JP4733661B2 - Silver halide photographic light-sensitive material and image forming method using the same - Google Patents

Description

  The present invention relates to an image forming technique using a silver halide color photographic light-sensitive material. The present invention also relates to a silver halide photographic light-sensitive material excellent in storage stability.

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

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

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

  When the original image is produced as digital information in a convenient manner as described above, and this is screened by conventional analog projection, the original image produced as digital information is printed on an intermediate film, which is compared with the conventional method. Similarly, the process of printing on movie positive film is performed.

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

  The main cause of image blur is the scattering of the recording light inside the photosensitive material, and the blur of the image can be remarkably improved by reducing the scattered light. Since light scattering is greatly affected by the silver halide fine particles in the photosensitive material, it is effective to reduce the amount of silver halide fine particles used as much as possible, but it is also effective to reduce the size of the silver halide fine particles It is. All of these means lead to a decrease in sensitivity of the photosensitive material. Therefore, increasing the sensitivity without increasing the size of the silver halide fine particles is a method for recording on a silver halide photographic photosensitive material without degrading digital information. Is the most basic and important issue.

In recent years, a technique for increasing sensitivity without deteriorating graininess by incorporating a compound having at least three heteroatoms into a silver halide photographic material has been disclosed (see, for example, Patent Documents 2 and 3). ).
Japanese Patent Laid-Open No. 10-20461 JP 2000-194085 A JP 2004-226971 A

  An object of the present invention is to provide a technique for recording digital information on a silver halide photographic light-sensitive material with high resolution and little deterioration.

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

As a result of intensive studies to solve the above problems, it has been surprisingly found that the problems can be achieved by the following.
(1) In a silver halide photographic material having at least one blue-sensitive layer, green-sensitive layer, and red-sensitive layer on a transparent support, at least one layer of the following compound (A): one containing, in all silver halide emulsion containing all of the photosensitive layer, Ri mean equivalent spherical diameter der following 0.35μm silver halide grains containing the digital image information in the 2000dpi or higher resolution A silver halide photographic light-sensitive material characterized in that the blur k of the obtained image satisfies the following formula (I) when recorded.

ｋ＜４．５×（Ｄ−０．２） ^２ (Ｉ)
式(Ｉ)において、Ｄはハロゲン化銀写真感光材料の発色濃度を表し、滲みｋは発色濃度Ｄにおける滲み(μｍ)を表す。 Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) Compound represented by the following general formula (M-3)
In the formula, R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) a compound represented by
3) Alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkoxycarbonyl group and carbamoyl The compound represented by the following general formula (Ca-8) which may have a substituent selected from a group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic material, and the blur k represents the blur (μm) at the color density D.

(2) In a silver halide photographic material having at least one blue-sensitive layer, green-sensitive layer, and red-sensitive layer on a transparent support, respectively, at least one layer of the following compound (A) one containing, in all silver halide emulsion containing all of the photosensitive layer, Ri mean equivalent spherical diameter der 0.35μm or less of the silver halide grains containing, more than 300 million pixels of the digital image information A silver halide photographic light-sensitive material characterized in that the blur k of the obtained image satisfies the following formula (I) when recorded.

ｋ＜４．５×（Ｄ−０．２） ^２ (Ｉ)
式(Ｉ)において、Ｄはハロゲン化銀写真感光材料の発色濃度を表し、滲みｋは発色濃度Ｄにおける滲み(μｍ)を表す。 Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) Compound represented by the following general formula (M-3)
In the formula, R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) a compound represented by
3) Alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkoxycarbonyl group and carbamoyl The compound represented by the following general formula (Ca-8) which may have a substituent selected from a group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic material, and the blur k represents the blur (μm) at the color density D.

(3) the image's rating record your Keru color purity rate color reproduction is characterized that at least 80% (1) or a silver halide photographic material according to (2).

ｋ＜４．５×（Ｄ−０．２）^２ (Ｉ)
式(Ｉ)において、Ｄはハロゲン化銀写真感光材料の発色濃度を表し、滲みｋは発色濃度Ｄにおける滲み(μｍ)を表す。
（９） ３００万画素以上のデジタル画像情報をハロゲン化銀写真感光材料に記録する画像形成方法であって、該ハロゲン化銀写真感光材料が、透明支持体上に、それぞれ少なくとも１層の青感光性層、緑感光性層、および赤感光性層を有し、少なくとも１層に下記化合物(Ａ)を少なくとも１種含有し、全ての感光性層に含有する全てのハロゲン化銀乳剤において、含有するハロゲン化銀粒子の平均球相当直径が０．３５μｍ以下であって、該ハロゲン化銀写真感光材料に記録して得られた画像の滲みｋが、下記式（Ｉ）を満たすことを特徴とする画像形成方法。
化合物(Ａ)：ヘテロ原子を１個以上持つ複素環化合物であり、下記１）〜３）から選択される化合物。
１）下記一般式（Ｍ−３）で表される化合物
式中、Ｒ_１５はｔ−ブチル基を表し、Ｘ_１１はアリールチオ基を表し、Ｒ_１７はアリール基を表す。
２）ハロゲン原子、アルキル基、アルコキシ基、アリールオキシ基、アルキルチオ基、アリールチオ基、アルキル若しくはアリールスルホニル基、アルキルアミノ基およびアシルアミノ基から選択される置換基を有してもよい下記一般式（Ｃａ−１）で表される化合物
３）アルキル基、アリール基、アルコキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アルキルチオ基、スルファモイル基、アルキル若しくはアリールスルフィニル基、アルキル若しくはアリールスルホニル基、アルコキシカルボニル基およびカルバモイル基から選択される置換基を有してもよい下記一般式（Ｃａ−８）で表される化合物

ｋ＜４．５×（Ｄ−０．２）^２ (Ｉ)
式(Ｉ)において、Ｄはハロゲン化銀写真感光材料の発色濃度を表し、滲みｋは発色濃度Ｄにおける滲み(μｍ)を表す。
（１０） 画像記録時の色再現において色純度率が８０％以上であること特徴とする（８）または（９）に記載の画像形成方法。
（１１） 前記全ての感光性層に含有する全てのハロゲン化銀乳剤において、含有するハロゲン化銀粒子の平均球相当径が０．２μｍ以下であることを特徴とする（８）〜（１０）のいずれか１項に記載の画像形成方法。
（１２） 前記ハロゲン化銀写真感光材料の全ての感光性層に含有する全てのハロゲン化銀乳剤において、含有するハロゲン化銀粒子が立方体粒子であることを特徴とする（８）〜（１１）のいずれか１項に記載の画像形成方法。
（１３） 前記感光性層で使用されるハロゲン化銀乳剤が、ヨウ化銀を２〜１０モル％含有するヨウ臭化銀またはヨウ塩臭化銀であることを特徴とする（８）〜（１２）のいずれか１項に記載の画像形成方法。
（１４） 前記ハロゲン化銀写真感光材料が、映画用インターメディエイトフイルム用のハロゲン化銀写真感光材料であることを特徴とする（８）〜（１３）のいずれか１項に記載の画像形成方法。
（１５） （８）〜（１４）のいずれか１項に記載の画像形成方法で得られた画像を、さらにハロゲン化銀写真感光材料にアナログ方式で記録することを特徴とする画像形成方法。 (4) In all the silver halide emulsions contained in all the photosensitive layers, the average sphere equivalent diameter of the contained silver halide grains is 0.2 μm or less (1) to (3) The silver halide photographic light-sensitive material according to any one of the above.
(5) The silver halide grains contained in all the silver halide emulsions contained in all the photosensitive layers of the silver halide photographic light-sensitive material are cubic grains (1) to (4) The silver halide photographic light-sensitive material according to any one of the above.
(6) The silver halide emulsion used in the light-sensitive layer, characterized in that the silver iodide is iodobromide or silver iodochlorobromide and silver containing 2-10 mole% (1) - ( The silver halide photographic light-sensitive material according to any one of 5) .
(7) The halogenated film as described in any one of (1) to (6 ) above, wherein the silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material for a film intermediate film. Silver photographic material.
(8) An image forming method for recording digital image information on a silver halide photographic light-sensitive material with a resolution of 2000 dpi or more, wherein the silver halide photographic light-sensitive material has at least one layer of blue light sensitive material on a transparent support. A photosensitive layer, a green photosensitive layer, and a red photosensitive layer, at least one of the following compounds (A) is contained in at least one layer, and contained in all silver halide emulsions contained in all photosensitive layers wherein the average equivalent spherical diameter of silver halide grains der less 0.35 .mu.m, bleeding k of an image obtained by recording to the silver halide photographic material that satisfies the following formula (I) to An image forming method.
Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) Compound represented by the following general formula (M-3) In the formula, R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) compound 3) alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or aryl A compound represented by the following general formula (Ca-8) which may have a substituent selected from a sulfonyl group, an alkoxycarbonyl group and a carbamoyl group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic light-sensitive material, and the blur k represents the blur (μm) at the color density D.
(9) An image forming method for recording digital image information of 3 million pixels or more on a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material has at least one layer of blue light sensitive material on a transparent support. A photosensitive layer, a green photosensitive layer, and a red photosensitive layer, at least one of the following compounds (A) is contained in at least one layer, and contained in all silver halide emulsions contained in all photosensitive layers wherein the average equivalent spherical diameter of silver halide grains der less 0.35 .mu.m, bleeding k of an image obtained by recording to the silver halide photographic material that satisfies the following formula (I) to An image forming method.
Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) Compound represented by the following general formula (M-3) In the formula, R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) compound 3) alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or aryl A compound represented by the following general formula (Ca-8) which may have a substituent selected from a sulfonyl group, an alkoxycarbonyl group and a carbamoyl group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic light-sensitive material, and the blur k represents the blur (μm) at the color density D.
(10) The image forming method as described in (8) or (9) , wherein the color purity ratio is 80% or more in color reproduction at the time of image recording.
(11) In all the silver halide emulsions contained in all the photosensitive layers, the average sphere equivalent diameter of the contained silver halide grains is 0.2 μm or less. (8) to (10) The image forming method according to any one of the above.
(12) The silver halide grains contained in all the silver halide emulsions contained in all the photosensitive layers of the silver halide photographic light-sensitive material are cubic grains (8) to (11) The image forming method according to any one of the above.
(13) The silver halide emulsion used in the photosensitive layer is silver iodobromide or silver iodochlorobromide containing 2 to 10 mol% of silver iodide (8) to ( 8) 12. The image forming method according to any one of 12) .
(14) The image formation as described in any one of (8) to (13) , wherein the silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material for a film intermediate film. Method.
(15) An image forming method, wherein an image obtained by the image forming method according to any one of (8) to (14) is further recorded on a silver halide photographic light-sensitive material by an analog method.

