, US Patent 3,576,638 French Patent 2,093,209, British Patent 1,246,311, US Patent 3,844,788, US Patent 3,535,115, British Patent 1,161,264, US Patent US Pat. No. 3,841,878, US Pat. No. 3,615,616, JP-A-48-39039, British Patent 1,249,077, JP-B 48-34166, US Pat. No. 3,671,255, UK Japanese Patent No. 1459160, Japanese Patent Laid-Open No. 50-6323, British Patent No. 1,402,819, OLS 2,031,314, Research Disclosure 13651, US Pat. No. 3,910,791 No. 3, U.S. Pat. No. 3,954,478, U.S. Pat. No. 3,813,249, British Patent No. 1,387,654, JP-A-57-135945, JP-A-57-96331, JP-A-57- 22234, JP 59-26731 A, OLS 2,217,153, British Patent 1,394,371, British Patent 1,308,777, British Patent 1,389,089, British Patent 1,347 544, German Patent 1,107,508, US Patent 3,386,831, British Patent 1,129,623, JP 49-14120, JP 46-34675, JP 50-43923, U.S. Patent 3,642,481, British Patent 1,269,268, U.S. Patent 3,128,185, U.S. Patent 3,295,981, U.S. Patent 3,396,023, Japanese Patent No. 2,895,827, Japanese Patent Publication No. 48-38418, Japanese Unexamined Patent Publication No. 48-47335, Japanese Unexamined Patent Publication No. 50-87028, US Pat. No. 3,236,652, US Pat. No. 3,443,951, British Patent 1,065,669, US Patent 3,312,552, US Patent 3,310,405, US Patent 3,300,312, British Patent 952,162, British Patent 952,162, British Patent 948,442, JP-A 49-120628, JP-B 48-35372, JP-B 47-5315, JP-B 39-18706, JP-B 43-4941, JP-A 59-34530 It can be synthesized with reference to these.

  Hy in the general formula (VII) of the present invention can be synthesized by various methods. For example, it can be synthesized by a method of alkylating hydrazine. Alkylation methods include substitution alkylation using alkyl halide and sulfonic acid alkyl ester, reductive alkylation using carbonyl compound and sodium cyanoborohydride, and hydrogenation after acylation. A method of reducing using lithium aluminum is known. For example, SR Sandler, W. Karo, “Organic Functional Group Preparation” Volume 1, Chapter 14, pages 434-465 (1968), Journal of The American Chemical Society, Vol. 112, No. 13, published by Academic Press, EL Clennan, etc. 5080 (1990), etc., and can be synthesized by referring to them.

  Moreover, methods known in organic chemistry can be used for bond formation reactions including amide bond formation reaction and ester bond formation reaction of-(M) k2- (Hy) moiety. That is, a method of linking Het and Hy, a method of synthesizing Het after linking Hy to a synthetic raw material and intermediate of Het, and conversely, Hy is synthesized after linking the synthetic raw material of Hy and the intermediate to the Het moiety. Any method such as a method may be used, and synthesis may be performed by appropriately selecting. For the synthesis reaction for these linkages, for example, the Chemical Society of Japan, New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds, Volume IV, Maruzen, Tokyo (1977), Yoshiro Ogata, Organic Reaction Theory , Maruzen, Tokyo (1962) LFFieser and M. Fieser, Advanced Organic Chemistry, Maruzen, Tokyo (1962), etc. More specifically, it can be synthesized by the method shown in Examples 1-2 of JP-A-7-135341.

  When added at the time of emulsion preparation, it can be added at any time during the process. For example, silver halide grain formation process, before desalting process start, desalting process, chemical ripening Examples include a process before starting, a chemical ripening process, and a process before preparing a finished emulsion. Moreover, it can also add in several steps in these processes. The compound represented by the general formula (VII) of the present invention is preferably added after being dissolved in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound having higher solubility when the pH is raised or lowered may be dissolved at a higher or lower pH and added.

The compound represented by formula (VII) is preferably used in the emulsion layer, but may be added to the protective layer or intermediate layer together with the emulsion layer and diffused during coating. The addition time of the compound represented by the general formula (VII) of the present invention is preferably 1 × 10 ^{−9 to} 5 × 10 ⁻² mol per mol of silver halide, more preferably before and after the sensitizing dye. Is contained in the silver halide emulsion at a ratio of 1 × 10 ^{−8 to} 2 × 10 ⁻³ mol.

  The compounds represented by the general formulas (VIII-1) and (VIII-2) are described in detail below. In the general formula (VIII-1), the substituent represented by Rb10, Rb11, Rb12 and Rb13 is an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20. For example, methyl, ethyl, iso- Propyl), an aralkyl group (preferably having a carbon number of 7 to 30, more preferably 7 to 20. For example, phenylmethyl), an alkenyl group (preferably having a carbon number of 2 to 20, more preferably 2 to 10. For example, allyl.) An alkoxy group (preferably having a carbon number of 1 to 20, more preferably 1 to 10. For example, methoxy or ethoxy.), An aryl group (preferably having a carbon number of 6 to 30, more preferably 6 to 20), an acylamino group (preferably Carbon number 2-30, more preferably 2-20, for example, acetylamino.), Sulfonylamino group (preferably 1-30 carbon atoms, more preferably 1 to 20. For example, methanesulfonylamino.), Ureido group (preferably 1 to 30 carbon atoms, more preferably 1 to 20. For example, methylureido), alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, more preferably). 2 to 20. For example, methoxycarbonylamino.), An aryloxycarbonylamino group (preferably 7 to 30 carbons, more preferably 7 to 20. For example, phenyloxycarbonylamino group), aryloxy groups (preferably carbon atoms). 6 to 30, more preferably 6 to 20. For example, phenyloxy.), Sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20, for example, methylsulfamoyl group), carbamoyl group (preferably having carbon number) 1-30, more preferably 1-20, for example carbamoyl, methylcal Moyl.), Mercapto group, alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20, for example, methylthio, carboxymethylthio), arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms). For example, phenylthio.), A sulfonyl group (preferably having a carbon number of 1 to 30, more preferably 1 to 20. For example, methanesulfonyl.), A sulfinyl group (preferably having a carbon number of 1 to 30, more preferably 1 to 20. For example, methane. Sulfinyl.), Hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxyl group, phosphono group, amino group (preferably having 0 to 30 carbon atoms, more preferably 1 to 20 carbon atoms). For example, methylamino.), Aryloxycarbonyl group (preferably having 7 to 3 carbon atoms) , More preferably 7 to 20. ), An acyl group (preferably having a carbon number of 2 to 30, more preferably 2 to 20. For example, acetyl, benzoyl.), An alkoxycarbonyl group (preferably having a carbon number of 2 to 30, more preferably 2 to 20. For example, methoxycarbonyl. ), An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20, for example, acetoxy), a nitro group, a hydroxamic acid group, a heterocyclic group (for example, pyridyl, furyl, thienyl) and the like. Moreover, these substituents may be further substituted.

  Preferred as the substituents represented by Rb10, Rb11, Rb12 and Rb13 are alkyl groups, alkoxy groups, hydroxy groups, halogen atoms, sulfo groups, carboxyl groups, acylamino groups, sulfonylamino groups, ureido groups, alkoxycarbonylamino groups. , Aryloxycarbonylamino group, alkylthio group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group, halogen atom, sulfo group, carboxyl group, acylamino group, sulfonylamino group, ureido group, alkoxy group A carbonylamino group and an aryloxycarbonylamino group, particularly preferably an alkyl group, a halogen atom, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, an aryloxycarbonyl group. An amino group.

Of Rb10, Rb11, Rb12 and Rb13, preferably 1 or more and 3 or less are hydrogen atoms, and more preferably 2 or more and 3 or less are hydrogen atoms. Particularly preferred is the case of 3 hydrogen atoms. Rb10 and Rb13 do not take substituents having exactly the same carbon number when they are alkyl groups at the same time. For _{example, Rb10 = t-C 8 H} 17, Rb13 = n-C 15 H 31 is likely never simultaneously Rb10, a Rb13 both t-C ₈ H _17. In the case of the same type of substituent, the difference in carbon number between the substituents of Rb10 and Rb13 is preferably 5 or more, more preferably 10 or more. Rb11 and Rb12 are the same as Rb10 and Rb13.

Of the compounds represented by the general formula (VIII-1), the general formula (VIII-1-a) is preferable, the general formula (VIII-1-b) is more preferable, and the (VIII-a) is particularly preferable. 1-c).

In the formula, Rb31 and Rb34 have the same meanings as Rb10 and Rb13 in formula (VIII-1), respectively, and the preferred ranges are also the same.

In the formula, Rb31 has the same meaning as Rb10 in formula (VIII-1), and the preferred range is also the same.

  In the formula, Rb70 is an alkyl group which may have a substituent. As the substituent which this alkyl group may have, those exemplified as the substituent represented by Rb31 can be applied.

  In the general formula (VIII-2), examples of the substituent represented by Rb14, Rb15 and Rb16 include the substituents which the substituents represented by Rb10, Rb11, Rb12 and Rb13 may have. . Preferred examples of the substituent represented by Rb14 include alkyl groups, alkoxy groups, hydroxy groups, halogen atoms, sulfo groups, carboxyl groups, acylamino groups, sulfonylamino groups, ureido groups, alkoxycarbonylamino groups, and aryloxycarbonylamino groups. , Alkylthio group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group, halogen atom, sulfo group, carboxyl group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, particularly preferably an alkyl group, a halogen atom, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, or an aryloxycarbonylamino group.

  Preferable substituents represented by Rb15 are alkyl groups, alkoxy groups, hydroxy groups, halogen atoms, acylamino groups, sulfonylamino groups, ureido groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups, alkylthio groups, arylthio groups. An amino group, an acyloxy group, more preferably an alkyl group, an alkoxy group, a hydroxy group, an acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group, particularly preferably an alkyl group, An acylamino group, a sulfonylamino group, a ureido group, an alkoxycarbonylamino group, and an aryloxycarbonylamino group;

  Preferable substituents represented by Rb16 are alkyl groups, alkoxy groups, hydroxy groups, halogen atoms, sulfo groups, carboxyl groups, acylamino groups, sulfonylamino groups, ureido groups, alkoxycarbonylamino groups, aryloxycarbonylamino groups. , Alkylthio group, arylthio group, amino group, acyloxy group, more preferably alkyl group, alkoxy group, halogen atom, sulfo group, carboxyl group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group, aryloxy A carbonylamino group, particularly preferably an alkyl group.

  Z represents a nonmetallic atom group necessary for forming a 4- to 6-membered ring. The nonmetallic atom is preferably a carbon atom, oxygen atom, nitrogen atom or sulfur atom, more preferably a carbon atom or oxygen atom, and particularly preferably a carbon atom. Moreover, the number of preferable ring members is 5 or 6, More preferably, it is a 6-membered ring. The ring may have a substituent, and examples of the substituent include those exemplified as the substituent represented by Rb14. The substituent is preferably an alkyl group, an alkenyl group, or an alkoxy group, and more preferably an alkyl group or an alkenyl group. These substituents may further have a substituent.

Of the compounds represented by the general formula (VIII-2), the compound represented by the general formula (VIII-2-a) is preferable, and the compound represented by the general formula (VIII-2-b) is more preferable.

In the formula, Rb14, Rb15 and Rb16 have the same meanings as those in formula (VIII-2), and preferred ranges are also the same. n represents 1 or 2. Rb71 and Rb72 each represents an alkyl group, an alkenyl group, or an alkoxy group.

  In the formula, Rb14, Rb15 and Rb16 have the same meanings as those in formula (VIII-2), and preferred ranges are also the same. Rb71 represents an alkyl group, an alkenyl group, or an alkoxy group. n is preferably 2. The alkyl group and alkenyl group represented by Rb71 and Rb72 may be linear, branched or cyclic, and preferably linear or branched. Moreover, a preferable carbon number is 1-30, More preferably, it is 1-20. Examples of the alkyl group include methyl, ethyl, and iso-propyl, and examples of the alkenyl group include allyl. In the alkoxy group represented by Rb71 and Rb72, the alkyl moiety may be linear, branched or cyclic, and Rb71 and Rb72 may form a ring like spirochromans. Preferably it is C1-C20, More preferably, it is 1-10. Examples include methoxy and ethoxy.

Specific examples of the compounds represented by the general formulas (VIII-1) and (VIII-2) are shown below, but are not limited thereto.

  Compounds represented by general formula (VIII-1) and general formula (VIII-2) are, for example, US Pat. Nos. 2,728,659, 2,549,118, 2,732,300, Journal of American Chemical Society 111, 20, 1989, 7932 (Journal of American Chemical Society, 111, 20, 1989, 7932), Synthesis, 12, 1995, 1549 (Synthesis, 12, 1995, 1549), QJ Pharm, Pharmacol., 17, 1944, 325, Chem. Pharm, Bull., 14, 1966, 1052, Chem. Pharm, Bull., 16, 1968, 853 etc. .

  The compounds represented by the general formula (VIII-1) and general formula (VIII-2) are, for example, U.S. Pat. Nos. 2,421,811, 2,421,812, 2,411,967, 681,371, J. Amer. Chem. Soc., 65, 1943, 1276, J. Amer. Chem. Soc., 65, 1943, 1281, J. Amer. Chem. Soc., 63, 1941, 1887, J Amer. Chem. Soc., 107, 24, 1985, 7053, Helv. Chim. Acta., 21, 1938, 939, Helv. Chim. Acta., 28, 1945, 438, Chem. Ber., 71, 1938 , 2637, J. Org. Chem., 4, 1939, 311, J. Org. Chem., 6, 1941, 229, J. Chem. Soc., 1938, 1382, Helv. Chim. Acta., 21, 1931 , 1234, Tetrahedron Lett., 33, 26, 1992, 3795, J. Chem. Soc. Perkin. Trans. 1, 1981, 1437, Synthesis, 6, 1995, 693, etc. it can.

  The compounds represented by formulas (VIII-1) and (VIII-2) of the present invention are preferably added as an emulsified dispersion by a known dispersion method. When emulsifying and dispersing, an additive generally used in the photographic industry such as a dye-forming coupler or a high-boiling organic solvent can be used together. It can also be added as a microcrystalline dispersion.

The amount of the compound represented by the formulas (VIII-1) and (VIII-2) of the present invention is 5 × 10 ⁻⁴ to 1 mol, more preferably 1 × 10 5 per mol of silver halide in the added emulsion layer. ^{-3 to} 5 x 10 ^-1 mol.

  The combination of the general formula (VII) and the compound of the general formula (VIII-1) or (VIII-2) is represented by the general formula (VII-F) and the general formula (VIII-1-b) or (VIII-2). A combination of compounds is preferred.

  In the present invention, the compound represented by the general formula (VII), the compound selected from the group consisting of the compounds represented by the general formulas (VIII-1) and (VIII-2), and the general formula (IX-1) , (IX-2) and a compound selected from the group consisting of compounds represented by (X) can be added to the same layer or to separate layers.

  The compound represented by formula (IX-1) will be described in more detail. In the formula, an alkyl group is a linear, branched, or cyclic alkyl group, which may have a substituent. In the general formula (IX-1), Rc1 is an alkyl group (preferably an alkyl group having 1 to 13 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl). , Hexadecyl, benzyl), a substituted or unsubstituted alkenyl group (preferably an alkenyl group having 2 to 14 carbon atoms such as allyl, 2-butenyl, isopropenyl, oleyl, vinyl), a substituted or unsubstituted aryl group (preferably Represents an aryl group having 6 to 14 carbon atoms, for example, phenyl or naphthyl). Rc2 represents a hydrogen atom or a group represented by Rc1. Rc3 represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (for example, methyl, i-butyl, cyclohexyl) or a substituted or unsubstituted alkenyl group (for example, vinyl, i-propenyl). The total number of carbon atoms contained in Rc1, Rc2 and Rc3 is 20 or less, and more preferably 12 or less. Examples of the substituent when Rc1 to Rc1 have a substituent include a hydroxy group, an alkoxy group, an aryloxy group, a silyl group, a silyloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, and an alkylamino group. , Arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, hydroxyamino group, heterocyclic ring Group and the like. Rc1 and Rc3 or Rc2 and Rc3 may be bonded to each other to form a 5- to 7-membered ring.

