JPH10111541A - Radiographic element and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure high sensitivity, high sharpness and rapid processability by adsorbing a specified benzimidazolo-carbocyanine dye on fine particles in a nonphotosensitive silver halide emulsion. SOLUTION: This radiographic element has a nonphotosensitive silver halide emulsion layer contg. nonphotosensitive fine silver halide particles with spectral sensitizing dyes adsorbed on the surfaces. At least one of the sensitizing dyes is a benzimidazolocarboxyanine dye represented by the formula. The emulsion layer absorbs light in a spectral region in which this radioactive element has response and the crossover of the emulsion layer is <10%. In the formula, each of R<11> -R<14> is alkyl, at least one of R<11> and R<12> is alkoxyalkyl, at least one of R<13> and R<14> is sulfoalkyl, each of X<11> -X<14> is H, cyano, etc., at least one of X<11> and X<13> is H, Z is an ion required to balance an electric charge and (n) is 1 or 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to radiographic elements, and more particularly to medical radiography, which is used between intensifying screen pairs that absorb X-rays and emit fluorescence in the visible spectral region. Related to radiographic elements.

[0002]

BACKGROUND OF THE INVENTION In radiography, especially medical radiography, a radiographic element having a silver halide emulsion layer coated on both sides of a film support is sensitized by absorbing X-rays and generating fluorescence in the visible spectral region. Used between screen pairs. This double-coated radiographic element can efficiently use X-rays, so that the radiation exposure dose during diagnosis can be kept low. On the other hand, part of the luminescence of the intensifying screen is not absorbed by the silver halide emulsion layer adjacent to the intensifying screen, which passes through the transparent support and exposes the opposite silver halide emulsion layer. Otherwise, the sharpness of the image is impaired. Techniques for suppressing this crossover have been conventionally proposed.

One of the methods for suppressing crossover is as follows.
There is a method in which a dye which absorbs screen emission in the responsive spectral region of the radiographic element is contained between the support and the silver halide emulsion layer to absorb crossover light. This crossover cut dye can be contained in the intermediate layer between the support and the silver halide emulsion layer or in the subbing layer of the support, but in any case, the crossover cut dye is fixed in some way. Must have been. Otherwise, the photographic sensitivity will be reduced due to the crossover cut dye diffused in the silver halide emulsion layer.

[0004] On the other hand, during processing after exposure, the crossover cut dye must be quickly diffused and decolored. Otherwise, a residual color failure due to the crossover cut dye remaining after the treatment is caused. A method of fixing a dye in a layer with a polymer mordant and performing crossover cut is described in, for example, European Patent Application No. 101295, etc. In this method, any of desensitization by a diffusion dye and residual color by a residual dye is used. Again, it was not enough.

A method of fixing a dye in the form of solid fine particles in a layer and performing crossover cutting is disclosed in, for example, JP-A No. 1-17.
2828 and the like. However, this method requires a large amount of dye for sufficient crossover cutting, in which case the decolorization of the dye is insufficient in rapid processing.

A method of performing crossover cut with a spectral sensitizing dye adsorbed and fixed on silver halide fine particles is described in, for example, JP-A-2-29641.
This method enables efficient crossover cut with a smaller amount of dye by forming a J band at the screen emission wavelength in the radiographic element response spectral region.
Nevertheless, the diffusion of the dye during processing is the rate-controlling of decolorization,
Even with this method, decolorization of the dye was insufficient in rapid processing.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a cross-over cut without adversely affecting photographic properties such as desensitization, and decolorization sufficiently fast during processing so as not to cause residual color, high sensitivity and high sharpness. It is to provide a radiographic element having rapid processing suitability.