The present invention will be described in detail.
(Bleeding evaluation method)
In the present invention, bleeding k at the time of image recording to satisfy the following formula (I).

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

  Further, it is preferable that the formula (I) holds for all the regions from Dmin + 0.2 to Dmax, but the evaluation is simply performed with two points of the color density Dmin + 1 and Dmin + 2, and the formula (I) is satisfied at any density. May be used as a condition. Here, Dmin represents the minimum value of the color density in the photosensitive material and corresponds to the density after processing of the unexposed film. Dmax represents the maximum value of the color density in the photosensitive material. The maximum value of the color density is made to correspond to the maximum value of the density of the digital image information. In the case of the widely used Cineon format, the maximum density is about Dmin + 2.

  As shown in FIG. 1, the blur k is a blurring of the color image in the surface direction of the photosensitive material at a density of Dmin + 0.2 when the exposure amount is adjusted so that the photosensitive material is colored to the density D and the stepwise exposure is performed. Measure the width and let it be k.

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

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

Color purity rate (%) = (a−b) / a × 100 (II)
The requirement that the color purity ratio represented by the formula (II) is not less than a specific value must be satisfied for all the regions where the main color density is from Dmin + 0.1 to Dmax, and single color exposure of red, green, and blue is performed. It is necessary to hold in either case. Dmin represents the minimum value of color density in the photosensitive material and corresponds to the density after processing of the unexposed film. Dmax represents the maximum value of the color density in the photosensitive material. The maximum value of the color density is made to correspond to the maximum value of the density of the digital image information. In the case of the widely used Cineon format, the maximum density is about Dmin + 2.

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

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

For example, ARRI ARRISER, ARRILASER HD using BGR laser as the light source system, CELCO FURY, FIRETORM using CRT system, IMAGEICA realtime, HSR high speed recorder using COS system, CINEVATIONor One, Cinevater Five, etc. are mentioned.

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

In the following, it is described in detail for the compounds used in the present invention (A).
In the present invention, when a specific moiety is referred to as a “group”, the moiety may be unsubstituted or substituted with one or more (up to the maximum possible) substituents. Means good. For example, “alkyl group” means a substituted or unsubstituted alkyl group. Moreover, the substituent which can be used for the compound in the present invention may be any substituent regardless of the presence or absence of substitution.

When such a substituent is W, the substituent represented by W is not particularly limited, and examples thereof include halogen atoms, alkyl groups (cycloalkyl groups, bicycloalkyl groups, tricycloalkyl groups). ), Alkenyl groups (including cycloalkenyl groups and bicycloalkenyl groups), alkynyl groups, aryl groups, heterocyclic groups (also referred to as heterocyclic groups), cyano groups, hydroxyl groups, nitro groups, carboxyl groups, Alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including alkylamino group, arylamino group, heterocyclic amino group) ), Ammonio group, acylamino group, aminocarbonyl Mino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and aryl Sulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino Group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group (-B (OH) ₂ ), phosphato group (-OPO (OH) ₂ ), sulfato group (-OSO ₃ H), other known Substituents are mentioned as examples.

  More specifically, W represents a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group [a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms, for example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-yl), a tricyclo structure with more ring structures Domo is intended to cover. An alkyl group (for example, an alkyl group of an alkylthio group) in the substituent described below represents an alkyl group having such a concept, but further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. They are alkenyl groups (preferably substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl groups (preferably substituted or substituted groups having 3 to 30 carbon atoms). An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl), Bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond. For example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo 2,2,2] oct-2-en-4-yl). An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as ethynyl, propargyl, trimethylsilylethynyl group), an aryl group (preferably a substituted or unsubstituted aryl having 6 to 30 carbon atoms) Groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocycles A monovalent group obtained by removing one hydrogen atom from a compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, and the like 1-methyl-2-pyridinio and 1-methyl-2-quinolinio A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms such as methoxy, ethoxy, Propoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 4- t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy A group (preferably a substitution of 2 to 30 carbon atoms or Unsubstituted heterocyclic oxy group, 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, A substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably having 1 carbon atom) To 30 substituted or unsubstituted carbamoyloxy groups such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn -Octylcarbamoyloxy), alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy) An aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy ), An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a heterocyclic amino group, Groups such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, 2-pyridylamino), ammonio groups (preferably ammonio groups, substituted or unsubstituted alkyls having 1 to 30 carbon atoms, aryl, An ammonio group substituted by a heterocycle, for example, trimethylammonio, triethylammonio, diphenylmethylammonio), an acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, A substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), A minocarbonylamino group (preferably a substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxy; Carbonylamino), aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p -Chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted having 6 to 30 carbon atoms) Or unsubstituted arylsulfonylamino such as methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto group, alkylthio (Preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxyphenylthio), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazole-5 -Ylthio), sulfamoyl groups (preferably substituted or unsubstituted sulfamoyl groups having 0 to 30 carbon atoms such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfa Moyl, N-acetylsulfamoyl, N-ben Ylsulfamoyl, N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, substituted or unsubstituted 6 to 30 carbon atoms) Substituted arylsulfinyl groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, 6 to 30 substituted or unsubstituted arylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl groups (preferably formyl group, substituted or unsubstituted 2 to 30 carbon atoms) An alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a heterocyclic carbonyl group bonded to the carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms, such as acetyl, Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl), aryloxycarbonyl group (preferably substituted or unsubstituted having 7 to 30 carbon atoms) Aryloxycarbonyl groups such as phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl), alkoxycarbonyl groups (preferably substituted or unsubstituted alkoxy having 2 to 30 carbon atoms) Rubonyl group such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl group (preferably substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms such as carbamoyl, N-methylcarbamoyl) N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms) A substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms, such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably N -Succinimide, N-phthalimide A phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably a substituent having 2 to 30 carbon atoms) Or an unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl), a phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms, For example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, such as dimethoxyphosphinylamino , Dimethylaminophosphinylamino), phospho Group, silyl group (preferably substituted or unsubstituted silyl group having 3 to 30 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), hydrazino group (preferably substituted having 0 to 30 carbon atoms) Alternatively, it represents an unsubstituted hydrazino group, such as trimethylhydrazino, or a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, such as N, N-dimethylureido).

  In addition, two Ws can be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocyclic ring. These can be further combined to form a polycyclic fused ring. For example, a benzene ring or naphthalene. Ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring, acridine ring, Phenanthroline ring, thian Ren ring, chromene ring, xanthene ring, phenoxathiin ring, a phenothiazine ring and a phenazine ring.) May also be formed.

Among the above substituents W, those having a hydrogen atom may be substituted with the above groups by removing this. Examples of such substituents, -CONHSO ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group ).

  More specifically, alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl), arylsulfonylamino A carbonyl group (for example, p-methylphenylsulfonylaminocarbonyl) is mentioned.

Ru of compounds used in the present invention for (A) will be described.
The compound (A) used in the present invention is a heterocyclic compound having one or more heteroatoms, and is a compound selected from the following 1) to 3).
1) Compound represented by the following general formula (M-3)
In the formula, R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) a compound represented by
3) Alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, alkoxycarbonyl group and carbamoyl The compound represented by the following general formula (Ca-8) which may have a substituent selected from a group

  The number of members of the heterocyclic ring may be any, but is preferably a 3- to 8-membered ring, more preferably a 5- to 7-membered ring, and particularly preferably a 5- and 6-membered ring.

These heterocyclic, the aforementioned substituents may be substituted. Moreover, the tertiary nitrogen atom contained in the heterocyclic ring may be substituted to become quaternary nitrogen. It should be noted that any case where another tautomeric structure of a heterocycle can be written is chemically equivalent.

The compounds of the present invention can contain the requisite number of necessary cations or anions when necessary to neutralize the charge of the compounds of the present invention. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium 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-toluene ion). Chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

The compound (A) of the present invention, are allowed to react even upon reaction with oxidized developing agent, either have good.

First, the compound represented by formula (M-3) of the present invention will be described.
The total number of carbon atoms of the substituents on the azole ring containing the phenyl group substituted by R ₁₅ , X ₁₁ , and R ₁₇ SO ₂ NH in the general formula (M-3) is not particularly limited. 13 to 60 or less is preferable, and 20 to 50 is more preferable in order to improve the adsorptivity to the surface and improve the effect of improving the sensitivity / granularity ratio.