Among the compounds represented by the general formula (IX-1), those having a total carbon number of 20 or less are preferable, and 12 or less are more preferable.
Specific examples of the compound represented by formula (IX-1) of the present invention are shown below, but the present invention is not limited thereby.

  These compounds used in the present invention are described in J. Org. Chem., 27, 4054 ('62), J. Amer. Chem. Soc., 73, 2981 ('51), Japanese Examined Patent Publication No. 49-10492, etc. It can be easily synthesized by the method of or a method analogous thereto.

  In the present invention, the compound represented by the general formula (IX-1) may be added by dissolving it in water, a water-soluble solvent such as methanol, ethanol, or a mixed solvent thereof, or by emulsification and dispersion. Good. In the case of dissolving in water, those having higher solubility when the pH is raised or lowered may be dissolved at a higher or lower pH and added, or a surfactant may be allowed to coexist.

  In the present invention, the compound represented by formula (IX-1) is preferably added during the preparation of the emulsion. When added at the time of emulsion preparation, it can be added at any time during the process. For example, silver halide grain formation process, before desalting process start, desalting process, chemical ripening Examples include a process before starting, a chemical ripening process, and a process before preparing a finished emulsion. Moreover, it can also add in several steps in these processes. Preferably, it is added before chemical sensitization, during chemical sensitization, or after completion of chemical sensitization. Further, it can be added before coating the coating solution, or it can be added to the adjacent layer or other layers at the time of coating and diffused into the emulsion layer. Further, a dispersion and solution in an emulsion can be used by mixing with the emulsion.

In the present invention, the amount of the compound represented by the general formula (IX-1) is preferably 1 × per mole of light-sensitive silver halide, although the preferable amount depends largely on the above-described addition method and the type of compound to be added. 10 ⁻⁶ mol to 5 × 10 ⁻² mol are preferable, and 1 × 10 ⁻⁵ mol to 5 × 10 −3 mol are more preferable.

Next, the compound represented by formula (IX-2) of the present invention will be described in detail. G1 and G2 each represent a hydrogen atom or a monovalent substituent. Moreover, it may combine with each other to form a ring. Any monovalent substituent may be used, and Yy described above is preferable. Preferred is a compound selected from the following formulas (AI), (A-II), (A-III), (A-IV), and (AV).

In the general formula (AI), Rd1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. Rd2 represents a hydrogen atom or a group represented by Rd1. However, when Rd1 is an alkyl group, alkenyl group or aryl group, Rd2 is an acyl group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group or aryloxycarbonyl group. Rd1 and Rd2 may be bonded to each other to form a 5- to 7-membered ring. In the general formula (A-II), X represents a heterocyclic group, and Re1 represents an alkyl group, an alkenyl group or an aryl group. X and Re1 may be bonded to each other to form a 5- to 7-membered ring. In general formula (A-III), Y represents a nonmetallic atom group necessary for forming a 5-membered ring together with —N═C—. Y further represents a group of nonmetallic atoms necessary for forming a 6-membered ring together with the —N═C— group, and the end of Y bonded to the carbon atom of the —N═C— group is —N (Rf1) —. , -C (Rf2) (Rf3)-, -C (Rf4) =, -O-, -S- (bonded to the carbon atom of -N = C- on the left side of each group) Represents. Rf1 to Rf4 each represents a hydrogen atom or a substituent. In general formula (A-IV), Rg1 and Rg2 may be the same or different and each represents an alkyl group or an aryl group. However, when Rg1 and Rg2 are simultaneously unsubstituted alkyl groups and Rg1 and Rg2 are the same group, Rg1 and Rg2 are alkyl groups having 8 or more carbon atoms. In the general formula (A-V), Rh1 and Rh2 may be the same or different and are each a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, Represents an arylthio group, an alkyl group or an aryl group; However, Rh1 and Rh2 are not simultaneously -NHRh3 (Rh3 is an alkyl group or an aryl group). Rd1 and Rd2, X and Re1 may be bonded to each other to form a 5- to 7-membered ring. The inventors of the present invention have found that oxygen is related to one of the causes of photographic change due to storage of the photosensitive material and photographic change after photographing until development processing. Some compound in the light-sensitive material reacts with oxygen, which affects photographic properties, but the compounds represented by the above general formulas (AI) to (AV) are capturing this. It is estimated that there is not. Variation in photographic properties may be increased by increasing the amount of gelatin applied. This is presumed that a minute amount of impurities in gelatin reacts with oxygen, which affects photographic properties. Moreover, it turned out that a pressure tolerance can be improved with the compound represented by general formula (AI)-(AV). Hereinafter, the present invention will be described in more detail.

  The compounds represented by formulas (AI) to (AV) will be described in more detail.

  In these formulas, the alkyl group is a linear, branched or cyclic alkyl group, which may have a substituent. In the general formula (AI), Rd1 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl, decyl, dodecyl). Hexadecyl, benzyl), an alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms such as allyl, 2-butenyl, isopropenyl, oleyl, vinyl), an aryl group (preferably an aryl group having 6 to 40 carbon atoms) For example, phenyl, naphthyl), acyl group (preferably an acyl group having 2 to 36 carbon atoms such as acetyl, benzoyl, pivaloyl, α- (2,4-di-tert-amylphenoxy) butyryl, myristoyl, stearoyl, naphthoyl, m -Pentadecylbenzoyl, isonicotinoyl), alkyl or ants Rusulfonyl group (preferably alkyl having 1 to 36 carbon atoms or arylsulfonyl group having 6 to 36 carbon atoms such as methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkyl or arylsulfinyl group (preferably having 1 to 3 carbon atoms) 40 alkyl or 6 to 40 carbon arylsulfinyl groups such as methanesulfinyl, benzenesulfinyl), carbamoyl groups (including N-substituted carbamoyl groups, preferably 0 to 40 carbon atoms such as N-ethylcarbamoyl) N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl), sulfamoyl groups (including N-substituted sulfamoyl groups, preferably sulfamoyl groups having 1 to 40 carbon atoms such as N- Tilsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (preferably carbon A C2-C36 alkoxycarbonyl group such as methoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyloxycarbonyl, hexadecyloxycarbonyl) or an aryloxycarbonyl group (preferably a C7-40 aryloxycarbonyl group, For example, phenoxycarbonyl, naphthoxycarbonyl). Rd2 represents a hydrogen atom or a group represented by Rd1.

  In general formula (A-II), X is a heterocyclic group (a group that forms a 5- to 7-membered heterocyclic ring having at least one of a nitrogen atom, a sulfur atom, an oxygen atom, or a phosphorus atom as a ring-constituting atom. The bond position of the heterocyclic ring (position of monovalent group) is preferably a carbon atom, such as 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, pyridine-2- Yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl, imidazolyl, 1,2,4-triazol-3-yl, benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinoline-2- Il). Re1 represents an alkyl group, an alkenyl group or an aryl group in the same meaning as Rd1 in formula (AI).

  In the general formula (A-III), Y represents a group of nonmetallic atoms necessary for forming a 5-membered ring with —N═C— (for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazole- 2-yl, 2-imidazolin-2-yl, purinyl, 3H-indol-2-yl). Y is a group of nonmetallic atoms necessary for forming a 6-membered ring together with —N═C— group, and the end of Y bonded to the carbon atom of —N═C— group is —N (Rf1) A group selected from-, -C (Rf2) (Rf3)-, -C (Rf4) =, -O-, -S- (bonded to the carbon atom of -N = C- on the left side of each group) ). Rf1 to Rf4 may be the same or different, and may be a hydrogen atom or a substituent (for example, alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylamino group, arylamino group, halogen atom) ). Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl, 1,3,5-triazin-5-yl, 6H-1,2,5-thiadiazin-6-yl.

  In the general formula (A-IV), Rg1 and Rg2 are alkyl groups (preferably alkyl groups having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, n-butyl, isobutyl, hexyl, cyclohexyl, t-octyl, decyl, dodecyl, hexadecyl, benzyl) or an aryl group (preferably an aryl group having 6 to 40 carbon atoms such as phenyl or naphthyl). However, when Rg1 and Rg2 are simultaneously unsubstituted alkyl groups and Rg1 and Rg2 are the same group, Rg1 and Rg2 are alkyl groups having 8 or more carbon atoms.

  In the general formula (AV), Rh1 and Rh2 are a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group (preferably an alkylamino group having 1 to 50 carbon atoms, such as methylamino, ethylamino, diethylamino, Methylethylamino, propylamino, dibutylamino, cyclohexylamino, t-octylamino, dodecylamino, hexadecylamino, benzylamino, benzylbutylamino), an arylamino group (preferably an arylamino group having 6 to 50 carbon atoms, For example, phenylamino, phenylmethylamino, diphenylamino, naphthylamino), an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms such as methoxy, ethoxy, butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyl Tiloxy, tridecyloxy, hexadecyloxy), an aryloxy group (preferably an aryloxy group having 6 to 40 carbon atoms, such as phenoxy, naphthoxy), an alkylthio group (preferably an alkylthio group having 1 to 36 carbon atoms, Methylthio, ethylthio, i-propylthio, butylthio, cyclohexylthio, benzylthio, t-octylthio, dodecylthio), arylthio groups (preferably arylthio groups having 6 to 40 carbon atoms such as phenylthio, naphthylthio), alkyl groups (preferably carbon numbers) An alkyl group having 1 to 36, for example, methyl, ethyl, propyl, butyl, cyclohexyl, i-amyl, sec-hexyl, t-octyl, dodecyl, hexadecyl), an aryl group (preferably an aryl group having 6 to 40 carbon atoms) For example Enyl, naphthyl). However, Rh1 and Rh2 are not simultaneously -NHR (R is an alkyl group or an aryl group).

  Rd1 and Rd2, X and Re1 may be bonded to each other to form a 5- to 7-membered ring, and examples thereof include a succinimide ring, a phthalimide ring, a triazole ring, a urazole ring, a hydantoin ring, and a 2-oxo-4-oxazolidinone ring. It is done. Each group of the compounds represented by the general formulas (AI) to (A-V) may be further substituted with a substituent. Examples of these substituents include alkyl groups, alkenyl groups, aryl groups, heterocyclic groups, hydroxy groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, acylamino groups, sulfonamido groups, alkylamino groups, Examples include arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, halogen atom, cyano group, nitro group, sulfonyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, hydroxyamino group, etc. .

  In general formula (AI), Rd2 is a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, and Rd1 is an acyl group, sulfonyl group, sulfinyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl Preferred are compounds in which Rd2 is an alkyl group or an alkenyl group, and Rd1 is an acyl group, a sulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Most preferably, Rd2 is an alkyl group and Rd1 is an acyl group.

In general formula (A-II), Re1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1), more preferably X is 1,3,5-triazin-2-yl. Most preferred is the compound represented by A-II-2).

In the general formula (A-II-1), Re1 represents Re1 in the general formula (A-II), and X1 represents a nonmetallic atom group necessary for forming a 5- to 6-membered ring. Of the compounds represented by formula (A-II-1), the case where X1 forms a 5- to 6-membered heteroaromatic ring is more preferred.

In general formula (A-II-2), Re1 has the same meaning as Re1 in general formula (A-II).
Re2 and Re3 may be the same or different and each represents a hydrogen atom or a substituent. Of the compounds represented by the general formula (A-II-2), Re2 and Re3 are hydroxyamino group, hydroxyl group, amino group, alkylamino group, arylamino group, alkoxy group, aryloxy group, alkylthio group, arylthio group Particularly preferred is an alkyl group or an aryl group.

  Of the compounds represented by the general formula (A-III), it is preferable that Y is a nonmetallic atom group necessary for forming a 5-membered ring. More preferably, the terminal atom is a nitrogen atom. Most preferred is when Y forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

  Of the compounds represented by formula (A-IV), those in which Rg1 and Rg2 are alkyl groups are preferred. On the other hand, in the general formula (A-V), Rh1 and Rh2 are preferably groups selected from a hydroxyamino group, an alkylamino group, and an alkoxy group. Particularly preferably, Rh1 is a hydroxylamino group and Rh2 is an alkylamino group.

Among the compounds represented by the general formulas (AI) to (AV), those having a total carbon number of 15 or less are preferable in that they also act on layers other than the additive layer. Those having a sum total of 16 or more are preferable for the purpose of acting only on the additive layer. Among the compounds represented by the general formulas (AI) to (AV), those represented by the general formulas (AI), (A-II), (A-IV), and (AV) More preferably, those represented by the general formulas (A-I), (A-IV), (A-V), and more preferably those represented by the general formulas (A-I), (A-V). Is. Specific examples of the compounds represented by the general formulas (AI) to (AV) of the present invention are shown below, but the present invention is not limited thereby.

The correspondence between these compounds and the general formulas (AI) to (AV) is as follows.
General formula (AI): A-33 to A-55
General formula (A-II): A-5 to A-7, A-10, A-20, A-30
Formula (A-III): A-21 to A-29, A-31, A-32
Formula (A-IV): A-8, A-11, A-19
General formula (AV): A-1 to A-4, A-9, A-12 to A-18

  These compounds of the present invention are described in J. Org. Chem., 27, 4054 ('62), J. Amer. Chem. Soc., 73, 2981 ('51), Japanese Patent Publication No. 49-10682 It can be easily synthesized by a method or a method similar thereto. In the present invention, the compounds represented by the general formulas (AI) to (AV) may be added by dissolving in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof, or adding them. You may add by dispersion | distribution. Further, it may be added in advance during the preparation of the emulsion. In the case of dissolving in water, if the solubility is increased when the pH is increased or decreased, it may be dissolved at a higher or lower pH and added. In this invention, you may use together 2 or more types among the compounds represented by general formula (AI)-(AV). For example, it is advantageous in terms of photographic performance to use a water-soluble one and an oil-soluble one together.

The coating amount of the compound (A-I) ~ (A -V) is preferably ^{10 -4 mmol / m 2 ~10mmol /} m 2, more preferably ^{10 -3 mmol / m 2 ~1mmol /} m 2.

Next, the compound represented by formula (X) will be described. In the general formula (X), Rb17, Rb18, and Rb19 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and Rb20 represents a hydrogen atom, an alkyl group, an alkenyl group, alkynyl group, an aryl group or a heterocyclic group, represents a NRb21Rb22, J represents -CO- or -SO ₂ - represents, n represents 0 or 1. Rb21 represents a hydrogen atom, a hydroxyl group, an amino group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, and Rb22 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic ring Represents a group.

  In Rb17, Rb18 and Rb19, the alkyl group, alkenyl group and alkynyl group are preferably those having 1 to 30 carbon atoms, and in particular, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, A alkenyl group having 10 carbon atoms and an alkynyl group having 2 to 10 carbon atoms. Examples of the alkyl group, alkenyl group, alkynyl group and aralkyl group include methyl, ethyl, propyl, cyclopropyl, allyl, propargyl and benzyl. In Rb17, Rb18 and Rb19, the aryl group preferably has 6 to 30 carbon atoms, and particularly a monocyclic or condensed aryl group having 6 to 12 carbon atoms, such as phenyl and naphthyl. In Rb17, Rb18 and Rb19, the heterocyclic group is a 3- to 10-membered saturated or unsaturated heterocyclic group containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom. These may be a single ring or may form a condensed ring with another aromatic ring. The heterocyclic ring is preferably a 5- to 6-membered aromatic heterocyclic ring, and examples thereof include pyridyl, imidazolyl, quinolyl, benzimidazolyl, pyrimidyl, pyrazolyl, isoquinolyl, thiazolyl, thienyl, furyl, benzothiazolyl and the like.