[0008]

The object of the present invention has been attained by the following means. (1) A radiographic element comprising a transparent support, at least one photosensitive silver halide emulsion layer coated on the support, and at least one layer coated between the support and the emulsion layer. A substantially light-insensitive silver halide emulsion layer, wherein the substantially light-insensitive silver halide emulsion layer has at least one spectral sensitizing dye adsorbed on its surface. The spectrally sensitizing dye is a benzimidazolocarbocyanine dye represented by the general formula [1], and the substantially light-insensitive silver halide emulsion layer is A radiographic element absorbing light in the spectral region of the response of the element and having a crossover of less than 10%. General formula [1]

[0009]

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In the general formula [1], R¹¹, R¹², R¹³, R¹⁴
Represents a substituted or unsubstituted alkyl group;¹¹, R¹²of
At least one of which represents an alkoxyalkyl group;¹³,
R¹⁴At least one represents a sulfoalkyl group.
X¹¹, X¹², X¹³, X¹⁴Are the same or different
May be substituted with a hydrogen atom, a cyano group, or a halogen.
X represents an alkyl group or a halogen atom; ¹¹, X¹³
At least one represents a hydrogen atom. Z is the balun of charge
Represents the ions required to remove the ions, n is 1 or 2
In the case where an inner salt is formed, n = 1.

(2) The radiographic element according to (1), wherein the non-photosensitive silver halide fine particles have an average particle size of 0.005 to 0.1 μm.

(3) The radiographic element according to (1) or (2), wherein the non-photosensitive silver halide fine particles are non-photosensitive silver halide fine particles having an epitaxial portion, and A radiographic element characterized in that the halogen composition is high iodine silver iodobromide or silver iodochloride, or high bromide silver chlorobromide.

(4) The silver halide fine particles in the radiographic element according to any one of (1) to (3), wherein a predetermined number of liquid supply ports through which a liquid to be stirred flows, and a liquid after the stirring processing. Tank having a liquid discharge port for discharging the liquid and a pair of stirring blades that are separately disposed at least at two locations in the stirring tank, are driven to rotate in opposite directions to each other, and control the stirring state of the liquid in the stirring tank. A radiographic element manufactured using an equipped stirrer.

(5) The radiographic element according to any one of (1) to (4), wherein the silver halide emulsion used in at least one of the photosensitive silver halide emulsion layers has a silver chloride content. A radiographic element comprising a silver halide emulsion of 90 mol% or more and 100 mol% or less.

(6) An image forming method in which the radiographic element according to any one of (1) to (5) is subjected to image exposure, development, fixing, washing and drying, followed by drying. Wherein the at least one processing step is carried out in the presence of a diaminostilbene type compound represented by the general formula [2]. General formula [2]

[0016]

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In the general formula [2], L ¹ and L ² may be the same or different, and are represented by —OR ¹ or —NR ² R
³ (R ¹ , R ² , and R ³ each represent a hydrogen atom or an alkyl group), and the following conditions (1) and (2)
At least one of the following is satisfied.

(1) The four substituents L ¹ and L ² in the general formula [ ² ] have a total of four or more substituents selected from the general formula [Group A].

(2) The four substituents L ¹ and L ² in the general formula [ ² ] have a total of two substituents selected from the general formula [Group A] and are selected from the general formula [Group B]. Has two or more substituents in total. General formula [Group A]

[0020]

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Formula [Group B]

[0022]

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In the general formula [Group A], X is a halogen atom, R
Represents an alkyl group. In the general formulas [2] and [Group A], M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The substantially light-insensitive silver halide fine particles of the present invention will be described in more detail. In the present invention, being substantially non-photosensitive is less than 1 in ASA sensitivity,
Preferably it is less than 0.1.

The smaller the size of the fine particles, the larger the specific surface area, and it is preferable because more dye can be adsorbed with a smaller amount of silver. Although the lower limit of the particle size depends solely on manufacturing constraints, it is difficult for extremely small-sized fine particles to exist alone alone, and unless the dye adsorbed on the surface suppresses Ostwald ripening, the fine particles dissolve and recrystallize. And the size increases.

The size of the fine particles can be confirmed with a transmission electron microscope as it is after placing the fine particles on a mesh, and the magnification is preferably from 20,000 to 40,000. The particle size of the present invention is preferably from 0.005 to 0.1 µm, more preferably from 0.005 to 0.05 µm, even more preferably from 0.
005 to 0.03 μm, particularly preferably 0.00
5 to 0.02 μm. The halogen composition of the fine particles is preferably silver iodide from the viewpoint of strong dye adsorption, but is preferably silver chloride from the viewpoint of good decolorization during processing. This is because the dye in the adsorbed state is stabilized and has a lower pKa than in the case where the dye is freely present in the solution, which makes it more difficult to add a proton. The fine particles of the present invention may be silver halide having a uniform composition of pure silver iodide, pure silver bromide or pure silver chloride, or a mixed crystal, core-shell of silver iodobromide, silver iodochloride or silver chlorobromide. Although it may be a particle or an epitaxial particle, it is preferably an epitaxial particle, and more preferably the epitaxial portion has a high iodine content (preferably an iodine content of 1 mol% to 10 mol%, more preferably 5 mol% to 10 mol%). Silver iodobromide or silver iodochloride, or an epitaxial part having a high bromo content (preferably a Br content of 10 mol%)
Or more and 99 mol% or less).