In the formula, R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group. The aryl group of R ₁₇ may have a substituent . In this case, examples of the substituent include a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom), an alkyl group (having 1 to 60 carbon atoms. For example, methyl, Ethyl, propyl, iso-butyl, t-butyl, t-octyl, 1-ethylhexyl, nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), an alkenyl group (having 2 to 60 carbon atoms, for example, Vinyl, allyl, oleyl), cycloalkyl group (5 to 60 carbon atoms, for example, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 1-indanyl, cyclododecyl), aryl group (6 to 60 carbon atoms, for example, phenyl) , P-tolyl, naphthyl), an acylamino group (having 2 to 60 carbon atoms. For example, acetylamino , N-butanamide, octanoylamino, 2-hexyldecanamide, 2- (2 ′, 4′-di-t-amylphenoxy) butanamide, benzoylamino, nicotinamide), sulfonamide group (having 1 to 60 carbon atoms). For example, methanesulfonamide, octanesulfonamide, benzenesulfonamide), ureido group (carbon number 2 to 60. For example, decylaminocarbonylamino, di-n-octylaminocarbonylamino), urethane group (carbon number 2 to 60). For example, dodecyloxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), alkoxy group (C1-C60. For example, methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, methoxyethoxy), aryloxy Base (charcoal Number 6 to 60. For example, phenoxy, 2,4-di-t-amylphenoxy, 4-t-octylphenoxy, naphthoxy), alkylthio group (carbon number 1 to 60. For example, methylthio, ethylthio, butylthio, hexadecylthio), Arylthio group (C6-C60. For example, phenylthio, 4-todecyloxyphenylthio), acyl group (C1-C60. For example, acetyl, benzoyl, butanoyl, dodecanoyl), sulfonyl group (C1-C60) For example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), cyano group, carbamoyl group (C1-C60. For example, N, N-dicyclohexylcarbamoyl), sulfamoyl group (C0-C60. For example, N, N- Dimethylsulfamoyl), hydroxy group, sulfo group, cal Boxyl group, nitro group, alkylamino group (C1-60. For example, methylamino, diethylamino, octylamino, octadecylamino), arylamino group (carbon number 6 to 60. For example, phenylamino, naphthylamino, N-methyl-N-phenylamino), heterocyclic group (carbon number 0 to 60. Preferably, the hetero atom having a ring structure is selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably includes a carbon atom in addition to the hetero atom as the ring atom. 8, more preferably 5 to 6, for example, a group exemplified in the section of X described later) and an acyloxy group (carbon 1 to 60. For example, formyloxy, acetyloxy, myristoyloxy, benzoyloxy) are preferable.

X ₁₁ represents an arylthio group , and examples thereof include 2 -octyloxy-5-t-octylphenylthio, 2- (2,4-di-t-amylphenoxy) butyrylaminophenylthio and the like .

Particularly preferred as the X _11, a substitution arylthio group.

Shows the general formula are preferably used in the present invention the following specific examples of (M-3) a compound represented by (couplers), the present invention is not limited thereto.

  The compounds of the present invention can be easily synthesized according to the synthesis methods described in, for example, JP-A-61-65245, JP-A-61-65246, JP-A-61-147254, JP-A-8-122984, etc. I can do it.

The compounds of the present invention (A) is preferably the case of reacting with oxidized developing agent, it is also possible to use a heterocyclic compound which does not react with oxidized developing agent. These will be described below.

The compound (A) of the present invention which is such a heterocyclic compound is represented by the following general formula (Ca-1) or (Ca-8).

The tetraazaindene ring of the general formula (Ca-1) is selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group, and an acylamino group. You may have a substituent. In the present invention, it is preferable that the secondary amino group is not bonded so that a ring atom can be conjugated to ring nitrogen to form a tautomer of a heterocyclic ring .

The heterocyclic ring of the above general formula (Ca-8) is an alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, It may have a substituent selected from an alkyl or arylsulfonyl group, an alkoxycarbonyl group, and a carbamoyl group.

These heterocyclic rings, tertiary nitrogen atom contained in the double ring may be a quaternary nitrogen substituted. It should be noted that any case where another tautomeric structure of a heterocycle can be written is chemically equivalent.

  The heterocyclic compounds mentioned here are compounds that do not react with the oxidized developing agent. That is, those that do not significantly cause chemical reaction or redox reaction (less than 5 to 10%) directly with the oxidized developing agent are preferred, and are not couplers and react with the oxidized developing agent to produce a dye or any other product. The thing which does not produce | generate a thing is preferable.

Hereinafter, specific examples of the general formula (Ca-1) or (Ca-8) in at represented Ru of compounds which do not react with the oxidized developing agent of the present invention. Of course, the present invention is not limited to these. The number in parentheses after the compound number is the ClogP value.

  As the compound (A) of the present invention, in addition to the specific examples described above, compounds corresponding to the present invention described in the specific examples of JP-A Nos. 2000-194085 and 2004-226971 can be preferably used. .

  As compounds of the present invention, Edward C. Taylor, edited by Arnold Weissberger, “The Chemistry of Heterocyclic Compounds— Series of Monographs, Volumes 1-59, published by John Wiley & Sons, edited by Robert C. Elderfield, "Hetero" Among the compounds described in “Heterocyclic Compounds” Vol. 1-6, published by John Wiley & Sons, etc., the compounds corresponding to the present invention can be used. Moreover, the compound of this invention is compoundable based on the method as described in these.

Mentioned above, as the substituent of the compounds of the present invention (A), or may be a hydrophobicity groups ranging from groups defined (ballast group). In general, these groups preferably have 1 to 60, more preferably 1 to 50 carbon atoms.

  The carbon number in a typical ballast group is preferably 8 to 60, more preferably 10 to 57, particularly preferably 12 to 55, and most preferably 16 to 53. As these substituents, substituted or unsubstituted C 8-60, preferably 10-57, more preferably 13-55, particularly preferably 16-53, most preferably 20-50 alkyl, aryl groups, Or a heterocyclic group is mentioned. Moreover, it is preferable that these contain a branch. Typical substituents on these groups include alkyl, aryl, alkoxy, aryloxy, alkylthio, hydroxy, halogen, alkoxycarbonyl, aryloxycarbonyl, carboxy, acyl, acyloxy, amino, anilino, carbonamido, carbamoyl. , Alkylsulfonyl, arylsulfonyl, sulfonamido, and sulfamoyl groups, the substituents generally having 1 to 42 carbon atoms. For example, W mentioned above is mentioned. Moreover, such a substituent may be further substituted.

  The ballast group will be described in more detail. Specifically, an alkyl group (having 1 to 60 carbon atoms, for example, methyl, ethyl, propyl, iso-butyl, t-butyl, t-octyl, 1-ethylhexyl, nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), alkenyl group (carbon number 2 to 60. For example, vinyl, allyl, oleyl), cycloalkyl group (carbon number 5 to 60. For example, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl, 1- Indanyl, cyclododecyl), aryl group (C6-C60. For example, phenyl, p-tolyl, naphthyl), acylamino group (C2-C60. For example, acetylamino, n-butanamide, octanoylamino, 2- Hexyldecanamide, 2- (2 ′, 4′-di-t-amylphenoxy ) Butanamide, benzoylamino, nicotinamide), sulfonamide group (C1-C60. For example, methanesulfonamide, octanesulfonamide, benzenesulfonamide), ureido group (C2-C60. For example, decylaminocarbonylamino) , Di-n-octylaminocarbonylamino), urethane group (2 to 60 carbon atoms, for example, dodecyloxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), alkoxy group (1 to 60 carbon atoms, for example, Methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, methoxyethoxy), aryloxy group (6 to 60 carbon atoms. For example, phenoxy, 2,4-di-t-amylphenoxy, 4-t-octylphenoxy, Naphthoxy) , Alkylthio groups (having 1 to 60 carbon atoms, such as methylthio, ethylthio, butylthio, hexadecylthio), arylthio groups (having 6 to 60 carbon atoms, such as phenylthio, 4-todecyloxyphenylthio), acyl groups (having 1 to 1 carbon atoms). 60. For example, acetyl, benzoyl, butanoyl, dodecanoyl), sulfonyl group (C1-C60. For example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), cyano group, carbamoyl group (C1-C60. For example, N, N-dicyclohexylcarbamoyl), sulfamoyl group (0 to 60 carbon atoms, for example, N, N-dimethylsulfamoyl), hydroxy group, sulfo group, carboxyl group, nitro group, alkylamino group (1 to 60 carbon atoms, for example). , Methylamino, diethylamino, octylami , Octadecyl amino), arylamino group (having 1 to 60 carbon atoms. For example, phenylamino, naphthylamino, N-methyl-N-phenylamino), heterocyclic group (0 to 60 carbon atoms, preferably selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a hetero atom of the ring structure Further, those containing a carbon atom in addition to a hetero atom as a ring-constituting atom are further preferred, and the number of ring members is 3 to 8, more preferably 5 to 6, for example, the group represented by the aforementioned W), an acyloxy group (Carbon 1-60. For example, formyloxy, acetyloxy, myristoyloxy, benzoyloxy) is preferable.

  Among them, alkyl group, cycloalkyl group, aryl group, acylamino group, ureido group, urethane group, alkoxy group, aryloxy group, alkylthio group, arylthio group, acyl group, sulfonyl group, cyano group, carbamoyl group, sulfamoyl group Includes those having a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an acylamino group, a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, and an acyl group. Sulfonyl group, cyano group, carbamoyl group, sulfamoyl group, and halogen atom.

  Among these substituents, an alkyl group, an aryl group, an alkoxy group, and an aryloxy group are preferable, and an alkyl group, an alkoxy group, and an aryloxy group are more preferable. Particularly preferred is a branched alkyl group.

  Although there is no restriction | limiting in particular in the sum total of carbon number of these substituents, Preferably it is 8-60, More preferably, it is 10-57, Especially preferably, it is 12-55, Most preferably, it is 16-53.

  When the compound of the present invention is contained in a silver halide photographic light-sensitive material, it is preferably a compound that can be fixed to a specific layer during storage and diffuses at an appropriate time of photographic processing (preferably during development processing). Is used. In order to prevent and fix the compound of the present invention during storage, any compound / method may be used, but the following compounds / methods are preferable.

  (1) A method in which a compound having a specific pKa is added after being emulsified and dispersed together with a high-boiling organic solvent, which will be described later, to dissociate the compound of the present invention from the oil only during development.

  The pKa of the compound of the present invention is preferably 5.5 or more, more preferably 6.0 or more and 10.0 or less, particularly preferably 6.5 or more and 8.4 or less, and most preferably 6.9 or more. This is the case of 8.3 or less.