  In Rb20, an alkyl group, an alkenyl group, an alkynyl group, an aryl group and a heterocyclic group have the same meanings as Rb17, Rb18 and Rb19. In NRb21Rb22 of Rb20, the alkyl group, alkenyl group, alkynyl group, aryl group and heterocyclic group of Rb21 and Rb22 have the same meanings as Rb17, Rb18 and Rb19. Each group represented by Rb17, Rb18, Rb19, Rb20, Rb21 and Rb22 in the general formula (X) may be substituted with the aforementioned substituent Yy.

  In the general formula (X), Rb17 and Rb18, Rb17 and Rb19, Rb19 and Rb20, or Rb20 and Rb18 may be linked to form a ring.

  In general formula (X), when n is 0, Rb17, Rb18 and Rb19 are preferably an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, An aryl group having 6 to 10 atoms and a nitrogen-containing heterocyclic group, and Rb20 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and a carbon number of 6 To R10, a nitrogen-containing heterocyclic group, more preferably Rb17, Rb18 and Rb19 are alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, An aryl group having 6 to 10 carbon atoms and a nitrogen-containing heterocyclic group, and Rb20 is a hydrogen atom. When n is 1, Rb17, Rb18 and Rb19 are preferably hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, alkynyl groups having 2 to 10 carbon atoms, 6 to 10 carbon atoms An aryl group, a nitrogen-containing heterocyclic group, J is —CO—, Rb 20 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkynyl group having 2 to 10 carbon atoms. An aryl group having 6 to 10 carbon atoms, a nitrogen-containing heterocyclic group, NRb21Rb22, wherein Rb21 is a hydrogen atom, a hydroxyl group, an amino group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, carbon An alkynyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group, and Rb22 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, A quinyl group, an aryl group having 6 to 10 carbon atoms, and a nitrogen-containing heterocyclic group, more preferably, Rb17 is an aryl group having 6 to 10 carbon atoms, Rb18 and Rb19 are hydrogen atoms, and J is —CO—. Rb20 is NRb21Rb22, and Rb21 is a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, or an alkynyl group.

Specific compounds represented by the general formula (X) are shown below, but the present invention is not limited thereto.

  The compound represented by the general formula (X) is easily available as a commercially available drug or as a compound synthesized from a commercially available drug by a known method.

The compound represented by the general formula (X) is preferably added to the adjacent layer or other layers of the emulsion layer before or during coating of the coating solution and diffused in the emulsion layer. It can also be added before chemical sensitization, during chemical sensitization, or after completion of chemical sensitization during emulsion preparation. The preferred addition amount largely depends on the above-mentioned addition method and the kind of compound to be added, but generally 5 × 10 ⁻⁶ mol to 0.05 mol, more preferably 1 × 10 ⁻⁵ mol per mol of photosensitive silver halide. To 0.005 mol is used. When the amount is more than the above-mentioned amount, an adverse effect such as an increase in fog occurs and is not preferable. The compound represented by the general formula (X) is preferably added after being dissolved in a water-soluble solvent. The pH may be lowered or raised with an acid or a base, or a surfactant may coexist. Moreover, it can also be dissolved in a high boiling point organic solvent and added as an emulsified dispersion, or may be added as a microcrystalline dispersion by a known dispersion method. Two or more compounds of the general formula (X) may be used in combination. When using 2 or more types together, you may add to the same layer and may add to a separate layer.

Here, the general formula (XI) will be described in more detail.
In the general formula (XI), X ² and Y ² each independently represent a hydroxyl group, —NRi 23 Ri 24, or —NHSO ₂ Ri 25. Ri21 and Ri22 each independently represent a hydrogen atom or an arbitrary substituent. The optional substituent is, for example, an alkyl group (preferably having 1 to 20 carbon atoms, such as methyl, ethyl, octyl, hexadecyl, t-butyl), an aryl group (preferably having 6 to 20 carbon atoms, For example, phenyl, p-tolyl), an amino group (having 0 to 20 carbon atoms is preferable, for example, unsubstituted amino, diethylamino, diphenylamino, hexadecylamino), an amide group (having 1 to 20 carbon atoms is preferable, for example, Acetylamino, benzoylamino, octadecanoylamino, benzenesulfonamide), an alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxy, ethoxy, hexadecyloxy), an alkylthio group (having 1 to 20 carbon atoms). Preferably, for example, methylthio, butylthio, octadecylthio), acyl group (carbon number -20 are preferable, for example, acetyl, hexadecanoyl, benzoyl, benzenesulfonyl), carbamoyl group (preferably having 1 to 20 carbon atoms, such as unsubstituted carbamoyl, N-hexylcarbamoyl, N, N-diphenylcarbamoyl) , Alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms, such as methoxycarbonyl, octyloxycarbonyl), hydroxyl groups, halogen atoms (F, Cl, Br, etc.), cyano groups, nitro groups, sulfo groups, carboxyl groups, etc. Can be mentioned.
These substituents may be further substituted with another substituent (for example, those listed as Yy).

  Ri21 and Ri22 may be bonded to each other to form a carbocycle or a heterocycle (both preferably 5 to 7-membered rings). Ri23 and Ri24 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms, such as ethyl, hydroxyethyl, octyl), an aryl group (preferably having 6 to 10 carbon atoms, such as phenyl, Naphthyl) or a heterocyclic group (preferably having 2 to 10 carbon atoms, for example, 2-furanyl, 4-pyridyl), which may be further substituted with a substituent.

  Ri23 and Ri24 may be bonded to each other to form a nitrogen-containing heterocyclic ring (preferably a 5- to 7-membered ring). Ri25 is an alkyl group (preferably having 1 to 20 carbon atoms, such as ethyl, octyl, hexadecyl) or an aryl group (preferably having 6 to 20 carbon atoms, such as phenyl, p-tolyl, 4-dodecyloxyphenyl). ), An amino group (having 0 to 20 carbon atoms, preferably N, N-diethylamino, N, N-diphenylamino, morpholino) or a heterocyclic group (preferably having 2 to 20 carbon atoms, for example, 3-pyridyl ), Which may be further substituted.

In the general formula (XI), X ² is preferably —NRi 23 Ri 24 or —NHSO ₂ Ri 25. Ri21 and Ri22 are preferably a hydrogen atom, an alkyl group or an aryl group, and may be bonded to each other to form a carbocycle or a heterocycle. The details of these groups are the same as Ri23 and Ri24.

Specific compounds represented by the general formula (XI) are shown below, but the present invention is not limited thereto.

  Among the compounds represented by the general formulas (VI) to (XI), the general formulas (IX-1), (IX-2), (VIII-1), (VIII-2), (VII), (VI ) And (X) are preferred, and compounds represented by the general formulas (IX-1), (IX-2), (VIII-1), (VIII-2), and (VII) are more preferred. The compounds represented by formulas (IX-1), (IX-2), (VIII-1), and (VIII-2) are more preferable. Particularly preferred are compounds represented by formulas (IX-1) and (IX-2).

  One or more photosensitive layers of the present invention can be provided on the support. Moreover, it can provide not only on one side of a support body but on both surfaces. The photosensitive layer of the present invention comprises a black-and-white silver halide photographic light-sensitive material (for example, an X-ray light-sensitive material, a squirrel-type light-sensitive material, a black-and-white negative film, etc.) and a color photographic light-sensitive material (for example, a color negative film, a color reversal film, Color paper). Furthermore, it can also be used for photosensitive materials for diffusion transfer (for example, color diffusion transfer elements, silver salt diffusion transfer elements), photothermographic materials (black and white, color), and the like.

Hereinafter, the color photographic light-sensitive material will be described in detail, but is not limited thereto.
In the light-sensitive material, it is sufficient that at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer is provided on a support. There is no restriction | limiting in particular in the number of layers of a photosensitive layer, and a layer order. As a typical example, a silver halide photographic light-sensitive material having at least one color-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. 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 unit photosensitive layer is generally used. Are arranged in the order of the red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer 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 contained in the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the above-described silver halide photosensitive layers and in the uppermost layer and the lowermost layer.
The intermediate layer includes couplers and DIR compounds as described in JP-A Nos. 61-43748, 59-111438, 59-113440, 61-20037, and 61-20038. It may also contain a color mixing inhibitor as is usually used.

  A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent 1,121,470 or British Patent 923,045. A two-layer structure can be preferably used. In general, it is preferable that the photosensitivity is sequentially decreased toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, as described in JP-A-57-112751, 62-200350, 62-206541 and 62-206543, the low-sensitivity emulsion layer is close to the support on the side away from the support. A high-sensitivity emulsion layer may be provided on the side.

As a specific example, from the side farthest from the support, for example, 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 / It can be installed in the order of RH.
Further, as described in JP-B-55-34932, it 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 62-63936, the blue photosensitive layer / GL / RL / GH / RH may be installed in this order from the side farthest from the support. .

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 photosensitivity is arranged, and an arrangement composed of three layers having different photosensitivities in which the photosensitivity is gradually lowered toward the support. Even in the case of the three layers having different sensitivities, as described in JP-A-59-202464, the medium-sensitive emulsion layer / from the side away from the support in the same color-sensitive layer / They may be arranged in the order of high sensitivity emulsion layer / low sensitivity 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.
As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The above-mentioned various additives are used in the light-sensitive material according to the present invention, but various additives can be used depending on the purpose.
These additives are described in more detail in Research Disclosure Item 17643 (December 1978), Item 18716 (November 1979), and Item 308119 (December 1989). These are summarized in the table below.

Additive type RD17643 RD18716 RD308119
1 Chemical sensitizer page 23 page 648 right column page 996
2 Sensitizer Same as above
3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998, right supersensitizer, page 649, right column
4 Brightener 24 pages 647 right column 998 right
5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right and stabilizer
6 Light absorber, page 25-26, page 649, right column to 1003, left to 1003 right Filter dye, page 650, left column, UV absorber
7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right
8 Dye image stabilizer 25 page 1002 right
9 Hardener page 26 page 651 left column 1004 right to 1005 left
10 Binder page 26 Same as above 1003 right to 1004 right
11 Plasticizer, Lubricant 27 pages 650 right column 1006 left to 1006 right
12 Coating aid, pages 26-27 Same as above 1005 Left to 1006 Left Surfactant
13 Static 27 pages Same as above 1006 Right to 1007 Left Anti-blocking agent
14 Matting agent 1008 left to 1009 left

  Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, a compound capable of reacting with formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503 is immobilized on a photosensitive material. It is preferable to add.

  Various color couplers can be used in the present invention, and specific examples thereof are the above-mentioned Research Disclosure No. 17643, VII-CG and No. 307105, described in the patents described in VII-CG.

Examples of the yellow coupler include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. No. 58-10739, British Patent No. 1,425,020, No. 1,476,760, U.S. Pat. No. 3,973,968, No. 4,314,023, No. 4 511,649, European Patent 249,473A, and the like.
The magenta coupler is preferably a 5-pyrazolone compound or a pyrazoloazole compound. US Pat. Nos. 4,310,619, 4,351,897, European Patent 73,636, US Pat. No. 061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35730, 55-1118034, 60-185951, US Pat. No. 4,500,630, Nos. 4,540,654, 4,556,630, and International Publication WO88 / 04795 are particularly preferable.

Examples of cyan couplers include phenolic and naphtholic couplers, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, and 4,296,200. No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826, No. 3,772,002, No. 3 758,308, 4,334,011, 4,327,173, West German Patent Publication 3,329,729, European Patents 121,365A, 249,453A, U.S. Pat.Nos. 3,446,622, 4,333,999, 4,775,616, 4,451,559, 4,427,767, 4, 690,889, 4,254,212 The No. 4,296,199, are preferred according to JP-61-42658 or the like.
Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, 4,409,320, No. 4,576,910, British Patent No. 2,102,137 and European Patent No. 341,188A.

As couplers in which the coloring dye has an appropriate diffusibility, U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570, West German Patent (Publication) 3,234 No. 533 is preferred.
Colored couplers for correcting unwanted absorption of coloring dyes are Research Disclosure No. No. 17643, VII-G, No. No. 307105, VII-G, U.S. Pat. No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Pat. No. 4,004,929, U.S. Pat. No. 4,138,258, British Patent 1,146, Those described in No. 368 are preferred. Further, it reacts with a coupler that corrects unnecessary absorption of a coloring dye by a fluorescent dye released during coupling described in US Pat. No. 4,774,181, and a developing agent described in US Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

  Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention. DIR couplers that release a development inhibitor include the above-mentioned RD17643, item VII-F, and No. 1 above. No. 307105, patents described in paragraph VII-F, JP-A 57-151944, 57-154234, 60-184248, 63-37346, 63-37350, US Pat. No. 4,248 No. 962, and No. 4,782,012 are preferred.

  Examples of couplers that release a nucleating agent or development accelerator in the form of an image during development include British Patent Nos. 2,097,140, 2,131,188, JP-A-59-157638, and 59-170840. Are preferred. Further, a fogging agent and a development accelerator are obtained by an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-60-107029, JP-A-60-252340, JP-A-1-44940, and JP-A-1-45687. Also preferred are compounds that release silver halide solvents and the like.

  Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. Nos. 4,283,472 and 4,338,393. No. 4,310,618, etc. Multi-equivalent couplers, JP-A-60-185950, JP-A-62-24252, etc. DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing A redox compound or a DIR redox-releasing redox compound, a coupler that releases a dye that recovers color after release described in European Patent Nos. 173,302A and 313,308A; No. 11449, 24241, bleach accelerator releasing couplers described in JP-A-61-201247, ligand releasing couplers described in U.S. Pat. No. 4,555,477, and leucos described in JP-A-63-75747. Examples include couplers that release a dye, and couplers that release a fluorescent dye described in US Pat. No. 4,774,181.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods.
Examples of high-boiling solvents used in the oil-in-water dispersion method are described, for example, in US Pat. No. 2,322,027.

  Specific examples of the high-boiling organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). Bis (2,4-di-tert-amylphenyl) phthalate, bis (2,4-di-tert-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate); phosphoric acid or phosphonic acid Esters (e.g., triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate Benzoates (eg 2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate); amides (eg N, N-diethyldodecanamide, N, N-diethyllaurylamide, N-tetradecylpyrrolidone); alcohols or phenols (eg, isostearyl alcohol, 2,4-di-tert-amylphenol); aliphatic carboxylic acid esters (eg, bis ( 2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate); aniline derivatives such as N, N-dibutyl-2-butoxy-5-tert-octylanily ); Hydrocarbons (e.g., can be exemplified paraffin, dodecylbenzene, and diisopropylnaphthalene). As the auxiliary solvent, for example, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples include, for example, ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone. , Cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

  Examples of latex dispersion process steps, effects, and impregnating latexes are described in, for example, U.S. Pat. No. 4,199,363, West German Patent Application (OLS) 2,541,274, and 2,541,230. In the issue.

  Examples of the color light-sensitive material of the present invention include phenethyl alcohol and those described in JP-A-63-257747, JP-A-62-272248, and JP-A-1-809441, for example, 1,2-benzisothiazolin-3-one. Various preservatives or antifungal agents such as n-butyl-p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, 2- (4-thiazolyl) benzimidazole It is preferable.

  The present invention can be applied to various color light-sensitive materials. For example, color negative films for general use or movies, color reversal films for slides or television, color paper, color positive film, and color reversal paper can be given as representative examples. The present invention can be particularly preferably used for a film for color duplication.

  Suitable supports that can be used in the present invention include, for example, the RD. No. 17643, page 28, ibid. No. 18716, from the right column on page 647 to the left column on page 648; 307105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the side having an emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, still more preferably 18 μm or less, and particularly preferably 16 μm or less. The membrane swelling speed T1 _{/ 2} is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness here means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days). The film swelling rate T _1/2 can be measured according to a method known in the art, and for example, A. Green et al., Photographic Science and Engineering (Photogr. Sci. Eng. ), Vol. 19, No. 2, pp. 124-129. Note that T _1/2 is 90% of the maximum swollen film thickness that is reached when processed at 30 ° C. for 3 minutes and 15 seconds with a color developer, and is the time required to reach 1/2 of the saturated film thickness. Define.