In general, the amount of the dye adsorbed on the fine particles is preferably in excess of the saturated coating amount. However, if the Ostwald ripening of the fine particles is suppressed and a sufficient crossover cut can be obtained, the amount of the dye added may be smaller. Although the optimum dye addition amount may vary depending on the halogen composition of the fine particles, the dye addition amount is generally selected in the range of 0.001 to 0.5 mol per mol of silver of the fine particles, More preferably, it is selected in the range of 0.001 to 0.05 mol. The content of the silver halide fine particles of the present invention may be the amount necessary for the above crossover cut, and the amount of silver coated on one side is preferably 10 per m ² of the light-sensitive material.
mg to 1 g, more preferably 25 mg to 800 mg, particularly preferably 50 mg to 500 mg.

The substantially light-insensitive silver halide fine grains of the present invention can be produced by any of the known methods. In particular, the silver halide fine grain emulsion production method described in Japanese Patent Application No. 8-207219 is used. Useful for the present invention.

FIG. 1 shows an example of a stirrer used in the production method. The stirrer includes a stirring tank having a predetermined number of liquid supply ports through which a liquid to be stirred is introduced, and a liquid discharge port through which the liquid after the stirring process is discharged.
And a pair of agitating blades which are arranged at a distance from each other and driven to rotate in opposite directions to each other.

The stirrer 10 has a cylindrical stirring tank 18 having three liquid supply ports 11, 12, 13 through which a liquid to be stirred is introduced, and a liquid discharge port 16 through which a mixed liquid having undergone the stirring process is discharged. And a pair of agitating blades 21 and 22 which are agitating means for controlling the agitating state of the liquid in the agitating tank 18 by being rotationally driven in the agitating vessel 18.

The stirring tank 18 is composed of a cylindrical tank main body 19 whose central axis is oriented in the vertical direction, and a seal plate 20 serving as a tank wall for closing upper and lower open ends of the tank main body 19. Further, the stirring tank 18 and the tank main body 19 are formed of a non-magnetic material having excellent magnetic permeability. Three liquid supply ports 1
The liquid outlets 1, 12, and 13 are provided near the lower end of the tank body 19, and the liquid outlet 16 is provided near the upper end of the tank body 19. In the case of this embodiment, the liquid supply port 11 provided at the lowermost end is for supplying a liquid of the main component to be stirred, and the liquid supply ports 12 and 13 provided above the liquid supply port 11 are added to the liquid of the main component. It is for supplying an additive liquid to be uniformly stirred and mixed with the liquid of the main component.

The pair of stirring blades 21 and 22 are spaced apart from each other at upper and lower ends of the stirring tank 18 opposite to each other.
They are driven to rotate in opposite directions. Each stirring blade 21, 22
Constitutes a magnetic coupling C with the external magnet 26 disposed outside the tank wall (seal plate 20) where the stirring blades 21 and 22 are close to each other. That is, the stirring blades 21 and 22 are connected to the respective external magnets 26 by magnetic force.
By rotationally driving at 9, the rotational operations are performed in opposite directions. In the stirring device 10 described above, the pair of stirring blades 21 and 22 arranged opposite to each other in the tank 18 have different directions as shown by a wavy arrow (X) and a solid line arrow (Y) in FIG. A stirring flow is formed in the tank 18.

According to this production method, an aqueous solution of a water-soluble silver salt and an aqueous solution of a water-soluble halide are supplied and mixed into the stirring tank having an inner volume of several ml to form silver halide fine particles.
By immediately discharging the fine particles from the stirring tank, it is possible to prevent the fine particles from growing and increasing in size, and to obtain extremely small silver halide fine particles.