The dissociation group may be any group, but is preferably a carboxyl group, —CONHSO ₂ — group (sulfonylcarbamoyl group, carbonylsulfamoyl group), —CONHCO— group (carbonylcarbamoyl group), —SO ₂ NHSO ₂ —. Group (sulfonylsulfamoyl group), sulfonamido group, sulfamoyl group, phenolic hydroxyl group, more preferably carboxyl group, —CONHSO ₂ — group, —CONHCO— group, —SO ₂ NHSO ₂ — group, Particularly preferred are a carboxyl group and a —CONHSO ₂ — group.

  (2) A method of making a compound of the present invention anti-diffusion by adding a ballast group.

  (3) A method using a blocking group. Compounds that change properties (eg, become diffusible) by chemical reactions such as nucleophilic reactions, electrophilic reactions, oxidation reactions, reduction reactions, etc. in the photographic processing process can be used. You can also use the method.

  As an example, the nucleophilic reaction will be described in detail. The nucleophilic reaction can occur under any conditions, but is promoted by a base or by heating, particularly in the presence of a base. As the base, any base can be selected from inorganic bases and organic bases. For example, tertiary amines such as triethylamine, aromatic heterocyclic amines such as pyridine, OH anions such as sodium hydroxide and potassium hydroxide. Bases having In particular, in the present invention, the nucleophilic reaction is promoted by photographic processing having a high pH, such as a developer, among photographic processing, so that it can be preferably used.

  The term “nucleophile” as used herein refers to an atom having a low electron density, such as carbonyl carbon, contained in a group of atoms that form a group that is eliminated when attacked by a nucleophile to give or share electrons. Represents a chemical species with properties. The nucleophile may have any structure, but preferred examples include reagents that give hydroxide ions (for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate), sulfite ions (For example, sodium sulfite, potassium sulfite), a hydroxylamide ion (for example, hydroxyamine), a hydrazide ion (for example, hydrazine hydrate, dialkylhydrazines), a hexacyanoferrate (II) ion And a reagent (eg, sodium methoxide) that gives a reagent (eg, yellow blood salt), cyanide ion, tin (II) ion, ammonia, or alkoxy ion. Examples of groups capable of leaving upon attack by a nucleophile include Can. J. et al. Chem. 44, 2315 (1966), JP-A-59-137,945, JP-A-60-41,034, and the like. Lett. 585 (1988), JP-A-59-218,439, JP-B-5-78,025, etc., a group using a nucleophilic reaction, a group using a hydrolysis reaction of an ester bond or an amide bond, etc. Can be mentioned.

  In order to impart the above functions, the compounds of the present invention may be substituted with blocking groups that release the compounds of the present invention during photographic processing. As the blocking group, known ones can be used. For example, the acyl groups described in JP-B-48-9968, JP-A-52-8828, JP-A-57-82834, U.S. Pat. No. 3,311,476 and JP-B-47-44805 (U.S. Pat. No. 3,615,617). Blocking groups such as sulfonyl groups, JP-B 55-17369 (US Pat. No. 3,888,677), 55-9696 (US Pat. No. 3,791,830), 55-34927 (US Pat. No. 4,009,029), JP No. 56-77842 (US Pat. No. 4,307,175), No. 59-105640, No. 59-105641 and No. 59-105642, etc. U.S. Pat.Nos. 3,674,478, 3,932,480, 3,993,661, JP-A-57-135944, 57-135945 (U.S. Pat. No. 4,420,554), 57-136640, 61-196239, Quinones by intramolecular electron transfer described in 61-196240 (US Pat. No. 4,702,999), 61-185743, 61-124941 (US Pat. No. 4,639,408) and JP-A-2-280140 Blocking group utilizing the formation of a compound similar to tide or quinone methide, U.S. Pat. Nos. 4,358,525, 4,330,617, JP 55-53330 (U.S. Pat. No. 4,310,612), 59-121328, 59-218439 No. 63-318555 (European Published Patent No. 0295729) and the like, a blocking group utilizing an intramolecular nucleophilic substitution reaction, JP-A 57-76541 (US Pat. No. 4,335,200), 57- 135949 (US Pat. No. 4,350,752), 57-179842, 59-137945, 59-140445, 59-219741, 59-202459, 60-41034 (US Pat. No. 4,618,563) No. 62-59945 (U.S. Pat. No. 4,888,268), 62-65039 (U.S. Pat. No. 4,772,537), 62-80647, JP-A-3-236047 and 3-238445, etc. Blocking groups utilizing a 5- or 6-membered ring cleavage reaction, JP-A-59-201057 (US Pat. No. 4,518,685), 61-43739 (US Pat. No. 4,659,651), 61 -95346 U.S. Pat. No. 4,690,885), 61-95347 (U.S. Pat. No. 4,892,811), JP-A Nos. 64-7035 and 4-42650 (U.S. Pat. No. 5,066,573), JP-A No. 1-245255, No. 2 No. 207249, 2-235055 (US Pat. No. 5,118,596) and 4-186344, etc., and a blocking group utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond, -93442, 61-32839, 62-163051, and the blocking group utilizing β-elimination reaction described in JP-B-5-37299, etc., described in JP-A-61-188540 Blocking group utilizing nucleophilic substitution reaction of diarylmethanes, Blocking group utilizing Rossen rearrangement described in JP-A-62-187850, JP-A-62-80646, JP-A-62-144163, and JP-A-62 -Block group utilizing reaction of N-acyl thiazolidine-2-thione with amines described in JP-A No. 147457, JP-A-2-296240 (US Pat. No. 5,019,492), 4-177243, 4-177244, 4-177245, 4-177246, 4-177247, 4-177248, 4-177248, 4-177249, 4-177948, 4 -184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419, JP-A-5-45816, etc. Examples thereof include blocking groups that react with nucleophiles, and JP-A-3-236047 and JP-A-3-238445. Of these blocking groups, JP-A-2-296240 (US Pat. No. 5,019,492), 4-177243, 4-177244, 4-177245, 4-177246, 4-177246, 4-177247, 4-177248, 4-177249, 4-179748, 4-184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 And a blocking group that reacts with a dinucleophile having two electrophilic groups described in JP-A-5-45816 and the like. These blocking groups may be groups containing a timing group that causes a cleavage reaction using an electron transfer reaction described in U.S. Pat.Nos. 4,409,323 or 4,421,845. It is preferable that the terminal which causes an electron transfer reaction is blocked.

  (4) A method using a dimer containing a partial structure of the compound of the present invention, or a polymer compound of trimer or higher.

  (5) A method of fixing using the compound (solid dispersion) of the present invention which is insoluble in water. As described in (1), the case where the compound of the present invention has a specific pKa is preferable because the compound of the present invention dissolves only during development. Examples using water-insoluble dye solids (solid dispersions) are disclosed in JP-A Nos. 56-12539, 55-155350, 55-155351, 63-27838, 63-197943, and Europe. This is disclosed in Japanese Patent No. 15,601.

  A detailed method for solid dispersion will be described later.

  (6) A method of immobilizing the compound of the present invention by coexisting a polymer having a charge opposite to that of the compound of the present invention as a mordant. Examples of fixing the dye are disclosed in U.S. Pat. Nos. 2,548,564, 4,124,386, and 3,625,694.

  (7) A method of adsorbing and fixing the compound of the present invention to a metal salt such as silver halide. Examples of fixing the dye are disclosed in US Pat. Nos. 2,719,088, 2,496,841, 2,496,843, and JP-A-60-45237.

  Typical examples of the adsorbing group to silver halide that can be used in the compound of the present invention include groups described in JP-A 2003-156823, page 16, right line 1 to page 17, right line 12. It is.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferred examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing telocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  Further, a quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing The quaternary salt structure of phosphorus includes a phosphonio group (trialkyl phosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.) Is mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salts include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As the counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.

  Of the above, the method for immobilizing the compound of the present invention is preferably (1) a method using a compound having a specific pKa, (2) a method using a compound having a ballast group, and (3) a compound having a blocking group. And (5) a method using a solid dispersion, and it is preferable to use a compound suitable for these. More preferred is the method / compound of (1), (2) or (3), and particularly preferred is the method / compound of (1) or (2). Most preferably, the methods (1) and (2) are used simultaneously, that is, the compound of the present invention having a specific pKa and a ballast group can be most preferably used.

The compounds of the present invention can contain the requisite number of necessary cations or anions when necessary to neutralize the charge of the compounds of the present invention. Typical cations include inorganic cations such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ions, potassium ions, lithium ions), alkaline earth metal ions (eg, calcium ions), ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8-diazabicyclo [5.4.0] -7-undecenium 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-toluene ion). Chlorobenzenesulfonate ion), aryl disulfonate ion (for example, 1,3-benzenesulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkyl sulfate ion (for example, methyl sulfate ion) ), Sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Furthermore, you may use the ionic polymer or the other pigment | dye which has a charge opposite to a pigment | dye. CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have hydrogen ions as counter ions.

  Preferred of the compounds of the present invention are combinations of the individual preferred above (particularly combinations of the most preferred of the individual).

  In addition, when the compound of the present invention has a plurality of asymmetric carbons in the molecule, there are a plurality of stereoisomers for the same structure. In this specification, all possible stereoisomers are shown. In the present invention, only one of a plurality of stereoisomerisms can be used, or several of them can be used as a mixture.

  The compounds of the present invention may be used alone or in combination, and the number and type of compounds used can be arbitrarily selected.

  Further, the compound of the present invention may be used in combination with a compound having at least 3 heteroatoms described in JP-A No. 2000-194085 and JP-A No. 2003-156823.

  The compound of the present invention can be used in combination with one or a plurality of methods having a high sensitivity effect or a compound having a high sensitivity effect. Also in this case, the method used and the number and types of the compounds to be contained can be arbitrarily selected.