The film swelling speed T1 _{/ 2} can be adjusted by adding a hardening agent to gelatin as a binder or changing the aging conditions after coating.

  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. The back layer preferably contains, for example, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. . The swelling ratio of the back layer is preferably 150 to 500%.

  The color photographic light-sensitive material according to the present invention has the RD. No. 17643, pp. 28-29, ibid. No. 18716, page 651, left column to right column; 307105, pages 880 to 881 can be used for development processing by a conventional method.

  The color developer used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly composed of an aromatic primary amine color developing agent. As this color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -Β-methoxyethylaniline, and sulfates, hydrochlorides, or p-toluenesulfonates of these salts. Of these, sulfate of 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline is particularly preferable. These compounds may be used in combination of two or more depending on the purpose.

  Color developers include, for example, pH buffering agents such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts, iodide salts, benzimidazoles, benzothiazoles or mercapto compounds. It is common to include a development inhibitor or an antifogging agent. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, catecholsulfonic acids; ethylene glycol, Organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines; dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity imparting Agents: Various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic acid can be used. Examples of chelating agents include ethylenediaminetetraacetic acid, nitrile triacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N- Typical examples include trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

  When reversal processing is performed, color development is usually performed after black and white development. This black-and-white developer includes, for example, dihydroxybenzenes such as hydroquinone, for example 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Known black-and-white developing agents can be used alone or in combination. The pH of these color developer and black-and-white developer is generally 9-12. Further, the replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 L or less per square meter of the light-sensitive material. You can also When reducing the replenishment amount, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing liquid with air.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below. That is,
Opening ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )]
The aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, a movable lid described in JP-A-1-82033 is used in addition to a method of providing a shielding object such as a floating lid on the photographic processing liquid surface of the processing tank. And a slit developing method described in JP-A-63-2106050. The reduction of the aperture ratio is preferably applied not only in both color development and black-and-white development processes but also in the subsequent processes such as bleaching, bleach-fixing, fixing, washing, and stabilization. Further, the replenishment amount can be reduced by using a means for suppressing the accumulation of bromide ions in the developer.

  The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by setting the temperature and pH to high and using the color developing agent at a high concentration.

  The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleaching and fixing process) or may be performed individually. Further, in order to speed up the processing, a processing method of performing bleach-fixing processing after the bleaching processing may be used. Further, depending on the purpose, it is possible to carry out the treatment in two continuous bleach-fixing baths, the fixing treatment before the bleach-fixing treatment, or the bleaching treatment after the bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (III), peracids (especially sodium persulfate is suitable for a color negative film for movies), quinones and nitro compounds are used. Typical bleaching agents include organic complex salts of iron (III) such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid. Complex salts with aminopolycarboxylic acids, or complex salts with citric acid, tartaric acid, malic acid, for example, can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are the viewpoints of rapid processing and prevention of environmental pollution. To preferred. Furthermore, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these iron (III) complex salts of aminopolycarboxylic acids is usually from 4.0 to 8, but it can be processed at a lower pH in order to speed up the processing.

  A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution, and their pre-bath, if necessary. Specific examples of useful bleach accelerators are described in the following specifications: for example, U.S. Pat. No. 3,893,858, West German Patents 1,290,812, and 2,059,988. JP-A-53-32736, 53-57831, 53-37418, 53-72623, 53-95630, 53-95631, 53-104232, 53-124424. 53-141623, 53-18426, Research Disclosure No. Compounds having mercapto groups or disulfide groups described in JP-A No. 17129 (July 1978); thiazolidine derivatives described in JP-A No. 51-140129; JP-B Nos. 45-8506, 52-20832 and 53 No. -32735, a thiourea derivative described in US Pat. No. 3,706,561, an iodide salt described in West German Patent No. 1,127,715 and JP-A No. 58-16235; West German Patent No. 966,410 No. 2,748,430; polyoxyethylene compounds described in JP-B No. 45-8836; other JP-A Nos. 49-40943, 49-59644, 53-94927 , 54-35727, 55-26506, 58-163940; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly described in US Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630. Are preferred. Furthermore, the compounds described in US Pat. No. 4,552,884 are also preferable. These bleach accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when a color light-sensitive material for photography is bleach-fixed.

  In addition to the above compounds, the bleaching solution or the bleach-fixing solution preferably contains an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specific examples include acetic acid, propionic acid, and hydroxyacetic acid.

  Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. Of these, thiosulfate is generally used, and ammonium thiosulfate is most widely used. Further, a combination of thiosulfate and, for example, thiocyanate, thioether compound, or thiourea is also preferable. As the preservative for the fixing solution or the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

  In the present invention, the fixing solution or bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2-methylimidazole and the like. It is preferable to add imidazoles in an amount of 0.1 to 10 mol / L.

  The total desilvering time is preferably as short as possible without causing desilvering failure. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In the preferred temperature range, the desilvering rate is improved, and the occurrence of stain after the treatment is effectively prevented.

  In the desilvering step, it is preferable that the stirring is strengthened as much as possible. Specific methods for strengthening stirring include the method of causing a jet of processing solution to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and stirring using a rotating means in JP-A-62-183461. The method of raising the effect is mentioned. Furthermore, the photosensitive material is moved while the wiper blade provided in the solution is in contact with the emulsion surface, and the emulsion surface is turbulent to improve the stirring effect, and the circulation flow rate of the entire processing solution is increased. The method of letting it be mentioned. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution, and the fixing solution. The improvement in stirring is considered to speed up the supply of the bleaching agent and the fixing agent into the emulsion film and consequently increase the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and the acceleration effect can be remarkably increased or the fixing inhibitory action can be eliminated by the bleaching accelerator.

  The automatic developing machine used for developing the photosensitive material of the present invention preferably has the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. As described in JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and has a high effect of preventing the performance deterioration of the processing liquid. Such an effect is particularly effective for shortening the processing time in each process and reducing the replenishment amount of the processing liquid.

  The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and / or a stabilization process after desilvering. The amount of water to be washed in the washing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the application, and further, for example, the temperature of the washing water, the number of washing tanks (number of stages), replenishment such as countercurrent and forward flow. A wide range can be set according to the system and other various conditions. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in Journal of the Society of Motion Picture and Television Engineers Vol. 64, p. 248 to 253 (May 1955).

  According to the multi-stage countercurrent system described in the above document, the amount of water to be washed can be greatly reduced. However, bacteria increase due to an increase in the residence time of water in the tank, and the generated suspended matter adheres to the photosensitive material. Problems arise. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, as described in JP-A-57-8542, for example, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated isocyanurate sodium, and others such as benzotriazole, written by Horiguchi Hiroshi “Chemistry of Antibacterial and Antifungal Agents” (1986) Sankyo Publishing, Hygiene Technology Association “Microbial Sterilization, Sterilization, and Antifungal Technology” (1982) Industrial Technology Association of Japan The fungicides described in “Enamel Encyclopedia” (1986) can also be used.

  The pH of the washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing water temperature and washing time can also be variously set depending on, for example, the characteristics and application of the photosensitive material. In general, the washing water temperature and washing time are 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 40 ° C. for 30 seconds to 5 minutes. A range is selected. Furthermore, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the water washing. In such stabilization treatment, all known methods described in JP-A-57-8543, 58-14834, and 60-220345 can be used.

  Further, a stabilization treatment may be further performed following the water washing treatment. Examples thereof include a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow liquid accompanying the washing with water and / or the replenishment of the stabilizing liquid can be reused in other processes such as a desilvering process.
For example, in the processing using an automatic developing machine, when each processing solution is concentrated by evaporation, it is preferable to correct the concentration by adding water.

  The silver halide color photographic light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate them, it is preferable to use various precursors of color developing agents. For example, an indoaniline compound described in US Pat. No. 3,342,597, for example, US Pat. No. 3,342,599, Research Disclosure No. 14,850 and No. No. 15,159, Schiff base type compounds, An aldol compound described in US Pat. No. 13,924, a metal salt complex described in US Pat. No. 3,719,492, and a urethane compound described in JP-A-53-135628 can be used.

  The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones for the purpose of accelerating color development, if necessary. Typical compounds are described, for example, in JP-A Nos. 56-64339, 57-144547, and 58-115438.

Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but the temperature is increased to accelerate the processing and shorten the processing time, or conversely, the temperature is lowered to achieve an improvement in image quality and stability of the processing solution. be able to.
The silver halide light-sensitive material of the present invention is disclosed in U.S. Pat. No. 4,500,626, JP-A-60-133449, 59-218443, 61-238056, European Patent 210,660A2, etc. It can also be applied to the photothermographic material described in 1.
In addition, the silver halide color photographic light-sensitive material of the present invention is more effective when it is applied to a film unit with a lens described in Japanese Patent Publication No. 2-332615, Japanese Utility Model Publication No. 3-39784, etc. It is.

[Example]
Examples of the present invention are shown below. However, the present invention is not limited to this example.
(Example 1)
Silver halide emulsions Em-A1 to A11 were prepared by the following production method.
(Em-A1)
42.2 L of an aqueous solution containing 31.7 g of phthalated low molecular weight gelatin having a phthalation rate of 97% and a molecular weight of 15000 and 31.7 g of KBr was kept at 35 ° C. and stirred vigorously. 1583 mL of an aqueous solution containing 316.7 g of AgNO ₃ and 1583 mL of an aqueous solution containing 52.7 g of low molecular weight gelatin having a KBr of 221.5 g and a molecular weight of 15000 were added over 1 minute by the double jet method. Immediately after the addition, 52.8 g of KBr was added, and 2485 mL of an aqueous solution containing 398.2 g of AgNO ₃ and 2581 mL of an aqueous solution containing 291.1 g of KBr were added over 2 minutes by the double jet method. Immediately after the addition, 47.8 g of KBr was added. Then, it heated up to 40 degreeC and fully matured. After completion of aging, 923 g of phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000 were added and KBr, 79.2 g, and 15947 mL of an aqueous solution containing 5103 g of AgNO ₃ and an aqueous KBr solution were added to the initial flow rate by the double jet method. The flow rate was accelerated to 1.4 times and added over 12 minutes. At this time, the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After washing with water, gelatin was added to adjust the pH to 5.7, pAg, 8.8, the mass in terms of silver per kg of emulsion of 131.8 g, and the gelatin mass of 64.1 g to obtain a seed emulsion.

1211 mL of an aqueous solution containing 46 g of phthalated gelatin having a phthalation rate of 97% and 1.7 g of KBr was kept at 75 ° C. and vigorously stirred. After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (product of Nippon Unicar Co., Ltd., L7602) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and KBr aqueous solution. Then, the flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 144.5 g of AgNO ₃ , a mixed solution of KBr and KI containing 410 mL and 7 mol% of KI, the final flow rate is the initial flow rate by the double jet method. The flow rate was accelerated so as to be 3.7 times that of the solution and added over 56 minutes. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI mass. Immediately after the addition, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. The silver potential was kept at −80 mV with an aqueous KBr solution for 5 minutes at the beginning of the addition. After washing with water, when measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 60 ° C. After addition of sensitizing dyes 11 and 12, potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compound 13 and Compound 14 were added at the end of chemical sensitization. Here, optimal chemical sensitization means that the sensitizing dye and each compound were selected from an addition amount range of 10 ⁻¹ to 10 ⁻⁸ mol per mol of silver halide.

  As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the vicinity of the side surface of the particle.

(Em-A2)
Emulsion Em-A2 was obtained in the same manner as (Em-A1) except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-A3)
Emulsion Em-A3 was obtained in the same manner as (Em-A2) except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (IX-2-3) of the present invention was added during chemical sensitization.

(Em-A4)
After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (product of Nippon Unicar Co., Ltd., L7602) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and KBr aqueous solution. Then, the flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ , an aqueous solution of 381 mL and KBr so that the final flow rate is 3.7 times the initial flow rate by the double jet method. The flow rate was accelerated to 56 minutes and added. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added while simultaneously accelerating the flow rate so that the silver iodide content was 7 mol%, and the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI mass. Immediately after the addition, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. The silver potential was kept at −80 mV with an aqueous KBr solution for 5 minutes at the beginning of the addition. After washing with water, when measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. Subsequent steps were performed in the same manner as Em-A1.
As a result of observing the obtained particle with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the vicinity of the particle side surface.

(Em-A5)
Emulsion Em-A5 was obtained in the same manner as Em-A4, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-A6)
Emulsion Em-A6 was obtained in the same manner as Em-A 5 except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-3) was added during chemical sensitization.

(Em-A7)
After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (Nihon Unicar Co., Ltd. product, L7602) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and KBr aqueous solution. Then, the flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ , an aqueous solution of 381 mL and KBr so that the final flow rate is 3.7 times the initial flow rate by the double jet method. The flow rate was accelerated to 56 minutes and added. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added while simultaneously accelerating the flow rate so that the silver iodide content was 7 mol%, and the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. After the temperature was lowered to 40 ° C. and KBr was added to adjust the silver potential to −40 mV, an aqueous solution containing 14.5 g of sodium p-iodoacetamidobenzenesulfonate (monohydrate) was added, and then 0.8M An aqueous solution of sodium sulfite (57 mL) was added in a fixed amount for 1 minute to produce iodide ions while controlling the pH to 9.0. After 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was returned to 5.5. It was. Thereafter, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. During the addition, the silver potential was kept at -50 mV with an aqueous KBr solution. After washing with water, when measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. Subsequent steps were performed in the same manner as Em-A1.

  As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the vicinity of the side surface of the particle. At this time, dislocations existing in the vicinity of the side surface were localized in the vicinity of the apex of the tabular grains.

(Em-A8)
The compounds of the present invention at the time of chemical sensitization (I-13) to 1 × 10 ^-4 mol / molAg, and compounds other than the (IX-2-3) was added 1 × 10 ^-4 mol / molAg includes Em-A7 Similarly, emulsion Em-A8 was obtained.

(Em-A9)
Emulsion Em-A9 was obtained in the same manner as Em-A 8 , except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-3) was added during chemical sensitization.

(Em-A10)
After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (product of Nippon Unicar Co., Ltd., L7602) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and KBr aqueous solution. Then, the flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ , an aqueous solution of 381 mL and KBr so that the final flow rate is 3.7 times the initial flow rate by the double jet method. The flow rate was accelerated to 56 minutes and added. At this time, an AgI fine grain emulsion having a grain size of 0.037 μm was added while simultaneously accelerating the flow rate so that the silver iodide content was 7 mol%, and the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 330.8 mL of an aqueous solution containing 102.4 g of AgNO ₃ and an aqueous KBr solution were added over 60 minutes by the double jet method. At this time, the silver potential was kept at +20 mV for the first 50 minutes with respect to the saturated calomel electrode and 120 mV for the remaining 10 minutes. After cooling to 50 ° C., 55 mL of 0.3% KI aqueous solution was added over 10 minutes. Immediately thereafter, 100 mL of an aqueous solution containing 14.2 g of AgNO ₃ , 120 mL of an aqueous solution containing 2.1 g of NaCl and 4.17 g of KBr, and a solution containing 0.0133 mol of AgI fine particles were added simultaneously. At this time, 9.4 × 10 ⁻⁴ mol of K ₄ [RuCN ₆ ] was present with respect to 1 mol of AgNO ₃ added. Thereafter, a sensitizing dye was added (for epitaxial stabilization). After washing with water, when the molecular weight distribution was measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. Subsequent steps were performed in the same manner as Em-A1.

  When the obtained particles were observed with a scanning electron microscope, an epitaxial layer was attached to the apex of the tabular grains.

(Em-A11)
The compounds of the present invention at the time of chemical sensitization (I-13) to 1 × 10 ^-4 mol / molAg, and compounds other than the (IX-2-3) was added 1 × 10 ^-4 mol / molAg includes Em-A10 Similarly, emulsion Em-A11 was obtained.

(Em-A12)
Emulsion Em-A12 was obtained in the same manner as Em-A11 1 except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-3) was added during chemical sensitization.

(Em-A13)
After adding 9.9 g of the seed emulsion described above, 0.3 g of modified silicone oil (product of Nippon Unicar Co., Ltd., L7602) was added. After adjusting the pH to 5.5 by adding H ₂ SO ₄ , the final flow rate is 5.1 times the initial flow rate by double jet method using 67.6 mL of an aqueous solution containing 7.0 g of AgNO ₃ and KBr aqueous solution. Then, the flow rate was accelerated and added over 6 minutes. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. After adding 2 mg of sodium benzenethiosulfonate and 2 mg of thiourea dioxide, an aqueous solution containing 134.4 g of AgNO ₃ , gelatin of 762 mL, KBr 90.1 g, KI 9.46 g, and molecular weight 20,000 is placed in a stirrer installed outside the reaction vessel. The AgBrI emulsion was added to the reaction vessel over 90 minutes while simultaneously preparing 762 mL of an aqueous solution containing 38.1 g of AgBrI fine grain emulsion (average size: 0.015 μm) having a silver iodide content of 7 mol%. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 121.3 mL of an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 22 minutes by the double jet method. At this time, the silver potential was kept at +20 mV with respect to the saturated calomel electrode. The temperature was raised to 82 ° C., KBr was added to adjust the silver potential to −80 mV, and then 6.33 g of an AgI fine grain emulsion having a grain size of 0.037 μm was added in terms of KI mass. Immediately after the addition, 206.2 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 16 minutes. The silver potential was kept at −80 mV with an aqueous KBr solution for 5 minutes at the beginning of the addition. After washing with water, when measured according to the PAGI method, gelatin containing 30% of a component having a molecular weight of 280,000 or more was added and adjusted to pH, 5.8, pAg, 8.7 at 40 ° C. Subsequent steps were performed in the same manner as Em-A1.
As a result of observing the obtained particle with a transmission electron microscope while cooling with liquid nitrogen, 10 or more dislocation lines per particle were observed in the vicinity of the particle side surface.

(Em-A14)
At the time of chemical sensitization, except that 1 × 10 ⁻⁴ mol / mol Ag of compound (I-13) of the present invention and 1 × 10 ⁻⁴ mol / mol Ag of compound (IX-2-3) were added during chemical sensitization. Emulsion Em-A14 was obtained in the same manner as Em-A13, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added.

(Em-A15)
The compounds of the present invention at the time of chemical sensitization (IX-2-3) except that the added 1 × 10 ^-4 mol / molAg is in the same manner as Em-A1 4 obtain an emulsion Em-A15.

(Em-B) (Emulsion for low sensitivity blue-sensitive layer)
1192 mL of an aqueous solution containing 0.96 g of low molecular weight gelatin, KBr, and 0.9 g was kept at 40 ° C. and stirred vigorously. 37.5 mL of an aqueous solution containing 1.49 g of AgNO ₃ and 37.5 mL of an aqueous solution containing 1.5 g of KBr were added over 30 seconds by the double jet method. After adding 1.2 g of KBr, the mixture was heated to 75 ° C. and aged. After sufficiently ripening, 30 g of trimellitated gelatin having a molecular weight of 100,000, whose amino group was chemically modified with trimellitic acid, was added to adjust the pH to 7. 6 mg of thiourea dioxide was added. 116 mL of an aqueous solution containing 29 g of AgNO ₃ and an aqueous KBr solution were added at an accelerated flow rate so that the final flow rate was three times the initial flow rate by the double jet method. At this time, the silver potential was kept at −20 mV with respect to the saturated calomel electrode. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over 30 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 15.8 mol%, and the silver potential was kept at 0 mV with respect to the saturated calomel electrode. It was. 96.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 3 minutes by the double jet method. At this time, the silver potential was kept at 0 mV. After adding 26 mg of sodium ethylthiosulfonate, the temperature was lowered to 55 ° C., and an aqueous KBr solution was added to adjust the silver potential to −90 mV. 8.5 g of the above-mentioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 228 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 5 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be + 20mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.

(Em-C) (low-sensitivity blue-sensitive emulsion)
1192 mL of an aqueous solution containing 1.02 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram and 0.97 g of KBr was maintained at 35 ° C. and stirred vigorously. An aqueous solution containing AgNO ₃ , 4.47 g, 42 mL and KBr, an aqueous solution containing 3.16 g, and 42 mL were added over 9 seconds by the double jet method. After adding 2.6 g of KBr, the temperature was raised to 66 ° C. and fully aged. After completion of aging, 41.2 g of trimellitated gelatin having a molecular weight of 100,000 used in the preparation of Em-B and NaCl, 18.5 g were added. After adjusting the pH to 7.2, 8 mg of dimethylamine borane was added. 203 mL of an aqueous solution containing 26 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method so that the final flow rate was 3.8 times the initial flow rate. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. 440.6 mL of an aqueous solution containing 110.2 g of AgNO ₃ and an aqueous KBr solution were added over 24 minutes while accelerating the flow rate so that the final flow rate was 5.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was added at an accelerated flow rate so that the silver iodide content was 2.3 mol%, and the silver potential was -20 mV to the saturated calomel electrode. Kept. After adding 10.7 mL of 1N aqueous potassium thiocyanate solution, 153.5 mL of an aqueous solution containing 24.1 g of AgNO ₃ and an aqueous KBr solution were added over 2 minutes and 30 seconds by the double jet method. At this time, the silver potential was kept at 10 mV. An aqueous KBr solution was added to adjust the silver potential to -70 mV. 6.4 g of the aforementioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 404 mL of an aqueous solution containing 57 g of AgNO ₃ was added over 45 minutes. At this time, it adjusted with KBr aqueous solution so that the electric potential at the time of completion | finish of addition might be -30mV. It was washed with water in the same manner as Em-A1, and chemically sensitized.

(Em-D) (Low-sensitivity blue-sensitive layer emulsion)
In the preparation of Em-C, the amount of AgNO ₃ added during nucleation was changed to 2.0 times. Then, the addition at the end of the potential of the aqueous solution 404mL, including the final AgNO _3, 57 g was changed to adjust an aqueous KBr solution to be + 90 mV. Otherwise, it was prepared in substantially the same manner as Em-C.

(Em-E) (magenta coloring layer having a spectral sensitivity peak at 480 to 550 nm)
(Layer that gives a layered effect to the red sensitive layer)
1200 mL of an aqueous solution containing 0.2 g of modified silicone oil used in the preparation of low molecular weight gelatin having a molecular weight of 15000, 0.71 g, KBr, 0.92 g, and Em-A1 is maintained at 39 ° C., and the pH is adjusted to 1.8 vigorously. Stir. An aqueous solution containing 0.45 g of AgNO ₃ and an aqueous KBr solution containing 1.5 mol% KI were added over 17 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 56 ° C. and aging was performed. After fully ripening, 20 g of phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol of methionine per gram was added. After adjusting the pH to 5.9, KBr, 2.9 g was added. 288 mL of an aqueous solution containing 28.8 g of AgNO ₃ and an aqueous KBr solution were added over 53 minutes by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After adding 2.5 g of KBr, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution are added over 63 minutes by accelerating the flow rate so that the final flow rate is 1.2 times the initial flow rate by the double jet method. did. At this time, the above-mentioned AgI fine grain emulsion was simultaneously added at a flow rate acceleration so that the silver iodide content was 10.5 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 25 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After adding 2 mg of sodium benzenethiosulfonate, the pH was adjusted to 7.3. After KBr was added to adjust the silver potential to -70 mV, 5.73 g of the above AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 609 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 10 minutes. During the initial 6 minutes of addition, the silver potential was kept at -70 mV with an aqueous KBr solution. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 1 and 2, the temperature was raised to 56 ° C. After adding 0.0004 mol of the above AgI fine grain emulsion to 1 mol of silver, sensitizing dyes 13 and 14 were added. Potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.

(Em-F) (Emulsion for medium sensitivity green sensitive layer)
Em-E was prepared in substantially the same manner as Em-E, except that the amount of AgNO ₃ added during nucleation was changed to 3.1 times. However, the sensitizing dye of Em-E was changed to sensitizing dyes 15, 16 and 17.

(Em-G) (Low-sensitivity green sensitive layer emulsion)
Maintain a pH of 1.30 mL of an aqueous solution containing 0.70 g of low molecular weight gelatin having a molecular weight of 15000, KBr, 0.9 g, KI, 0.175 g, and 0.2 g of modified silicone oil used in the preparation of Em-A1 at 33 ° C. 8 and stirred vigorously. An aqueous solution containing 1.8 g of AgNO ₃ and an aqueous KBr solution containing 3.2 mol% KI were added over 9 seconds by the double jet method. At this time, the excessive concentration of KBr was kept constant. The temperature was raised to 69 ° C. and aging was performed. After completion of ripening, 27.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 6.3, KBr, 2.9 g was added. 270 mL of an aqueous solution containing 27.58 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes by the double jet method. At this time, particles prepared by mixing a low molecular weight gelatin aqueous solution having a molecular weight of 15000, an AgNO ₃ aqueous solution, and a KI aqueous solution immediately before addition in another chamber having a magnetic coupling induction stirrer described in JP-A-10-43570 An AgI fine grain emulsion having a size of 0.008 μm was simultaneously added so that the silver iodide content was 4.1 mol%, and the silver potential was kept at −60 mV with respect to the saturated calomel electrode. After adding KBr, 2.6 g, an aqueous solution containing 87.7 g of AgNO ₃ and an aqueous KBr solution are accelerated over a period of 49 minutes by the double jet method so that the final flow rate is 3.1 times the initial flow rate. did. At this time, the AgI fine grain emulsion prepared by mixing immediately before the above addition was simultaneously accelerated in flow rate so that the silver iodide content was 7.9 mol%, and the silver potential was kept at -70 mV. After adding 1 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was +20 mV. After raising the temperature to 78 ° C. and adjusting the pH to 9.1, KBr was added to bring the potential to −60 mV. 5.73 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, 321 mL of an aqueous solution containing 66.4 g of AgNO ₃ was added over 4 minutes. The silver potential was kept at −60 mV with an aqueous KBr solution for 2 minutes at the beginning of the addition. It was washed with water in the same manner as Em-F and chemically sensitized.

(Em-H) (Low-sensitivity green sensitive layer emulsion)
An aqueous solution containing 17.8 g of ion-exchanged gelatin having a molecular weight of 100,000, KBr, 6.2 g, KI, and 0.46 g was kept at 45 ° C. and vigorously stirred. An aqueous solution containing 11.85 g of AgNO ₃ and an aqueous solution containing 3.8 g of KBr were added over 47 seconds by the double jet method. After raising the temperature to 63 ° C., 24.1 g of ion-exchanged gelatin having a molecular weight of 100,000 was added and aged. After sufficiently aging, an aqueous solution containing 133.4 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes so that the final flow rate was 2.6 times the initial flow rate by the double jet method. At this time, the silver potential was kept at +40 mV with respect to the saturated calomel electrode. In addition, 0.1 mg of K ₂ IrCl ₆ was added 10 minutes after the start of the addition. After adding 7 g of NaCl, an aqueous solution containing 45.6 g of AgNO ₃ and an aqueous KBr solution were added over 12 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. Further, 100 mL of an aqueous solution containing 29 mg of yellow blood salt was added over 6 minutes from the start of addition. After adding 14.4 g of KBr, 6.3 g of the AgI fine grain emulsion used in the preparation of Em-A1 was added in terms of KI mass. Immediately after the addition, an aqueous solution containing 42.7 g of AgNO ₃ and an aqueous KBr solution were added over 11 minutes by the double jet method. At this time, the silver potential was kept at +90 mV. It was washed with water in the same manner as Em-F and chemically sensitized.

(Em-I) (emulsion for low sensitivity green sensitive layer)
Em-H was prepared in substantially the same manner except that the temperature during nucleation was changed to 38 ° C.

(Em-J1) (Emulsion for high-sensitivity red-sensitive layer)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g and KBr, 0.99 g was kept at 60 ° C., pH was adjusted to 2, and vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing KBr, 1.97 g and KI, 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g, and NaCl 6.2 g were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at −50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was simultaneously added at a flow rate acceleration so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. After adding 1.5 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, KBr was added to adjust the silver potential to -100 mV. 6.2 g of the above-mentioned AgI fine grain emulsion was added in terms of KI mass. Immediately after the addition, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 8 minutes. Adjustment was made by adding an aqueous KBr solution so that the potential at the end of the addition was +60 mV. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. After adding compounds 11 and 12, the temperature was raised to 61 ° C. After adding sensitizing dyes 18, 19, 20 and 21, K ₂ IrCl ₆ , potassium thiocyanate, chloroauric acid, sodium thiosulfate, and N, N-dimethylselenourea were added for optimum chemical sensitization. Compounds 13 and 14 were added at the end of chemical sensitization.

(Em-J2)
Emulsion Em-J2 was obtained in the same manner as Em-J1, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-J3)
The compounds of the present invention at the time of chemical sensitization (IX-2-50), except that the added 1 × 10 ^-4 mol / molAg was obtained emulsion Em-J3 in the same manner as Em-J 2.

(Em-J4-J8)
Emulsion in the same manner as Em-J1 except that the compound (IV-2) of the present invention was added so as to have a content as shown in (Table 1) with respect to the sensitizing dye added during chemical sensitization. Em-J4 to J8 were obtained.

(Em-J9 ~ J13)
Em-J9 is the same as Em-J2 except that the compound of the present invention was added as shown in (Table 1) to the sensitizing dye added during chemical sensitization when (IV-2) was added during chemical sensitization. ~ J13 was obtained.

(Em-J14)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g and KBr, 0.99 g was kept at 60 ° C., pH was adjusted to 2, and vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing KBr, 1.97 g and KI, 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g and NaCl 6.2 g were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at −50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was added at the same time with the flow rate accelerated so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. After adding 1.5 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, the temperature was lowered to 40 ° C., and KBr was added to adjust the silver potential to −40 mV. While keeping the temperature at 40 ° C., an aqueous solution containing 14.2 g of sodium p-iodoacetamidobenzenesulfonate (monohydrate) was added, and then 57 mL of 0.8 M sodium sulfite aqueous solution was added in a fixed amount for 1 minute, and pH was adjusted. Iodide ions were generated while controlling at 9.0, and after 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was returned to 5.5. Immediately thereafter, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 20 minutes. During the addition, it was kept at -50 mV with an aqueous KBr solution. After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. Subsequent processes were the same as Em-J1.

(Em-J15)
Em-J15 was obtained in the same manner as Em-J14, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-J16)
Em-J16 was obtained in the same manner as Em-J15, except that it was added at 25 mol% with respect to the sensitizing dye to which the compound (IV-2) of the present invention was added during chemical sensitization.

(Em-J17)
Emulsion Em-J17 was obtained in the same manner as Em-J16, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

(Em-J18)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g, KBr, and 0.99 g was maintained at 60 ° C., pH was adjusted to 2, and vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing KBr, 1.97 g, KI, and 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g, and NaCl 6.2 g were added. 60.7 mL of an aqueous solution containing 27.3 g of AgNO ₃ and an aqueous KBr solution were added over 35 minutes by the double jet method. At this time, the silver potential was kept at −50 mV with respect to the saturated calomel electrode. An aqueous solution containing 65.6 g of AgNO ₃ and an aqueous KBr solution were added over 37 minutes while accelerating the flow rate so that the final flow rate was 2.1 times the initial flow rate by the double jet method. At this time, the AgI fine grain emulsion used in the preparation of Em-A1 was added at the same time with the flow rate accelerated so that the silver iodide content was 6.5 mol%, and the silver potential was kept at -50 mV. After adding 1.5 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, the temperature was lowered to 50 ° C. While maintaining the temperature at 50 ° C., 55 mL of 0.3% KI aqueous solution was added over 10 minutes. Immediately thereafter, 100 mL of an aqueous solution containing 14.2 g of AgNO ₃ , 120 mL of an aqueous solution containing 2.1 g of NaCl and 4.17 g of KBr, and a solution containing 0.0133 mol of AgI fine particles were added simultaneously. At this time, 9.4 × 10 ⁻⁴ mol of K ₄ [RuCN ₆ ] was present with respect to 1 mol of AgNO ₃ added. Thereafter, a sensitizing dye was added (for epitaxial stabilization). After washing with water, gelatin was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. Subsequent processes were the same as Em-J1.