In the present invention, it is sufficient that the compound (A) of the present invention is allowed to act on a silver halide photographic light-sensitive material (preferably a silver halide color photographic light-sensitive material). May be used for either the photosensitive layer or the non-photosensitive layer.
When used for a silver halide photosensitive layer, when the photosensitive layer is divided into a plurality of layers having different sensitivities, it may be used for any sensitive layer, but is preferably used for the most sensitive layer.
When used for the non-photosensitive layer, it is preferably used for the non-photosensitive layer located between the red-sensitive layer and the green-sensitive layer or between the green-sensitive layer and the blue-sensitive layer. The non-photosensitive layer refers to all layers other than the silver halide emulsion layer, and examples thereof include an antihalation layer, an intermediate layer, a yellow filter layer, and a protective layer.

  The method of adding the compound of the present invention to the light-sensitive material is not particularly specified, but the method of adding by emulsifying and dispersing together with a high boiling point organic solvent, the method of adding by dispersing solid, the method of adding to the coating solution in the form of a solution (For example, it is added by dissolving in an organic solvent such as water or methanol, or a mixed solvent), and a method of adding at the time of preparing a silver halide emulsion. However, it can be introduced into a light-sensitive material by emulsion dispersion and solid dispersion. Preferably, it is a case where it introduce | transduces into a sensitive material by emulsification dispersion | distribution.

  As the emulsification dispersion method, an oil-in-water dispersion method in which it is dissolved in a high boiling point organic solvent (a low boiling point organic solvent can be used in combination), emulsified and dispersed in an aqueous gelatin solution and added to the silver halide emulsion is used.

  Examples of high boiling point organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the latex dispersion method as one of the polymer dispersion methods include US Patent No. 4,199,363, West German Patent (OLS) No. 2,541,274, Japanese Patent Publication No. 53-41091, and European Patent Application Published Nos. 0,727,703 and 0,727,704 and the like. Furthermore, a dispersion method using an organic solvent-soluble polymer is described in International Publication No. WO88 / 723.

  Examples of the high-boiling organic solvent that can be used in the oil-in-water dispersion method include phthalic acid esters (for example, dibutyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate), phosphoric acid or phosphonic acid esters ( For example, triphenyl phosphate, tricresyl phosphate, tri-2-ethylhexyl phosphate, fatty acid esters (eg, di-2-ethylhexyl succinate, tributyl citrate), benzoic acid esters (eg, benzoic acid) 2-ethylhexyl, dodecyl benzoate, etc.), amides (eg, N, N-diethyldodecanamide, N, N-dimethyloleinamide, etc.), alcohols or phenols (eg, isostearyl alcohol, 2,4-di-) tert-amylphenol), anilines (for example, N, N-dibuty) 2-butoxy-5-tert-octylaniline, etc.), chlorinated paraffins, hydrocarbons (eg, dodecylbenzene, diisopropylnaphthalene, etc.), carboxylic acids (eg, 2- (2,4-di-tert-amyl) Phenoxy) butyric acid, etc.). Further, an organic solvent having a boiling point of 30 ° C. or higher and 160 ° C. or lower (for example, ethyl acetate, butyl acetate, methyl ethyl ketone, cyclohexanone, methyl cellosolve acetate, dimethylformamide, etc.) may be used in combination as an auxiliary solvent. The high boiling point organic solvent is preferably used in an amount of 0 to 10 times, preferably 0 to 4 times the mass ratio of the compound of the present invention.

  From the viewpoint of improving stability over time during storage in the emulsion dispersion state, suppressing photographic performance changes in the final coating composition mixed with emulsion, and improving stability over time, the emulsion dispersion may be reduced in pressure as necessary. All or part of the auxiliary solvent can be removed by a method such as distillation, washing with noodles or ultrafiltration.

  The average particle size of the lipophilic fine particle dispersion thus obtained is preferably 0.04 to 0.50 μm, more preferably 0.05 to 0.30 μm, and most preferably 0.08 to 0.20 μm. It is. The average particle size can be measured using a Coulter submicron particle analyzer model N4 (trade name, Coulter Electronics).

  As the solid fine particle dispersion method, the powder of the compound of the present invention is dispersed in a suitable solvent such as water by a ball mill, colloid mill, vibration ball mill, sand mill, jet mill, roller mill or ultrasonic wave, The method of producing is mentioned. At that time, a protective colloid (for example, polyvinyl alcohol) and a surfactant (for example, an anionic surfactant such as sodium triisopropylnaphthalenesulfonate (a mixture of three isopropyl groups having different substitution positions)) are used. Also good. In the mills, beads such as zirconia are usually used as a dispersion medium, and Zr and the like eluted from these beads may be mixed in the dispersion. Although it depends on the dispersion conditions, it is usually in the range of 1-1000 ppm. If the content of Zr in the light-sensitive material is 0.5 mg or less per 1 g of silver, there is no practical problem. The aqueous dispersion can contain a preservative (eg, benzoisothiazolinone sodium salt).

  In the present invention, for the purpose of obtaining a solid dispersion having a high S / N, a small particle size, and no aggregation, a dispersion method in which an aqueous dispersion is converted into a high-speed flow and then subjected to pressure drop can be used. As for the solid dispersion apparatus and its technology used for carrying out such a dispersion method, for example, “Dispersion Rheology and Dispersion Technology” (Toshio Kajiuchi, Hiroki Arai, 1991, Shinyamasha Publishing Co., Ltd.) p.357 to p403), “Progress of Chemical Engineering Vol. 24” (Chemical Engineering Society, Tokai Branch, 1990, Tsuji Shoten, p.184 to p185).

The addition amount of the compounds of the present invention is preferably from 0.1 to 1000 mg / m ^2, more preferably ^{1~500mg / m 2, 5~100mg / m} 2 is particularly preferred. When used in a light-sensitive silver halide emulsion layer, it is preferably 1 × 10 ⁻⁵ to 1 mol, more preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻¹ mol per mol of silver in the same layer, 1 × 10 ^{−3 to} 5 × 10 ⁻² mol is particularly preferred. Two or more compounds of the present invention may be used in combination. In this case, those compounds may be added to the same layer or to another layer.

  The pKa of the compound of the present invention is determined by the following method. Add 0.5 mL of 1N sodium chloride to 100 mL of a 6: 4 (mass ratio) tetrahydrofuran / water solution in which 0.01 mmol of the compound of the present invention is dissolved (hereinafter, mL is also referred to as “mL”). The solution is titrated with a 0.5N aqueous potassium hydroxide solution while stirring under a nitrogen gas atmosphere. The pH at the center of the inflection point of the titration curve with the horizontal axis representing the dropping amount of the aqueous potassium hydroxide solution and the vertical axis representing the pH value was defined as pKa. In the case of a compound having a plurality of dissociation sites, there are a plurality of inflection points, and a plurality of pKa values can be obtained. The inflection point can also be determined by monitoring the ultraviolet / visible absorption spectrum and examining the change in absorption.

  In general, the photographic speed is determined by the size of the silver halide emulsion grains. The larger the emulsion grains, the more the photographic speed increases. However, since the graininess deteriorates with an increase in the size of silver halide grains, sensitivity and graininess are in a trade-off relationship.

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

The present invention is not a method for increasing sensitivity with granular deterioration commensurate with sensitivity increase.
The present invention provides a method for increasing sensitivity without accompanying deterioration in graininess, or a method for increasing sensitivity, in which the increase in sensitivity is large compared to deterioration in graininess. In the present invention, when an increase in sensitivity and a deterioration in graininess occur at the same time, the sensitivity is compared after combining the graininess using the “adjusting means”, and a substantial increase in sensitivity is observed.

  A substantial increase in sensitivity is defined as a sensitivity difference of 0.02 or more when the photosensitive material is exposed through a continuous wedge and the sensitivity is compared with the logarithm of the reciprocal of the exposure amount giving the minimum density +0.5.

  The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods. A coupler dispersion for use in the present invention can be prepared by dissolving the coupler in a low boiling or partially water soluble auxiliary organic solvent. In one embodiment of the invention, such a dispersion can be made with or without a high boiling permanent organic solvent. The resulting organic solution can then be mixed with an aqueous gelatin solution, and the mixture is a mechanical stirrer suitable for high shear or turbulent mixing generally suitable for preparing photographic emulsion dispersions, for example , Colloid mills, homogenizers, microfluidizers, high-speed mixers, ultrasonic dispersers, blade mixers, devices that pump liquid streams at high pressure through orifices or interaction chambers, gorin mills, blenders, etc. Forms small particles of cloudy organic phase.

  The dispersion may be prepared using one or more devices. The auxiliary organic solvent is removed by evaporation, noodle washing, or membrane dialysis. The dispersion particles preferably have an average particle size of less than 2 μm, generally about 0.02 to 2 μm, more preferably about 0.02 to 0.5 μm. These methods are described in U.S. Pat. Nos. 2,322,027, 2,787,544, 2,801,170, 2,801,171, 2,949,360, and 3, 396,027 is described in detail.

  Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of high-boiling organic solvents having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid ester (Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethyl hex Sylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecanamide, N, N-diethyllaurylamide, N -Tetradecylpyrrolidone), alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol) Tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, dii) And propyl naphthalene), and the like. As an auxiliary solvent, 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 ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples thereof include ethoxyethyl acetate and dimethylformamide.

  The aqueous phase of the coupler dispersion of the present invention preferably comprises gelatin as a hydrophobic colloid. This can be gelatin or modified gelatin such as acetylated gelatin, phthalated gelatin, oxidized gelatin and the like. Gelatin may be base-treated like lime-treated gelatin or acid-treated like acid-treated ossein gelatin. Other hydrophilic colloids such as water-soluble polymers or copolymers may also be used. These include, but are not limited to, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate-co-vinyl alcohol, hydroxyethyl cellulose, polyacrylic acid, poly (1-vinylpyrrolidone), sodium polystyrene sulfonate, poly (2 -Acrylamide-2-methanesulfonic acid), polyacrylamide. Copolymers of these polymers with hydrophobic monomers may be used.