(Em-J19)
Em-J19 was obtained in the same manner as Em-J18, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-J20)
Em-J20 was obtained in the same manner as Em-J19, except that it was added at 25 mol% with respect to the sensitizing dye to which the compound (IV-2) of the present invention was added during chemical sensitization.

(Em-J21)
Emulsion Em-J21 was obtained in the same manner as Em-J20, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

(Em-J22)
1200 mL of an aqueous solution containing phthalated gelatin having a phthalation rate of 97% and a molecular weight of 100,000, 0.38 g, KBr, and 0.99 g was maintained at 60 ° C., pH was adjusted to 2, and vigorously stirred. An aqueous solution containing 1.96 g of AgNO ₃ and an aqueous solution containing KBr, 1.97 g and KI, 0.172 g were added over 30 seconds by the double jet method. After completion of ripening, 12.8 g of trimellitated gelatin obtained by chemically modifying an amino group having a molecular weight of 100,000 containing 35 μmol of methionine per gram with trimellitic acid was added. After adjusting the pH to 5.9, KBr, 2.99 g, and NaCl 6.2 g were added. Silver iodide content by simultaneously adding an aqueous solution containing 92.9 g of AgNO ₃ , 762 mL and KBr 60.8 g, KI 5.9 g, and 762 mL of an aqueous solution containing 38.1 g of gelatin having a molecular weight of 20000 to a stirrer installed outside the reaction vessel While preparing a 6.5 mol% AgBrI fine grain emulsion (average size: 0.015 μm), this AgBrI emulsion was added to the reaction vessel over 90 minutes. At this time, the silver potential was kept at −30 mV with respect to the saturated calomel electrode. After adding 1.5 mg of thiourea dioxide, 132 mL of an aqueous solution containing 41.8 g of AgNO ₃ and an aqueous KBr solution were added over 13 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the silver potential at the end of the addition was +40 mV. After adding 2 mg of sodium benzenethiosulfonate, the temperature was lowered to 50 ° C. The temperature was lowered to 40 ° C., and KBr was added to adjust the silver potential to −40 mV. While keeping the temperature at 40 ° C., an aqueous solution containing 14.2 g of sodium p-iodoacetamidobenzenesulfonate (monohydrate) was added, and then 57 mL of 0.8 M sodium sulfite aqueous solution was added in a fixed amount for 1 minute, and pH was adjusted. Iodide ions were generated while controlling at 9.0, and after 2 minutes, the temperature was raised to 55 ° C. over 15 minutes, and then the pH was returned to 5.5. Immediately thereafter, 300 mL of an aqueous solution containing 88.5 g of AgNO ₃ was added over 20 minutes. During the addition, it was kept at -50 mV with an aqueous KBr solution. After washing with water, gelatin containing 30% of a component having a molecular weight of 280,000 or more as measured according to the PAGI method was added and adjusted to pH 6.5, pAg, 8.2 at 40 ° C. Subsequent processes were the same as Em-J1.

(Em-J23)
Em-J23 was obtained in the same manner as Em-J22, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-J24)
Em-J24 was obtained in the same manner as Em-J23, except that it was added at 25 mol% with respect to the sensitizing dye to which the compound (IV-2) of the present invention was added during chemical sensitization.

(Em-J25)
The compounds of the present invention at the time of chemical sensitization (I-13) to 1 × 10 ^-4 mol / molAg, and compound (IX-2-50), except that the added 1 × 10 ^-4 mol / molAg includes Em-J24 Similarly, Em-J25 was obtained.

(Em-K) (Emulsion for medium sensitivity red sensitive layer)
1200 mL of an aqueous solution containing 4.9 g of low molecular weight gelatin having a molecular weight of 15000, KBr, and 5.3 g was kept at 60 ° C. and stirred vigorously. 27 mL of an aqueous solution containing 8.75 g of AgNO ₃ and 36 mL of an aqueous solution containing 6.45 g of KBr were added by a double jet method over 1 minute. After raising the temperature to 77 ° C., 21 mL of an aqueous solution containing 6.9 g of AgNO ₃ was added over 2.5 minutes. NH ₄ NO ₃ , 26 g, 1N, NaOH, and 56 mL were sequentially added, followed by aging. After completion of aging, the pH was adjusted to 4.8. 438 mL of an aqueous solution containing 141 g of AgNO ₃ and 458 mL of an aqueous solution containing 102.6 g of KBr were added by the double jet method so that the final flow rate was four times the initial flow rate. After the temperature was lowered to 55 ° C., 240 mL of an aqueous solution containing 7.1 g of AgNO ₃ and an aqueous solution containing 6.46 g of KI were added over 5 minutes by the double jet method. After adding 7.1 g of KBr, 4 mg of sodium benzenethiosulfonate and 0.05 mg of K ₂ IrCl ₆ were added. 177 mL of an aqueous solution containing 57.2 g of AgNO ₃ and 223 mL of an aqueous solution containing 40.2 g of KBr were added by the double jet method over 8 minutes. It was washed with water in the same manner as Em-J and chemically sensitized.

(Em-L) (Emulsion for medium sensitivity red sensitive layer)
Em-K was prepared in substantially the same manner except that the temperature during nucleation was changed to 42 ° C.

(Em-M, N, O) (Low-sensitivity red-sensitive emulsion)
Prepared in substantially the same manner as Em-H or Em-I. However, chemical sensitization was carried out in substantially the same manner as Em-J1.

(Em-P1) (Emulsion for high sensitivity green sensitive layer)
For Em-J1, the sensitizing dye was changed to 15, 16 and 17, and chemical sensitization was optimally performed to obtain Em-P1.

(Em-P2)
Em-P2 was obtained in the same manner as Em-P1, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-P3)
Emulsion Em-P3 was obtained in the same manner as Em-P 2 except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

(Em-P4)
For Em-J14, the sensitizing dye was changed to 15, 16 and 17, and chemical sensitization was optimally performed to obtain Em-P4.

(Em-P5)
Em-P5 was obtained in the same manner as Em-P4, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-P6)
Emulsion Em-P6 was obtained in the same manner as Em-P5, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

(Em-P7)
For Em-J18, the sensitizing dye was changed to 15, 16 and 17, and chemical sensitization was optimally performed to obtain Em-P7.

(Em-P8)
Em-P8 was obtained in the same manner as Em-P7, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-P9)
Emulsion Em-P9 was obtained in the same manner as Em-P8, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

(Em-P10)
For Em-J22, the sensitizing dye was changed to 15, 16 and 17, and chemical sensitization was optimally performed to obtain Em-P10.

(Em-P11)
Em-P11 was obtained in the same manner as Em-P10, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-P12)
Emulsion Em-P12 was obtained in the same manner as Em-P11 except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

The characteristics of the thus obtained silver halide emulsions Em-A to P are shown in Table 2.

  Moreover, the outline of preparation formulation of the emulsion of this invention is shown below.

  A 10% gelatin solution containing a coupler dissolved in ethyl acetate, a high-boiling organic solvent, and a surfactant are added and emulsified using a mixed homogenizer (Nippon Seiki) to obtain an emulsion.

1) Support The support used in this example was prepared by the following method.

  100 parts by mass of polyethylene-2,6-naphthalate polymer and Tinuvin P.I. 326 (manufactured by Ciba-Geigy Ciba-Geigy) was dried, melted at 300 ° C, extruded from a T-die, and stretched 3.3 times at 140 ° C, followed by 130 ° C. The film was stretched by 3.3 times and further heat-fixed at 250 ° C. for 6 seconds to obtain a PEN (polyethylene naphthalate) film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye, and a yellow dye (public techniques: I-1, I-4, I-6, I-24, I-26, I- 27, II-5) was added in an appropriate amount. Further, it was wound around a stainless steel core having a diameter of 20 cm to give a thermal history of 110 ° C. and 48 hours, thereby providing a support that is difficult to curl.

2) Coating of undercoat layer The above support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides, and then gelatin 0.1 g / m ² and sodium α-sulfodi-2 on each side. - ethylhexyl succinate 0.01 g / m ^2, salicylic acid 0.04 g / m @ 2, p-chlorophenol _{^{0.2g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.012g / m 2 Polyamide-epichlorohydrin polycondensate 0.02 g / m ² undercoat solution was applied (10 mL / m ² , using bar coater), and an undercoat layer was provided on the high-temperature surface side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and conveyors in the drying zone were at 115 ° C.).

3) Coating of Back Layer An antistatic layer having the following composition, a magnetic recording layer, and a sliding layer were coated as a back layer on one surface of the support after undercoating.

3-1) Coating of antistatic layer The specific resistance of the tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm is 0 of a dispersion of fine powder of 5 Ω · cm (secondary aggregate particle diameter of about 0.08 μm). .2g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.02g / m 2, poly (polymerization degree 10) oxyethylene -p- nonylphenol 0. 005 g / m ² and resorcin.

3-2) Coating of magnetic recording layer 3-Cobalt-γ-iron oxide coated with poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) (specific surface area 43 m ² / g, (Major axis 0.14μm, uniaxial 0.03μm, saturation magnetization 89Am ² / kg, Fe ⁺² / Fe ⁺³ = 6/94, the surface is treated with 2% by mass of iron oxide with silicon oxide oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide was carried out with an open kneader and a sand mill), C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a magnetic recording layer having a thickness of 1.2 μm. 10 mg each of abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by mass) as a matting agent / M ² was added. Drying was performed at 115 ° C. for 6 minutes (all rollers and transporting devices in the drying zone were 115 ° C.). X- light (blue filter) saturation magnetization moment of about 0.1, and the magnetic recording layer is color density increment of D ^B of the magnetic recording layer of the 4.2Am ² / kg, a coercive force 7.3 × 10 ⁴ A / m, the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetylcellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by melting at 105 ° C. in xylene / propylene monomethyl ether (1/1) and pouring and dispersing in propylene monomethyl ether at room temperature (10 times the amount). The average particle size was 0.01 μm) and then added. 15 mg / m each of aluminum particles (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (polymerization degree 15) oxyethylenepropyloxytrimethoxysilane (15% by mass) as a matting agent It added so that it might become ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were 115 ° C.). The sliding layer has a dynamic friction coefficient of 0.06 (5 mmφ stainless hard balls, load of 100 g, speed of 6 cm / min), static friction coefficient of 0.07 (clipping method), and the dynamic friction coefficient of the emulsion surface and the sliding layer described later is 0.12. Excellent characteristics.

4) Coating of photosensitive layer Next, on the opposite side to the support of the back layer obtained above, each layer having the following composition was applied in layers to prepare a sample which is a color negative photosensitive material. Samples were made using emulsions, emulsions and couplers as shown in (Table 3), (Table 4), and (Table 5). Emulsions, couplers, high boiling point organic solvents and surfactants were replaced in equal amounts. Moreover, when using two or more, it replaced so that the sum might be equivalent replacement. Specifically, two cases were replaced by 1/3, and three cases were replaced by 1/3.

(Composition of photosensitive layer)
The main materials used in each layer are classified as follows:
ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin hardener The chemical formula is mentioned)
The number corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver.

First layer (first antihalation layer)
Black colloidal silver Silver 0.155
0.07 μm surface fogging AgBrI (2) Silver 0.01
Gelatin 0.87
ExC-1 0.002
ExC-3 0.002
Cpd-2 0.001
HBS-1 0.004
HBS-2 0.002

Second layer (second antihalation layer)
Black colloidal silver Silver 0.066
Gelatin 0.407
ExM-1 0.050
ExF-1 2.0 × 10 ⁻³
HBS-1 0.074
Solid disperse dye ExF-2 0.015
Solid disperse dye ExF-3 0.020

Third layer (intermediate layer)
0.07 μ AgBrI (2) 0.020
ExC-2 0.022
Polyethyl acrylate latex 0.085
Gelatin 0.294

4th layer (low sensitivity red sensitive emulsion layer)
Silver iodobromide emulsion M Silver 0.065
Silver iodobromide emulsion N Silver 0.100
Silver iodobromide emulsion O Silver 0.158
ExC-1 0.109
ExC-3 0.044
ExC-4 0.072
ExC-5 0.011
ExC-6 0.003
Cpd-2 0.025
Cpd-4 0.025
HBS-1 0.17
Gelatin 0.80

5th layer (medium sensitivity red emulsion layer)
Silver iodobromide emulsion K Silver 0.21
Silver iodobromide emulsion L Silver 0.62
ExC-1 0.14
ExC-2 0.026
ExC-3 0.020
ExC-4 0.12
ExC-5 0.016
ExC-6 0.007
Cpd-2 0.036
Cpd-4 0.028
HBS-1 0.16
Gelatin 1.18

6th layer (high-sensitivity red-sensitive emulsion layer)
Silver iodobromide emulsion J Silver 1.67
ExC-1 0.18
ExC-3 0.07
ExC-6 0.047
Cpd-2 0.046
Cpd-4 0.077
HBS-1 0.25
HBS-2 0.12
Gelatin 2.12

7th layer (intermediate layer)
Cpd-1 0.089
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.83
Gelatin 0.84

Eighth layer (Multilayer effect donor layer (layer that gives a multilayer effect to the red-sensitive layer))
Silver iodobromide emulsion E Silver 0.560
Cpd-4 0.030
ExM-2 0.096
ExM-3 0.028
ExY-1 0.031
ExG-1 0.006
HBS-1 0.085
HBS-3 0.003
Gelatin 0.58

9th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion G Silver 0.39
Silver iodobromide emulsion H Silver 0.28
Silver iodobromide emulsion I Silver 0.35
ExM-2 0.36
ExM-3 0.045
ExG-1 0.005
HBS-1 0.28
HBS-3 0.01
HSB-4 0.27
Gelatin 1.39

10th layer (medium sensitive green sensitive emulsion layer)
Silver iodobromide emulsion F Silver 0.20
Silver iodobromide emulsion G Silver 0.25
ExC-6 0.009
ExM-2 0.031
ExM-3 0.029
ExY-1 0.006
ExM-4 0.028
ExG-1 0.005
HBS-1 0.064
HBS-3 2.1 × 10 ^-3
Gelatin 0.44

11th layer (high sensitivity green emulsion layer)
Emulsion Em-P1 Silver of Example 1 1.200
ExC-6 0.004
ExM-1 0.016
ExM-3 0.036
ExM-4 0.020
ExM-5 0.004
ExY-5 0.008
ExM-2 0.013
Cpd-4 0.007
HBS-1 0.18
Polyethyl acrylate latex 0.099
Gelatin 1.11

12th layer (yellow filter layer)
Yellow colloidal silver Silver 0.047
Cpd-1 0.16
ExF-5 0.010
Solid disperse dye ExF-6 0.010
HBS-1 0.082
Gelatin 1.057

13th layer (low sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion B Silver 0.18
Silver iodobromide emulsion C Silver 0.20
Silver iodobromide emulsion D Silver 0.07
ExC-1 0.041
ExC-8 0.012
ExY-1 0.035
ExY-2 0.71
ExY-3 0.10
ExY-4 0.005
Cpd-2 0.10
Cpd-3 4.0 × 10 ⁻³
HBS-1 0.24
Gelatin 1.41

14th layer (high sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion A Silver 0.75
ExC-1 0.013
ExY-2 0.31
ExY-3 0.05
ExY-6 0.062
Cpd-2 0.075
Cpd-3 1.0 × 10 ⁻³
HBS-1 0.10
Gelatin 0.91

15th layer (first protective layer)
0.07 μm AgBrI (2) Silver 0.30
UV-1 0.21
UV-2 0.13
UV-3 0.20
UV-4 0.025
F-11 0.009
F-18 0.005
F-19 0.005
HBS-1 0.12
HBS-4 5.0 × 10 ^-2
Gelatin 2.3

16th layer (second protective layer)
H-1 0.40
B-1 (diameter 1.7 μm) 5.0 × 10 ⁻²
B-2 (diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 0.75

Furthermore, storage stability, processability, pressure resistance, antifungal and antibacterial properties, B-4 to B-6, F-1 to F-17, and iron salts, lead salts, gold salts, platinum salts, as appropriate for each layer , Palladium salts, iridium salts, ruthenium salts and rhodium salts. Further, 8.5 × 10 ⁻³ gram per mole of silver halide was added to the eighth layer coating solution and 7.9 × 10 ⁻³ gram calcium was added to the eleventh layer with a calcium nitrate aqueous solution to prepare a sample. . Further, at least one of W-1, W-6, W-7, and W-8 is contained for improving antistatic properties, and at least one of W-2 and W-5 is used for improving coating properties. Contains.

Preparation of organic solid disperse dye The following ExF-3 was dispersed by the following method. That is, 21.7 mL of water and 3 mL of 5% aqueous p-octylphenoxyethoxyethoxyethane sulfonate and 0.5 g of 5% aqueous p-octylphenoxypolyoxyethylene ether (degree of polymerization 10) were placed in a 700 mL pot mill. Then, 5.0 g of dye ExF-3 and 500 mL of zirconium oxide beads (diameter 1 mm) were added, and the contents were dispersed for 2 hours. A BO-type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After dispersion, the contents were taken out and added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle diameter of the dye fine particles was 0.44 μm.

  Similarly, a solid dispersion of ExF-4 was obtained. The average particle size of the fine dye particles was 0.24 μm. ExF-2 was dispersed by the microprecipitation dispersion method described in Example 1 of EP 549,489A. The average particle size was 0.06 μm.

A solid dispersion of ExF-6 was dispersed by the following method.
To 2800 g of ExF-6 wet cake containing 18% of water, 376 g of 4000 g of water and a 3% solution of W-2 was added and stirred to obtain a slurry of ExF-6 having a concentration of 32%. Next, 1700 mL of zirconia beads having an average particle diameter of 0.5 mm was filled in Ultraviscomil (UVM-2) manufactured by Imex Co., Ltd., and pulverized for 8 hours through the slurry at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 L / min. did. The average particle size was 0.45 μm.
The compounds used for forming each of the above layers are as shown below.

  The sample evaluation method is as follows. The film was exposed for 1/100 second through a gelatin filter SC-39 (long wavelength light transmission filter having a cut-off wavelength of 390 nm) and a continuous wedge manufactured by FUJIFILM Corporation. Development was performed as follows using an automatic processor FP-360B manufactured by Fuji Photo Film Co., Ltd. In addition, the overflow solution of the bleaching bath was remodeled so as not to flow to the rear bath but to discharge all to the waste liquid tank. This FP-360B is equipped with an evaporation correction means described in Japanese Society of Invention and Innovation technique 94-4992.

  The treatment process and the treatment liquid composition are shown below.

(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ℃ 20 mL 11.5 L
Whitening 50 seconds 38.0 ℃ 5 mL 5L
Fixing (1) 50 seconds 38.0 ℃ -5L
Fixing (2) 50 seconds 38.0 ℃ 8 mL 5L
Washing with water 30 seconds 38.0 ℃ 17 mL 3L
Stable (1) 20 seconds 38.0 ℃ -3L
Stable (2) 20 seconds 38.0 ℃ 15 mL 3L
Dry 1 min 30 sec 60.0 ℃
* Replenishment amount per photosensitive material 35mm width 1.1m (equivalent to 24Ex. 1)
The stabilizing solution and the fixing solution were counter-current from (2) to (1), and all the overflow solution of the washing water was introduced into the fixing bath (2). The amount of developer brought into the bleaching step, the amount of bleaching solution brought into the fixing step, and the amount of fixing solution brought into the water washing step were 2.5 mL and 2.0 mL for a photosensitive material 35 mm width 1.1 m, respectively. 2.0 mL. In addition, the crossover time is 6 seconds, and this time is included in the processing time of the previous process.
Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the treatment liquid is shown below.
(Color developer) Tank solution (g) Replenisher (g)
Diethylenetriaminepentaacetic acid 3.0 3.0
Catechol-3,5-disulfonic acid disodium 0.3 0.3
Sodium sulfite 3.9 5.3
Potassium carbonate 39.0 39.0
Disodium-N, N-bis (2-sulfonateethyl) hydroxylamine 1.5 2.0
Potassium bromide 1.3 0.3
Potassium iodide 1.3mg −
4-hydroxy-6-methyl-1,3
3a, 7-tetrazaindene 0.05-
Hydroxylamine sulfate 2.4 3.3
2-Methyl-4- [N-ethyl-N-
(Β-hydroxyethyl) amino]
Aniline sulfate 4.5 6.5
Add water 1.0L 1.0L
pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

(Bleaching solution) Tank solution (g) Replenisher solution (g)
1,3-diaminopropanetetraacetic acid ferric ammonium monohydrate 113 170
Ammonium bromide 70 105
Ammonium nitrate 14 21
Succinic acid 34 51
Maleic acid 28 42
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia] 4.6 4.0

(Fixing (1) Tank liquid)
5:95 (volume ratio) mixture of the above bleach tank solution and the following fixing tank solution (pH 6.8)

(Fixing (2)) Tank liquid (g) Replenisher (g)
Ammonium thiosulfate aqueous solution 240 mL 720 mL
(750g / L)
Imidazole 7 21
Ammonium methanethiosulfonate 5 15
Ammonium methanesulfinate 10 30
Ethylenediaminetetraacetic acid 13 39
Add water 1.0L 1.0L
pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water)
Tap water is passed through a mixed bed column packed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type strongly basic anion exchange resin (Amberlite IR-400). Then, the calcium and magnesium ion concentrations were adjusted to 3 mg / L or less, and then sodium isocyanurate dichloride 20 mg / L and sodium sulfate 150 mg / L were added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizer) Tank fluid and replenisher common (Unit: g)
Sodium p-toluenesulfinate 0.03
Polyoxyethylene-p-monononylphenyl ether 0.2
(Average polymerization degree 10)
1,2-Benzisothiazoline-3-one sodium 0.10
Ethylenediaminetetraacetic acid disodium salt 0.05
1,2,4-triazole 1.3
1,4-bis (1,2,4-triazole-1-
Ilmethyl) piperazine 0.75
Add water and add 1.0L
pH 8.5

  The said process was performed with respect to the samples 101-125. The same treatment was applied to samples that had been aged for 3 days under conditions of 50 ° C. and 80% RH. Photographic performance was evaluated by measuring the density of the processed sample with a blue filter. The obtained results are shown in (Table 6).

In the emulsion of the present invention, a combination of the compound of the general formula (I) of the present invention and the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention, and the high By the combination with the boiling organic solvent and the combination of the general formula (I) of the present invention with the general formula (IV) or (V) of the present invention, a light-sensitive material with low covering and high sensitivity could be achieved. Furthermore, a light-sensitive material having high storage cover resistance could be achieved by combining the compounds of the general formulas (VI) to (X) of the present invention as described above.

  The said process was performed with respect to the samples 201-216. The same treatment was applied to samples that had been aged for 3 days under conditions of 50 ° C. and 80% RH. Photographic performance was evaluated by measuring the density of the processed sample with a green filter. The obtained results are shown in (Table 7).

In the emulsion of the present invention, a combination of the compound of the general formula (I) of the present invention and the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention, and the high By the combination with the boiling organic solvent and the combination of the general formula (I) of the present invention with the general formula (IV) or (V) of the present invention, a light-sensitive material with low covering and high sensitivity could be achieved. Furthermore, a light-sensitive material having high storage cover resistance could be achieved by combining the compounds of the general formulas (VI) to (X) of the present invention as described above.

  The said process was performed with respect to the samples 301-330. The same treatment was applied to samples that had been aged for 3 days under conditions of 50 ° C. and 80% RH. Photographic performance was evaluated by measuring the density of the processed sample with a red filter. The obtained results are shown in (Table 8).

In the emulsion of the present invention, a combination of the compound of the general formula (I) of the present invention and the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention, and the high By the combination with the boiling organic solvent and the combination of the general formula (I) of the present invention with the general formula (IV) or (V) of the present invention, a light-sensitive material with low covering and high sensitivity could be achieved. Furthermore, a light-sensitive material having high storage cover resistance could be achieved by combining the compounds of the general formulas (VI) to (X) of the present invention as described above.

  From the above results, it can be seen that a silver halide photographic light-sensitive material with high sensitivity and low fog, little desensitization after thermography, and little increase in fog is obtained by the combination of the compounds of the present invention.

(Example 2)
Emulsion Em-X1: (100) Silver iodobromide tabular emulsion Polyvinyl alcohol (polyvinyl alcohol having a polymerization degree of vinyl acetate of 1700 and an average saponification rate of 98%, hereinafter polymer (PV)) and gelatin aqueous solution in a reaction vessel Prepare 1200 g water (containing 5 g polymer (PV) and 8 g deionized alkali-treated gelatin), adjust pH to 11 and maintain temperature at 55 ° C. While stirring, 200 mL of Ag-1 solution (containing 0.58 mol / L AgNO ₃ ) and 200 mL of X-1 solution (containing KBr 0.58 mol / L) were added over 40 minutes. The addition was performed by a double jet method using a precision liquid feed pump.

After 5 minutes, adjust the pH to 6 and use Ag-2 solution (containing AgNO ₃ 1.177 mol / L) and X-2 solution (containing KBr 1.177 mol / L). 600 mL quantitative double jet was added at / min. Next, an aqueous gelatin solution (containing 30 g of gelatin in 200 mL of water) and spectral sensitizing dyes 22, 23, and 24 were added, and Ag-3 solution (containing 2.94 mol / L of AgNO ₃ ) and X-3 solution (KBr 2.7 mol / L) 100 mL of L and KI (containing 0.24 mol / L) were added at a rate of 5 mL / min to complete the particle formation. Thereafter, the temperature was lowered to 35 ° C. and washed with a precipitation washing method. An aqueous gelatin solution was added to redisperse the emulsion, and the pH was adjusted to 6 and the pAg to 8.3.

As a result of obtaining from the replica TEM image of the emulsion grains, 93% of the total projected area of the grains prepared by the above method was the following grains. The main plane was a (100) plane, a sphere equivalent diameter of 0.4 μm or more, a particle thickness of 0.08 μm, and an aspect ratio of 9.5 or more.
The emulsion was optimally chemically sensitized with reference to Em-J1 shown in Example 1, except for the sensitizing dye, to obtain Em-X1.

(Em-X2)
Em-X2 was obtained in the same manner as Em-X1, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-X3)
Em-X3 was obtained in the same manner as Em-X 2 except that 10 mol% was added to the sensitizing dye to which the compound (IV-2) of the present invention was added during chemical sensitization.

(Em-X4)
Emulsion Em-X4 was obtained in the same manner as Em-X3 except that 1 × 10 ^-4 mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

Each emulsion was dissolved for 30 minutes at 40 ° C. on a cellulose triacetate film support provided with an undercoat layer, and then the above emulsions Em-X1 to X4 were applied under the coating conditions shown in Table 9 below. It was.

Samples 401 to 405 were prepared by changing the emulsion to be coated as shown in Table 10.

These samples were subjected to hardening for 14 hours under conditions of 40 ° C. and 70% relative humidity. Thereafter, exposure was performed through a continuous wedge for 1/100 second, and the density of a sample subjected to the following development processing was measured with a green filter to determine the photographic sensitivity and fog density before long-term storage. The sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to reach a fog density plus 0.2. As an evaluation of the storage fog of the light-sensitive material, it was stored for 14 days under the conditions of 40 ° C. and 60% relative humidity, then exposed to 1/100 second, and the density of a sample subjected to the following development processing was measured with a green filter and long-term. The fog density after storage was determined, and the fog density difference before and after storage was determined.
Development was performed as follows using an automatic processor FP-362B manufactured by Fuji Photo Film Co., Ltd.

  The treatment process and the treatment liquid composition are shown below.

(Processing process)
Process Processing time Processing temperature Replenishment amount * Tank capacity
Color development 3 minutes 5 seconds 38.0 ° C 15 mL 10.3 L
Bleaching 50 seconds 38 ° C 5mL 3.6L
Fixing (1) 50 seconds 38 ° C-3.6L
Fixing (2) 50 seconds 38 ° C 7.5mL 3.6L
Stable (1) 30 seconds 38 ° C-1.9L
Stable (2) 20 seconds 38 ° C-1.9L
Stable (3) 20 seconds 38 ° C 30 mL 1.9 L
Dry 1 min 30 sec 60 ° C
* Replenishment amount per photosensitive material 35mm width 1.1m (24Ex. 1 equivalent)
The stabilizing liquid is a countercurrent system from (3) → (2) → (1), and the fixing liquid is also connected from (2) to (1) by countercurrent piping. In addition, 15 mL of the tank liquid of the stabilizing liquid (2) is flowing into the fixing liquid (2) corresponding to the replenishing amount. Further, the color developer is replenished as a total of 15 mL by dividing the color developer (A) replenisher and color developer (B) replenisher of the following formulation into 12 mL and 3 mL, respectively, corresponding to the replenishment amount. The amount of the developer brought into the bleaching process, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the water washing step were all 2.0 mL per 1.1 m width of the photosensitive material 35 mm wide. The crossover time is 6 seconds, and this time is included in the processing time of the previous process.

The composition of the treatment liquid is shown below.
(Color developer (A)) <Tank solution><Replenisher>
Diethylenetriaminepentaacetic acid 2.0 g 4.0 g
Sodium 4,5-dihydroxybenzene-1,3-disulfonate
0.4g 0.5g
Disodium-N, N-bis (sulfonate ethyl) hydroxylamine
10.0g 15.0g
Sodium sulfite 4.0 g 9.0 g
Hydroxylamine sulfate 2.0 g −
Potassium bromide 1.4g −
Diethylene glycol 10.0 g 17.0 g
Ethyleneurea 3.0g 5.5g
2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino]
Aniline sulfate 4.7 g 11.4 g
Potassium carbonate 39g 59g
Add water 1.0L 1.0L
pH (prepared with sulfuric acid and KOH) 10.05 10.50
The tank solution has the following composition after mixing (color developer (B)).

(Color developer (B)) <Tank solution><Replenisher>
Hydroxylamine sulfate 2.0 g 4.0 g
Add water 1.0L 1.0L
pH (prepared with sulfuric acid and KOH) 10.05 4.0
The tank solution shows the composition after mixing the (color developer (A)).

(Bleaching solution) <Tank solution><Replenishersolution>
1,3-diaminopropanetetraacetic acid ferric ammonium salt-hydrate
120g 180g
Ammonium bromide 50g 70g
Succinic acid 30g 50g
Maleic acid 40g 60g
Imidazole 20g 30g
Add water 1.0L 1.0L
pH (adjusted with aqueous ammonia and nitric acid) 4.6 4.0

(Fixing solution) <Tank solution><Replenishersolution>
Ammonium thiosulfate (750 g / L) 280 mL 1000 mL
Ammonium bisulfite aqueous solution (72%) 20g 80g
Imidazole 5g 45g
1-mercapto-2- (N, N-dimethylaminoethyl) -tetrazole
1g 3g
Ethylenediaminetetraacetic acid 8g 12g
Add water 1L 1L
pH (adjusted with aqueous ammonia and nitric acid) 7.0 7.0

(Stabilizer) <Common tank fluid and replenisher>
Sodium p-toluenesulfinate 0.03g
p-nonylphenoxypolyglycidol (average glycidol polymerization degree 10)
0.4g
Ethylenediaminetetraacetic acid disodium salt 0.05g
1,2,4-triazole 1.3g
1,4-bis (1,2,4-triazol-1-ylmethyl)
Piperazine 0.75g
1,2-benzisothiazolin-3-one 0.10 g
Add water and add 1.0L
pH 8.5

Table 11 shows the results of evaluation by the above method. The sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to reach a fog density plus 0.2. In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention and the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention, and the high By the combination with the boiling organic solvent and the combination of the general formula (I) of the present invention and the general formula (IV) of the present invention, a light-sensitive material with low covering and high sensitivity could be achieved. Further, by combining the compounds of the general formulas (VI) to (X) of the present invention with the above, a light-sensitive material having high storage cover resistance could be achieved.