  Surfactants may be present in the aqueous or organic phase, and dispersions can be prepared without surfactants. Surfactants can be cationic, anionic, zwitterionic, or nonionic. The ratio of the surfactant to the liquid organic solution is generally in the range of 0.5 to 25% by weight when forming a small particle photographic dispersion. In a preferred embodiment of the present invention, an anionic surfactant is contained in the gelatin aqueous solution.

  Particularly preferred surfactants for use in the present invention include alkali metal salts of alkali-lene sulfonic acids, such as sodium salt of dodecylbenzene sulfonic acid or sodium salt of isopropyl naphthalene sulfonic acid, di-isopropyl- and triisopropyl-naphthalene. Mixtures of sodium sulfonates; alkali metal salts of alkyl sulfonic acids such as sodium dodecyl sulfate; or alkali metal salts of alkyl sulfosuccinates such as sodium bis (2-ethylhexyl) succinate sulfonate.

Next, the silver halide emulsion used in the present invention will be described in detail.
Particle size of the preferred silver halide emulsion in the present invention has an average equivalent sphere diameter of 0.35μm or less, preferably 0.3μm or less, Ri more preferably 0.2μm der hereinafter, in the present invention, all the photosensitive In all silver halide emulsions contained in the active layer, the average equivalent sphere diameter of the contained silver halide grains is 0.35 μm or less .

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

  The silver halide grains in photographic emulsions have regular (three-dimensional equidirectional) crystals such as cubes, octahedrons, and tetradecahedrons, and irregular crystal shapes such as spheres and plates. However, in the present invention, it is preferable to use a cubic emulsion.

  The grain size of the silver halide grains used in the present invention can be evaluated using an electron microscope. Specifically, in the case of those having a regular crystal, the projected area equivalent diameter obtained by observation with an electron microscope (the diameter of this circle when the projected area of the particle is equivalent to the area of the circle) is obtained. The particle volume is calculated from the projected area equivalent diameter using the fact that the crystal is regular (isotropic in three dimensions), and the diameter of the sphere when the particle volume is equivalent to the volume of the sphere. Can be obtained by calculating. In the case of irregular particles such as a plate (not three-dimensional isotropic), the volume is calculated from the projected area equivalent diameter and the particle thickness obtained by electron microscope observation, and the sphere equivalent diameter is obtained. I can do it. The equivalent sphere diameter can also be determined by the turbidity measurement method described in Particle Characterrization, 2nd edition, pages 14 to 19 (1985).

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

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

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

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

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

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

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

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

As a reduction sensitizer, stannous salt, ascorbic acid and its derivatives, hydroquinone and its derivatives, catechol and its derivatives, hydroxylamine and its derivatives, amine and polyamines, hydrazine and its derivatives, paraphenylenediamine and its derivatives, 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 (VII) and (VIII) are also preferred reduction sensitizers.

In the general formulas (VII) and (VIII), 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. (A) organic thioethers described in Japanese Patent Application Laid-Open No. 54-158917 and the like (b) thiourea derivatives described in Japanese Patent Application Laid-Open Nos. 53-82408, 55-77737, 55-2982, (C) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, as described in JP-A No. 53-144319, and (d) imidazoles as described in JP-A No. 54-1000071 (E) ammonia, (f) thiocyanate and the like.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used for the purpose of supersensitization. Typical examples thereof are U.S. Pat. Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703 377, 3,769,301, 3,814,609, 3,837,862, 4,026,707, British Patent 1,344,281, No. 1,507,803, Japanese Patent Publication Nos. 43-4936, 53-12375, Japanese Patent Application Laid-Open Nos. 52-110618, and 52-109925.

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

  The silver halide photographic light-sensitive material of the present invention preferably contains the following type 1 and type 2 compounds.

Compound (Type 1)
A compound in which a one-electron oxidant produced by one-electron oxidation can further emit one or more electrons with a subsequent bond cleavage reaction.

Compound (Type 2)
A compound capable of emitting one or more electrons after a one-electron oxidant produced by one-electron oxidation undergoes a subsequent bond formation reaction.

First, the compound of type 1 will be described.
JP-A-9-211769 (specific example: 28-) shows a compound that can be emitted from a one-electron oxidant produced by one-electron oxidation of a type 1 compound, with a subsequent bond cleavage reaction. Compounds PMT-1 to S-37 described in Table E and Table F on page 32), JP-A-9-211774, JP-A-11-95355 (specific examples: compounds INV1-36), JP-T 2001-500996 (Specific Examples: Compounds 1-74, 80-87, 92-122), US Pat. No. 5,747,235, US Pat. No. 5,747,236, European Patent 786662A1 (Specific Examples: Compounds INV1-35), “One-photon two-electron sensitizer” or “deprotonated electron-donating sensitizer” described in patents such as European Patent No. 893732A1, US Pat. No. 6,054,260, US Pat. Compounds referred to. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

Further, as a compound of type 1 that can be emitted by one-electron oxidant formed by one-electron oxidation and further undergoing bond cleavage reaction, one or more electrons can be emitted from the general formula (1) ( General formula (1) described in JP-A-2003-114487), general formula (2) (synonymous with general formula (2) described in JP-A-2003-114487), general formula (3) (JP-A-2003-114487) General formula (1) described in 2003-114488), general formula (4) (synonymous with general formula (2) described in Japanese Patent Application Laid-Open No. 2003-114488), general formula (5) (Japanese Patent Application Laid-Open No. 2003-114488). 114488 (synonymous with general formula (3)), general formula (6) (synonymous with general formula (1) described in Japanese Patent Application Laid-Open No. 2003-75950), and general formula (7) (Japanese Patent Application Laid-Open No. 2003-75950). In the general formula (2)), the general formula (8) The reaction represented by the general formula (1) described in 004-239934) or the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in JP-A-2004-245929) may occur. Among the compounds, a compound represented by the general formula (9) (synonymous with the general formula (3) described in JP-A No. 2004-245929) can be given. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formulas (1) and (2), RED ₁ and RED ₂ represent a reducing group. R ₁ is a non-metallic atomic group capable of forming a cyclic structure corresponding to a tetrahydro form or hexahydro form of a 5-membered or 6-membered aromatic ring (including aromatic heterocycle) together with carbon atom (C) and RED ₁ To express. R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Lv ₁ and Lv ₂ represent a leaving group. ED represents an electron donating group.

In the general formulas (3), (4) and (5), Z ₁ represents an atomic group capable of forming a 6-membered ring with a nitrogen atom and two carbon atoms of the benzene ring. _{R 5, R 6, R 7} , R 9, R 10, R 11, R 13, R 14, R 15, R 16, R 17, R 18, R 19 represents a hydrogen atom or a substituent. R ₂₀ represents a hydrogen atom or a substituent. When R ₂₀ represents a group other than an aryl group, R ₁₆ and R ₁₇ are bonded to each other to form an aromatic ring or an aromatic heterocycle. R ₈ and R ₁₂ represent a substituent that can be substituted on the benzene ring, m1 represents an integer of 0 to 3, and m2 represents an integer of 0 to 4. Lv ₃ , Lv ₄ and Lv ₅ represent a leaving group. ED represents an electron donating group.

In the general formulas (6) and (7), RED ₃ and RED ₄ represent a reducing group. R _{21 to} R ₃₀ represent a hydrogen atom or a substituent. Z ₂ represents —CR ₁₁₁ R ₁₁₂ —, —NR ₁₁₃ —, or —O—. R ₁₁₁ and R ₁₁₂ each independently represents a hydrogen atom or a substituent. _R113 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

In general formula (8), RED ₅ is a reducing group and represents an arylamino group or a heterocyclic amino group. R ₃₁ represents a hydrogen atom or a substituent. X represents an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylamino group, an arylamino group, or a heterocyclic amino group. Lv ₆ is a leaving group and represents a carboxy group or a salt thereof, or a hydrogen atom.

The compound represented by the general formula (9) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by further oxidation after two-electron oxidation accompanied by decarboxylation. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5- or 6-membered heterocycle with C═C. Z ₄ represents a group which forms a 5-membered aryl group or heterocyclic group with C═C. Z ₅ represents a group that forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group with CC. Z ₆ represents a group that forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group with CC. M represents a radical, a radical cation, or a cation. In the general formula (9), R ₃₂ , R ₃₃ , Z ₃ and Z ₅ have the same meanings as in the chemical reaction formula (1).

  Next, the type 2 compound will be described.

As a compound in which a one-electron oxidant produced by one-electron oxidation with a type 2 compound can further emit one or more electrons with a subsequent bond formation reaction, a compound represented by the general formula (10) A compound capable of causing the reaction represented by the general formula (1) described in 2003-140287) and the chemical reaction formula (1) (synonymous with the chemical reaction formula (1) described in JP-A-2004-245929). And a compound represented by the general formula (11) (synonymous with the general formula (2) described in JP-A No. 2004-245929). An organic compound that generates an (n + m) -valent cation with an intramolecular cyclization reaction from an n-valent cation radical described in JP-A-2003-121954 and the like (where n and m are each independently an integer of 1 or more) Are also included in type 2 compounds. The preferred ranges of these compounds are the same as the preferred ranges described in the cited patent specifications.

In the general formula (10), RED ₆ represents a reducing group that is one-electron oxidized. Y reacts with one-electron oxidant produced by one-electron oxidation of RED ₆ to form a new bond, a carbon-carbon double bond site, a carbon-carbon triple bond site, an aromatic group site, or Reactive group containing a non-aromatic heterocyclic moiety of a benzo-fused ring. Q represents a linking group that links RED ₆ and Y.