(Example 3)
Emulsion Em-Y1: (111) Silver chloride tabular grains In 1.2 L of water, 2.0 g of sodium chloride and 2.8 g of inert gelatin were added, and 60 mL of Ag-1 solution (silver nitrate) was stirred into a container kept at 35 ° C. 9 g) and 60 mL of X-1 solution (containing 3.2 g of sodium chloride) were added in 1 minute by the double jet method. One minute after completion of the addition, 0.8 mmol of N-benzyl-4-phenylpyridinium chloride was added. After another minute, 3.0 g of sodium chloride was added. The temperature of the reaction vessel was raised to 60 ° C. over the next 25 minutes. After aging at 60 ° C. for 16 minutes, 560 g of 10% phthalated gelatin aqueous solution and 1 × 10 ⁻⁵ mol of sodium thiosulfonate were added. After this, 317.5 mL of Ag-2 solution (containing 127 g of silver nitrate), X-2 solution (containing 54.1 g of sodium chloride), and 160 mL of crystal phase control agent 1 aqueous solution (M / 50) were added at an accelerated flow rate over 20 minutes. did. Furthermore, Ag-3 solution (containing 34 g of silver nitrate) and X-3 solution (containing 11.6 g of sodium chloride and 1.27 mg of yellow blood salt) were added in 5 minutes after 2 minutes. Next, 33.5 mL of 0.1N thiocyanic acid solution and 0.32 mmol of sensitizing dye 25, 0.48 mmol of sensitizing dye 26, and 0.05 mmol of sensitizing dye 27 were added.

The temperature was lowered to 40 ° C. and washed with a precipitation washing method. An aqueous gelatin solution was added to redisperse the emulsion, and the pH was adjusted to 6.2 and the pAg to 7.5.
The grains prepared by the above method were determined from the replica TEM image of the emulsion grains. As a result, 50% or more of the total projected area was the following grains. The main plane was a (111) plane, a sphere equivalent diameter of 0.56 to 0.66 μm, a projected area diameter of 0.95 to 1.15 μm, and a particle thickness of 0.12 to 0.16 μm.
The emulsion was optimally chemically sensitized with reference to Em-J1 shown in Example 1, except for the sensitizing dye, to obtain Em-Y1.

(Em-Y2)
Em-Y2 was obtained in the same manner as Em-Y1, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-Y3)
Except for adding 10 mol% with respect to the sensitizing dye was added compound (IV-2) of the present invention at the time of chemical sensitization was obtained Em-Y3 in the same manner as Em-Y 2.

(Em-Y4)
Emulsion Em-Y4 was obtained in the same manner as Em-Y3 except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

After each emulsion was dissolved for 30 minutes at 40 ° C. on a cellulose triacetate film support provided with an undercoat layer, the emulsions Em-Y1 to Y4 were coated under the coating conditions shown in Table 9 above. went.
Samples 501 to 505 were prepared by changing the emulsion to be coated as shown in Table 12.

Table 13 shows the results of evaluation performed in the same manner as in Example 3. The sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to reach a fog density plus 0.2. In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention and the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention, and the high By the combination with the boiling organic solvent and the combination of the general formula (I) of the present invention and the general formula (IV) of the present invention, a light-sensitive material with low covering and high sensitivity could be achieved. Further, by combining the compounds of the general formulas (VI) to (X) of the present invention with the above, a light-sensitive material having high storage cover resistance could be achieved.

(Example 4)
Emulsion Em-Z1: (100) Silver chloride tabular grains containing 0.4 mol% of iodine with respect to the total silver amount in the shell portion Put 1200 mL of water, 25 g of gelatin, 0.4 g of sodium chloride, 4.5 mL of 1N nitric acid aqueous solution into the reaction vessel ( The pH was 4.5) and kept at 40 ° C. Next, Ag-1 solution (silver nitrate 0.2 g / mL) and X-1 solution (sodium chloride 0.069 g / mL) were added and mixed at 48 mL / min for 4 minutes with vigorous stirring. 15 seconds later, 150 mL of an aqueous polyvinyl alcohol solution (average polymerization degree of vinyl acetate is 1700, polyvinyl alcohol having an average saponification rate of 98% or more (hereinafter referred to as PVA-1) in alcohol is contained in 1 L of water) is added to 150 mL of pH 3 Adjusted to .5. The temperature was raised to 75 ° C. over 15 minutes, 23 mL of 1N aqueous sodium hydroxide solution was added to adjust the pH to 6.5, 4.0 mL of 1- (5-methylureidophenyl) -5-mercaptotetrazole (0.05%), N, N ′ -4.0 mL of dimethyl imidazolidine-2-thione (1% aqueous solution) was added.

  After adding 4 g of sodium chloride and adjusting the silver potential (vs. room temperature saturated calomel electrode) to 100 mV, as the growth process, increase the Ag-1 and X-1 solutions linearly from a flow rate of 40 mL / min to 42 mL / min. Simultaneously added while maintaining the silver potential at 100 mV for a minute. Furthermore, 12.5 mL of 1N nitric acid aqueous solution was added to adjust the pH to 4.0. After adding 28.8 g of sodium chloride and adjusting the silver potential to 60 mV, 0.38 mmol of sensitizing dye 25, 0.56 mmol of sensitizing dye 26, and 0.06 mmol of sensitizing dye 27 were added, and Ag-2 solution (silver nitrate 0.1 / mL) was added. ) And solution X-2 (an aqueous solution containing 33.8 g of sodium chloride and 1.95 g of potassium iodide in 1 liter so that the total amount of iodine is 0.4 mol% of the total silver amount) at a flow rate of 40 mL / min for 10 minutes, Thereafter, it was left at 75 ° C. for 10 minutes.

The temperature was lowered to 40 ° C. and washed with a precipitation washing method. An aqueous gelatin solution was added to redisperse the emulsion, and the pH was adjusted to 6.0 and the pAg to 7.3.
The grains prepared by the above method were determined from the replica TEM image of the emulsion grains. As a result, 50% or more of the total projected area was the following grains. The main plane was a (100) plane, a sphere equivalent diameter of 0.4 to 0.5 μm, a particle thickness of 0.10 to 0.12 μm, an aspect ratio of 6.5 or more, and an adjacent side ratio of 1.1 to 1.3.
The above emulsion was optimally chemically sensitized with reference to Em-J1 shown in Example 1 except for the sensitizing dye to obtain Em-Z1.

(Em-Z2)
Em-Z2 was obtained in the same manner as Em-Z1, except that 1 × 10 ⁻⁴ mol / mol Ag of the compound (I-13) of the present invention was added during chemical sensitization.

(Em-Z3)
Em-Z3 was obtained in the same manner as Em-Z 2 except that 10 mol% was added to the sensitizing dye to which the compound (IV-2) of the present invention was added during chemical sensitization.

(Em-Z4)
Emulsion Em-Z4 was obtained in the same manner as Em-Z3 except that 1 × 10 ⁻⁴ mol / mol Ag of the compound of the present invention (IX-2-50) was added during chemical sensitization.

After each emulsion was dissolved for 30 minutes at 40 ° C. on a cellulose triacetate film support provided with an undercoat layer, the emulsions Em-Z1 to Z4 were coated under the coating conditions shown in Table 9 above. went.
Samples 601 to 605 were prepared by changing the emulsion to be coated as shown in Table 14.

Table 15 shows the results of evaluation performed in the same manner as in Example 3.

The sensitivity is expressed as a relative value of the reciprocal of the exposure amount necessary to reach a fog density plus 0.2.
In the emulsion of the present invention, the combination of the compound of the general formula (I) of the present invention and the general formula (II) or (III), the general formula (I) of the present invention, the surfactant of the present invention, and the high By the combination with the boiling organic solvent and the combination of the general formula (I) of the present invention with the general formula (IV) or (V) of the present invention, a light-sensitive material with low covering and high sensitivity could be achieved. Further, by combining the compounds of the general formulas (VI) to (X) of the present invention with the above, a light-sensitive material having high storage cover resistance could be achieved.

Claims (14)

A silver halide color photographic light-sensitive material having at least one blue-sensitive layer, green-sensitive layer and red-sensitive layer on a support , wherein the blue-sensitive layer is in the same layer and has a critical micelle concentration of 4.0. It contains an emulsified dispersion containing 0.01% by mass or more of all the components contained in the blue-sensitive layer, and a compound represented by the following general formula (I): a surfactant of × 10 ⁻³ mol / L or less. A characteristic silver halide color photographic light-sensitive material.
Formula (I)
(X) _k- (L) _m- (AB) _n
In the formula, X represents a silver halide adsorbing group or a light absorbing group having at least one atom selected from the group consisting of N, S, P, Se and Te. L represents a divalent linking group having at least one atom selected from the group consisting of C, N, S and O. A represents an electron donating group, B represents a leaving group or a hydrogen atom, and after oxidation, is eliminated or deprotonated to generate a radical A. k and m each independently represents an integer of 0 to 3, and n represents 1 or 2. 2. The silver halide color photographic material according to claim 1, wherein the emulsified dispersion contains a high boiling point organic solvent having a dielectric constant of 7.0 or less. 3. The silver halide color photographic light-sensitive material according to claim 1, wherein 50% or more of the total projected area of the silver halide grains contained in the photosensitive layer satisfies the following (a) to (d): .
(A) Parallel main plane is (111) plane (b) Aspect ratio is 2 or more (c) At least 10 dislocation lines per grain (d) Silver chloride content is less than 10 mol% Tabular silver halide grains made of silver or silver chloroiodobromide 3. The halogenation according to claim 1, wherein 50% or more of the total projected area of the silver halide grains contained in the photosensitive layer satisfies the following (a), (d), and (e): Silver color photographic light-sensitive material.
(A) tabular silver halide grains made of (111) plane parallel plane (d) silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol% (e) hexagonal halide At least one epitaxial junction per grain at the apex and / or side and / or main plane of the silver grain 3. The silver halide according to claim 1, wherein 50% or more of the total projected area of the silver halide grains contained in the photosensitive layer satisfies the following (d), (f), and (g): Color photographic material.
(D) Tabular silver halide grains made of silver iodobromide or silver chloroiodobromide having a silver chloride content of less than 10 mol%. (F) Parallel main plane is (100) plane (g) Aspect ratio is 2. that's all 3. The silver halide color according to claim 1, wherein 50% or more of the total projected area of the silver halide grains contained in the photosensitive layer satisfies (g), (h), and (i). 4. Photosensitive material.
(G) Tabular grains having an aspect ratio of 2 or more, (h) parallel main plane containing (111) plane or (100) plane (i) at least 80 mol% or more of silver chloride The silver halide photographic light-sensitive material has the following general formulas (VI), (VII), (VIII-1), (VIII-2), (IX-1), (IX-2), (X) and (X) The silver halide color photographic light-sensitive material according to any one of claims 1 to 6, comprising at least one selected from compounds represented by XI).

In the formula (VI), Rb1, Rb2, Rb3 and Rb4 each independently represent a hydrogen atom, an aryl group, a chain or cyclic alkyl group, a chain or cyclic alkenyl group, or an alkynyl group, and Rb5 represents a chain Alternatively, it represents a cyclic alkyl group, a chain or cyclic alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

In formula (VII), Het is an adsorbing group to silver halide. M represents a divalent linking group composed of an atom or an atomic group containing at least one of a carbon atom, a nitrogen atom, a sulfur atom and an oxygen atom. Hy represents a group having a hydrazine structure represented by Rb6Rb7N-NRb8Rb9. Rb6, Rb7, Rb8 and Rb9 each independently represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and Rb6 and Rb7, Rb8 and Rb9, Rb6 and Rb8 or Rb7 and Rb9 are bonded to each other. A ring may be formed. However, at least one of Rb6, Rb7, Rb8 and Rb9 is an alkylene group, alkenylene group, alkynylene group, arylene group or divalent complex for substitution by-(M) k2 (Het) k1 in the general formula (VII). It is a ring residue. k1 and k3 each independently represent 1, 2, 3 or 4, and k2 represents 0 or 1.

In formula (VIII-1), Rb10, Rb11, Rb12 and Rb13 each independently represent a hydrogen atom or a substituent. However, when Rb10 and Rb13 or Rb11 and Rb12 are each an alkyl group, they do not take a substituent having exactly the same carbon number. In formula (VIII-2), Rb14, Rb15 and Rb16 each independently represent a hydrogen atom or a substituent. Z represents a nonmetallic atom group forming a 4-6 membered ring.

In formula (IX-1), Rc1 represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and Rc2 represents a hydrogen atom or a group represented by Rc1. Rc3 represents a hydrogen atom or a substituted or unsubstituted alkyl or alkenyl group having 1 to 10 carbon atoms. Rc1 and Rc2, Rc1 and Rc3, or Rc2 and Rc3 may be bonded to each other to form a 5- to 7-membered ring.

In formula (IX-2), G1 and G2 each represent a hydrogen atom or a monovalent substituent. Moreover, it may combine with each other to form a ring.

In the formula (X), Rb17, Rb18 and Rb19 each independently represent a hydrogen atom, alkyl group, alkenyl group, aryl group or heterocyclic group, and Rb20 represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group or aryl group. , A heterocyclic group, or NRb21Rb22, J represents —CO— or —SO ₂ —, and n represents 0 or 1. Rb21 represents a hydrogen atom, hydroxy group, amino group, alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group, and Rb22 represents a hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group. Represent. Rb17 and Rb18, Rb17 and Rb19, Rb19 and Rb20, or Rb20 and Rb18 may be linked to form a ring.

In formula (XI), X ² and Y ² each independently represent a hydroxyl group, —NRi23Ri24 or —NHSO ₂ Ri25. Ri21 and Ri22 each independently represent a hydrogen atom or an arbitrary substituent. Ri21 and Ri22 may be bonded to each other to form a carbocyclic or heterocyclic ring. Ri23 and Ri24 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Ri23 and Ri24 may be bonded to each other to form a heterocyclic ring. Ri25 represents an alkyl group, an aryl group, an amino group or a heterocyclic ring. The silver halide color photographic material according to any one of claims 1 to 7, wherein the silver halide grains contained in the silver halide photographic material are subjected to reduction sensitization. When the silver halide emulsion contained in the silver halide photographic light-sensitive material is prepared, at least of the compound selected from the compound represented by the following general formula (3) and the compound represented by the following general formula (4): 9. The silver halide color photographic light-sensitive material according to claim 1, wherein one kind is added.

In the general formulas (3) and (4), 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 silver halide grains contained in the silver halide photographic light-sensitive material are Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, It contains at least one metal ion selected from the group consisting of Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb and Bi inside the particle. The silver halide color photographic light-sensitive material according to any one of claims 1 to 9. 11. The silver halide color photographic light-sensitive material according to claim 1, wherein an average particle size of the emulsified dispersion is 10 [mu] m or less. 12. The silver halide color photographic light-sensitive material according to claim 2, wherein the content of the high-boiling organic solvent in the silver halide emulsion is 0.05 to 10% by mass. The blue-sensitive layer includes a high-sensitivity blue-sensitive layer and a low-sensitivity blue-sensitive layer, and the layer containing the emulsified dispersion and the compound of the general formula (I) is a high-sensitivity blue-sensitive layer. The silver halide color photographic material according to any one of claims 1 to 12. The silver halide color photographic light-sensitive material according to any one of claims 1 to 13, wherein the silver halide color photographic light-sensitive material is a color negative photographic light-sensitive material.