The compound represented by the general formula (11) is a compound that undergoes a bond formation reaction represented by the chemical reaction formula (1) by being oxidized. In the chemical reaction formula (1), R ₃₂ and R ₃₃ represent a hydrogen atom or a substituent. Z ₃ represents a group which forms a 5- or 6-membered heterocycle with C═C. Z ₄ represents a group which forms a 5-membered aryl group or heterocyclic group with C═C. Z ₅ and Z ₆ represent a group which forms a 5- or 6-membered cyclic aliphatic hydrocarbon group or heterocyclic group together with C—C. M represents a radical, a radical cation, or a cation. In the general formula (11), R ₃₂ , R ₃₃ , Z ₃ and Z ₄ have the same meaning as in the chemical reaction formula (1).

  Of the compounds of types 1 and 2, “a compound having an adsorptive group to silver halide in the molecule” or “a compound having a partial structure of a spectral sensitizing dye in the molecule” is preferable. Typical examples of the adsorptive group to silver halide are those described in JP-A No. 2003-156823, page 16, right line 1 to page 17, right line 12. The partial structure of the spectral sensitizing dye is a structure described on page 17, right line 34 to page 18, left line 6 of the same specification.

  More preferably, the compound of type 1 or 2 is “a compound having at least one adsorptive group to silver halide in the molecule”. More preferred is “a compound having two or more adsorptive groups to silver halide in the same molecule”. When two or more adsorptive groups are present in a single molecule, these adsorptive groups may be the same or different.

  The adsorptive group is preferably a mercapto-substituted nitrogen-containing heterocyclic group (for example, 2-mercaptothiadiazole group, 3-mercapto-1,2,4-triazole group, 5-mercaptotetrazole group, 2-mercapto-1,3,4). -Oxadiazole group, 2-mercaptobenzoxazole group, 2-mercaptobenzthiazole group, 1,5-dimethyl-1,2,4-triazolium-3-thiolate group, etc.) or imino silver (> NAg) And a nitrogen-containing heterocyclic group having a —NH— group as a heterocyclic partial structure (for example, a benzotriazole group, a benzimidazole group, an indazole group, etc.). Particularly preferred are 5-mercaptotetrazole group, 3-mercapto-1,2,4-triazole group, and benzotriazole group, most preferred are 3-mercapto-1,2,4-triazole group, and 5 -Mercaptotetrazole group.

  It is also particularly preferred that the adsorptive group has two or more mercapto groups as a partial structure in the molecule. Here, the mercapto group (—SH) may be a thione group if it can be tautomerized. Preferred examples of the adsorptive group having two or more mercapto groups as a partial structure (such as a dimercapto-substituted nitrogen-containing heterocyclic group) include 2,4-dimercaptopyrimidine group, 2,4-dimercaptotriazine group, 3, A 5-dimercapto-1,2,4-triazole group may be mentioned.

  A quaternary salt structure of nitrogen or phosphorus is also preferably used as the adsorptive group. Specific examples of the quaternary salt structure of nitrogen include an ammonio group (such as a trialkylammonio group, a dialkylaryl (or heteroaryl) ammonio group, an alkyldiaryl (or heteroaryl) ammonio group) or a quaternized nitrogen atom. A group containing a nitrogen-containing heterocyclic group containing The quaternary salt structure of phosphorus includes a phosphonio group (trialkylphosphonio group, dialkylaryl (or heteroaryl) phosphonio group, alkyldiaryl (or heteroaryl) phosphonio group, triaryl (or heteroaryl) phosphonio group, etc.). Can be mentioned. More preferably, a quaternary salt structure of nitrogen is used, and more preferably, a 5-membered or 6-membered nitrogen-containing aromatic heterocyclic group containing a quaternized nitrogen atom is used. Particularly preferably, a pyridinio group, a quinolinio group, or an isoquinolinio group is used. These nitrogen-containing heterocyclic groups containing a quaternized nitrogen atom may have an arbitrary substituent.

Examples of counter anions of quaternary salts include halogen ions, carboxylate ions, sulfonate ions, sulfate ions, perchlorate ions, carbonate ions, nitrate ions, BF ₄ ⁻ , PF ₆ ⁻ , Ph ₄ B ^{− and the} like. It is done. When a group having a negative charge in the carboxylate group or the like is present in the molecule, an inner salt may be formed together with the group. As the counter anion not present in the molecule, a chlorine ion, a bromo ion or a methanesulfonate ion is particularly preferable.

A preferred structure of the compound represented by types 1 and 2 having a quaternary salt structure of nitrogen or phosphorus as the adsorptive group is represented by the general formula (X).

In general formula (X), P and R each independently represent a quaternary salt structure of nitrogen or phosphorus that is not a partial structure of a sensitizing dye. Q ₁ and Q ₂ each independently represent a linking group, specifically, a single bond, an alkylene group, an arylene group, a heterocyclic group, —O—, —S—, —NR _N —, —C (═O ) —, —SO ₂ —, —SO—, —P (═O) — each independently or a combination of these groups. Here, _RN represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. S is a residue obtained by removing one atom from a compound represented by type (1) or (2). i and j are integers of 1 or more, and are selected from a range in which i + j is 2 to 6. Preferably, i is 1 to 3, and j is 1 to 2, more preferably i is 1 or 2, and j is 1, and particularly preferably i is 1 and j is 1. The compound represented by the general formula (X) preferably has a total carbon number in the range of 10 to 100. More preferably, it is 10-70, More preferably, it is 11-60, Most preferably, it is 12-50.

Specific examples of the compounds represented by type 1 and type 2 are listed below, but the present invention is not limited thereto.

  The type 1 and type 2 compounds of the present invention 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 addition position is preferably from the end of particle formation to before the desalting step, at the time of chemical sensitization (from immediately before the start of chemical sensitization to immediately after the end), and before application, more preferably at the time of chemical sensitization and before application.

  The compounds of type 1 and type 2 of the present invention are 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 type 1 and type 2 compounds of the present invention are 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 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 the light-sensitive material to which the method of the present invention can be applied, it is sufficient that at least one blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer and a non-photosensitive layer are provided on the support. As a typical example, a blue-sensitive, green-sensitive, and red-sensitive photosensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity are provided on a support. A silver halide photographic material having at least one non-photosensitive layer. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the arrangement of unit photosensitive layers is generally The red color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are installed in this order from the support side. However, depending on the purpose, the installation order may be reversed, or the installation order may be such that different photosensitive layers are sandwiched in the same color-sensitive layer. A non-photosensitive layer may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. These may contain couplers, DIR compounds, color mixing inhibitors and the like described later. A plurality of silver halide emulsion layers constituting each unit light-sensitive layer is composed of two layers of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in German Patent 1,121,470 or British Patent 923,045. Are preferably arranged such that the photosensitivity decreases sequentially toward the support. In addition, as described in JP-A-57-112751, 62-200350, 62-206541, 62-206543, a low-sensitivity emulsion layer on the side away from the support, A high-sensitivity emulsion layer may be provided on the side close to the body.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Example 1
(Preparation of emulsion Em-A)
An AgBrI monodisperse cubic emulsion was prepared according to the following. The following solutions were prepared.

<< Solution A >> Lime-treated ossein gelatin: 30 g, KBr: 0.4 g, and water: 1.3 L aqueous solution;
<< Solution B >> 0.2 L of an aqueous solution containing 20 g of AgNO ₃ ;
<< Solution C >> 0.2 L of aqueous solution containing KBr: 15 g and KI: 0.6 g;
<< Solution D >> 0.65 L of an aqueous solution containing 162.5 g of AgNO ₃ ;
<< Solution E >> 0.7 L of an aqueous solution containing KBr: 124.8 g, KI: 5.4 g, and NaCl: 0.6 g.

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

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

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

  The temperature of the solution in the reaction vessel, the composition and concentration of the solutions A to E, the addition rate of the solutions B to E, the pBr of the solution in the reaction solution, the addition amount of thiourea dioxide, sodium benzenesulfonate, K2IrCl6, and the desorption The amount of the sensitizing dye after completion of the salt and the amount of the chemical sensitizer were appropriately changed, and Em-i was prepared so as to have almost the same sensitivity as Em-D.

(Preparation of emulsion Em-C)
An AgBrI monodisperse cubic emulsion was prepared according to the following. The following solutions were prepared.

"The solution A" lime-: 30 g, KBr: 0.4 g, and water: an aqueous solution containing 1.5 L "solution _B" AgNO 3: aqueous solution containing 162.5 g 0.65 L
<< Solution C >> 0.7 L of an aqueous solution containing KBr: 125.4 g, KI: 4.5 g, and NaCl: 0.3 g.

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

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

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

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

(Back layer)
Methyl methacrylate-methacrylic acid copolymer (copolymerization molar ratio 1: 1) 1.5 parts by mass Cellulose acetate hexahydrophthalate (hydroxypropyl group 4%, methyl group 15%, acetyl group 8%,
(Phthalyl group 36%) 1.5 parts by weight Acetone 50 parts by weight Methanol 25 parts by weight Methyl Cellosolve 25 parts by weight Colloidal carbon 1.2 parts by weight A coating solution is prepared at a ratio of 1 or more and the concentration is 1. It was applied so as to be 0.

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

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

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

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

Third layer: low-sensitivity red-sensitive emulsion layer Em-I silver coating amount 0.280
Gelatin 1.900
ExC-1 0.130
ExC-2 0.194
ExC-3 0.030
ExC-4 0.034
ExC-5 0.029
Cpd-2 0.105
Solv-1 0.440.

Fourth layer: Intermediate red-sensitive emulsion layer Em-H Silver coating amount 0.250
Gelatin 1.050
ExC-1 0.103
ExC-2 0.125
ExC-3 0.019
ExC-4 0.028
ExC-5 0.008
Cpd-2 0.069
Solv-1 0.292.

5th layer: High sensitivity red-sensitive emulsion layer Em-G Silver coating amount 0.240
Gelatin 0.757
ExC-1 0.060
ExC-2 0.076
ExC-3 0.019
ExC-5 0.005
Cpd-2 0.043
Solv-1 0.167.

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

Seventh layer: low-sensitivity green-sensitive emulsion layer Em-F silver coating amount 0.297
Gelatin 1.614
ExM-1 0.164
ExM-3 0.095
ExM-4 0.148
Solv-1 0.473
Solv-2 0.050.

Eighth layer: Medium sensitivity green-sensitive emulsion layer Em-E Silver coating amount 0.200
Gelatin 0.500
ExM-1 0.048
ExM-2 0.037
ExM-3 0.020
ExM-4 0.050
Solv-1 0.171
Solv-2 0.020.

Ninth layer: High-sensitivity green-sensitive emulsion layer Em-D Silver coating amount 0.270
Gelatin 0.447
ExM-1 0.040
ExM-2 0.031
ExM-3 0.018
ExM-4 0.036
Solv-1 0.150
Solv-2 0.010.

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

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

12th layer: Medium sensitivity blue-sensitive emulsion layer Em-B Silver coating amount 0.150
Gelatin 0.859
ExY-1 0.039
ExY-2 0.391
ExC-3 0.009
Solv-1 0.163.

13th layer: High-sensitivity blue-sensitive emulsion layer Em-A Silver coating amount 0.302
Gelatin 0.371
ExY-1 0.010
ExY-2 0.101
ExC-3 0.003
Solv-1 0.042
Compound 7 5.0 * 10 <^-5> .

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

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

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

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

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

The compound (A) described in Table A was added from the sample 101 to the ninth layer, and photosensitive materials 102 to 104 were prepared in the same manner as the sample 101 except that.
Further, based on the obtained sample 101, the emulsion used in the ninth layer was changed to Em-i to prepare sample 105.
Moreover, based on the obtained sample 105, the compound (A) described in Table A was added to the ninth layer to prepare samples 106 to 111.
Samples 112, 113, and 114 were prepared by multiplying Em-i used for the ninth layer by 0.89 times based on the obtained samples 107, 109, and 111, respectively.

  The sensitivity of the green sensitive layer is indicated by the logarithm of the reciprocal of the exposure amount at which the magenta color image density gives the lowest density +0.5, and the experiment No1 to 4 are shown by the difference in absolute value when the experiment No1 is used as a reference. Experiment Nos. 5 to 14 are shown by the difference in absolute value when experiment No. 5 is used as a reference.

  Bleeding and color purity were evaluated using a G laser after exposure and development, and evaluated by the method described in the text. The results are shown in Table A below.

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

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

The prescription of the treatment liquid used in each treatment step is as follows.
Prescription of each treatment solution (1) Pre-bath Prescription value Water of 27-38 ° C 800ml
Borax (10 hydrate) 20.0g
Sodium sulfate (anhydrous) 100g
Sodium hydroxide 1.0g
Add water 1.00 liter pH (27 ° C.) 9.25.

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

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

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

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

(6) Stable Prescription Value 21-27 ° C Water 1.00 L Kodak Stabilizer Additive 0.14 ml
Formalin (37.5% solution) 1.5 ml.

Sensory evaluation of the image quality of samples 101 to 114 was performed by the following method.
Negative images obtained by exposing landscape images having digital information of the number of pixels (1024 × 778) and (2048 × 1556) to the samples 101 to 114 with B, G, R lasers with a size of 0.8 × 0.6 inch The image was projected and viewed by 20 inspectors. The number of pixels (1024 × 778) was used, and the evaluation value when using the sample 104 was set to 3 (standard), and the relative evaluation was performed. Further, the negative image was further exposed to a Fuji color positive film F-CP, and then developed by the method described in the section “FUJIFILM PROCESSING MANUAL Motion Picture Films”, to obtain a positive image. This was projected and the same evaluation was performed.

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

表Ａより、本発明の画像記録技術を採用すれば、鮮鋭性、色彩度の優れた映写画像を得られ、ハロゲン化銀写真感光材料が得られることがわかる。 0: very inferior 1: inferior 2: slightly inferior 3: (standard)
4: slightly superior 5: excellent 6: very excellent

From Table A, it can be seen that if the image recording technique of the present invention is employed, a projected image having excellent sharpness and color saturation can be obtained, and a silver halide photographic light-sensitive material can be obtained.

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

Explanation of symbols

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

Claims (15)

In a silver halide photographic material having at least one blue-sensitive layer, green-sensitive layer, and red-sensitive layer on a transparent support, at least one of the following compounds (A) is contained in at least one layer: and, in all of the silver halide emulsion containing all of the photosensitive layer, Ri mean equivalent spherical diameter of der below 0.35μm silver halide grains containing, when recording digital image information in the 2000dpi or higher resolution In addition, the silver halide photographic light-sensitive material is characterized in that the blur k of the obtained image satisfies the following formula (I).
Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) In the compound represented by the following general formula (M-3), R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) compound 3) alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or aryl A compound represented by the following general formula (Ca-8) which may have a substituent selected from a sulfonyl group, an alkoxycarbonyl group and a carbamoyl group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic light-sensitive material, and the blur k represents the blur (μm) at the color density D. In a silver halide photographic material having at least one blue-sensitive layer, green-sensitive layer, and red-sensitive layer on a transparent support, at least one of the following compounds (A) is contained in at least one layer: and, in all of the silver halide emulsion containing all of the photosensitive layer, when the mean equivalent spherical diameter of silver halide grains contained in the Ri der less 0.35 .mu.m, were recorded 3,000,000 pixels or more digital image information In addition, the silver halide photographic light-sensitive material is characterized in that the blur k of the obtained image satisfies the following formula (I).
Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) In the compound represented by the following general formula (M-3), R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) compound 3) alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or aryl A compound represented by the following general formula (Ca-8) which may have a substituent selected from a sulfonyl group, an alkoxycarbonyl group and a carbamoyl group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic light-sensitive material, and the blur k represents the blur (μm) at the color density D.   The silver halide photographic light-sensitive material according to claim 1 or 2, wherein a color purity ratio in color reproduction of image recording is 80% or more.   The average equivalent sphere diameter of silver halide grains contained in all of the silver halide emulsions contained in all the photosensitive layers is 0.2 μm or less. The silver halide photographic light-sensitive material described in 1. In all of the silver halide emulsion containing all of the light-sensitive layer of the silver halide photographic light-sensitive material, any one of claims 1 to 4, wherein the silver halide grains contained in the a cubic grains The silver halide photographic light-sensitive material described in 1. The silver halide emulsions used in the light-sensitive layer, any one of claims 1-5, characterized in that the silver iodide is iodobromide or silver iodochlorobromide and silver containing 2-10 mole% 2. A silver halide photographic light-sensitive material according to item 1. The silver halide photographic light-sensitive material according to any one of claims 1 to 6 , wherein the silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material for a film intermediate film. An image forming method for recording digital image information on a silver halide photographic light-sensitive material with a resolution of 2000 dpi or more, wherein the silver halide photographic light-sensitive material has at least one blue-sensitive layer on a transparent support, Halogenation contained in all silver halide emulsions having a green photosensitive layer and a red photosensitive layer and containing at least one compound (A) below in at least one layer and contained in all photosensitive layers mean equivalent spherical diameter of silver particles der less 0.35 .mu.m, image blurring k of the image obtained by recording to the silver halide photographic light-sensitive material, and satisfies the following formula (I) Forming method.
Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) In the compound represented by the following general formula (M-3), R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) compound 3) alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or aryl A compound represented by the following general formula (Ca-8) which may have a substituent selected from a sulfonyl group, an alkoxycarbonyl group and a carbamoyl group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic light-sensitive material, and the blur k represents the blur (μm) at the color density D. An image forming method for recording digital image information of 3 million pixels or more on a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material has at least one blue-sensitive layer on a transparent support, Halogenation contained in all silver halide emulsions having a green photosensitive layer and a red photosensitive layer and containing at least one compound (A) below in at least one layer and contained in all photosensitive layers mean equivalent spherical diameter of silver particles der less 0.35 .mu.m, image blurring k of the image obtained by recording to the silver halide photographic light-sensitive material, and satisfies the following formula (I) Forming method.
Compound (A): A heterocyclic compound having one or more heteroatoms and selected from the following 1) to 3).
1) In the compound represented by the following general formula (M-3), R ₁₅ represents a t-butyl group, X ₁₁ represents an arylthio group, and R ₁₇ represents an aryl group.
2) The following general formula (Ca) which may have a substituent selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyl or arylsulfonyl group, an alkylamino group and an acylamino group -1) compound 3) alkyl group, aryl group, alkoxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, alkylthio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or aryl A compound represented by the following general formula (Ca-8) which may have a substituent selected from a sulfonyl group, an alkoxycarbonyl group and a carbamoyl group

k <4.5 × (D−0.2) ² (I)
In the formula (I), D represents the color density of the silver halide photographic light-sensitive material, and the blur k represents the blur (μm) at the color density D. The image forming method according to claim 8 or 9 , wherein a color purity ratio is 80% or more in color reproduction at the time of image recording. In all of the silver halide emulsion contained in the all light sensitive layer, any one of claims 8 to 10, wherein the mean equivalent spherical diameter of silver halide grains contained in the at 0.2μm or less The image forming method described in 1. In all of the silver halide emulsion containing all of the light-sensitive layer of the silver halide photographic light-sensitive material, any one of claims 8 to 11, wherein the silver halide grains contained in the a cubic grains The image forming method described in 1. The silver halide emulsions used in the light-sensitive layer, any one of claims 8 to 12, wherein the silver iodide is iodobromide or silver iodochlorobromide and silver containing 2-10 mole% 2. The image forming method according to item 1. 14. The image forming method according to any one of claims 8 to 13 , wherein the silver halide photographic light-sensitive material is a silver halide photographic light-sensitive material for a film intermediate film. Image forming method characterized in that the image obtained by the image forming method according to any one of claims 8 to 14, further recording an analog method to a silver halide photographic light-sensitive material.

Images