The size of the fine particles obtained by the above-mentioned production method strongly depends on the number of rotations of stirring. In order to obtain small-sized fine particles, the higher the number of rotations of stirring, the better. If the stirring is insufficient, the particles become coarse due to coalescence aging (contact and adhesion of fine particles). The preferred stirring rotation speed is selected in the range of 500 to 10000 rpm, and more preferably in the range of 1000 to 10000 rpm.
Further, the size of the fine particles obtained by the above-mentioned production method strongly depends on the residence time of the fine particle emulsion in the mixing vessel. In order to obtain small-sized fine particles, generally, the shorter the residence time, the better. Here, the residence time is defined below.

T = c / v t: retention time of fine grain emulsion (sec) c: internal volume of mixing vessel (ml) v: total amount of liquid added to mixing vessel per unit time (ml
sec ^-1 )

The preferred residence time t in the present invention is 60
Seconds or less, more preferably 10 seconds or less, and most preferably 2 seconds or less.
Seconds or less.

The substantially light-insensitive silver halide fine grain emulsion contains a benzimidazolocarbocyanine dye represented by the general formula [1] in the fine grain in order to contain the emulsion and form a crossover cut layer. Adsorb.

The benzimidazolocarbocyanine dye may be added as an aqueous solution or dissolved in an organic solvent, such as methanol, during or after the formation of the fine particles. However, the Ostwald ripening of the fine particles can be more effectively performed. In order to suppress and obtain small-sized fine particles, it is most preferable to add them during the formation of the fine particles. It is preferable that ripening can be suppressed more effectively, more preferably, a method of adding a fine particle emulsion immediately after preparation to a dye solution, and more preferably, fine particles are formed in the first mixer, and the fine particles are immediately formed. A preferred method is to discharge the mixture from the mixer, introduce the mixture into the second mixer, add a dye thereto, and mix with the fine grain emulsion. The dye to be added may be an aqueous solution or a solution prepared by dissolving in an organic solvent. However, in order to form the dye more efficiently into a J-aggregate, the dye is preferably added as a solution of a polar solvent, more preferably as an aqueous solution. Good to do.

Certain of the benzimidazolocarbocyanine dyes have low hydrophilicity, are poorly soluble in water, and cannot be added as such as an aqueous solution. In the case of such a poorly water-soluble dye, the pH is adjusted to the pKa of the dye.
In the following, the dye is converted into a water-soluble protonated product, and the dye-protonated aqueous solution may be added simultaneously with an alkaline aqueous solution having a concentration sufficient to make the pH equal to or higher than the pKa of the dye. The protonated dye adsorbs protons promptly, becomes poorly water-soluble again, and can be efficiently adsorbed to a more hydrophobic and covalently bonded silver halide surface.

The above-mentioned benzimidazolocarbocyanine dye is adsorbed on silver halide fine particles and acts as a growth inhibitor, but has no protective colloid itself. Therefore, it is generally used in combination with gelatin or a protective colloid polymer. Specifically, the gelatin or protective colloid polymer may be (1) contained in a water-soluble silver salt aqueous solution, (2) contained in a water-soluble halide aqueous solution, (3) contained in a dye solution, or may be contained in a plurality of these. May be. The dye itself may be contained in either or both of (1) an aqueous solution of a water-soluble silver salt and (2) an aqueous solution of a water-soluble halide. In this case, the gelatin or the protective colloid polymer may be contained in one or both of the above. It may be contained in both, or may be added as another aqueous solution.

The protective colloid polymer used in the present invention is gelatin and other natural polymers and synthetic polymers. In particular, it suppresses physical ripening (coalescing ripening and Ostwald ripening) of fine silver halide particles. A polymer having a high degree is preferably used. The specific example is shown below.

(1) A gelatin inhibitor having a high degree of physical inhibition A gelatin rich in adenine and guanine.

(2) Polyvinylpyrrolidone Homopolymer of vinylpyrrolidone, French Patent 203
1396. A copolymer of acrolein and pyrrolidone according to 1396.

(3) Polyvinyl alcohol Homopolymer of vinyl alcohol, US Pat.
14. An organic acid monoester of vinyl alcohol described in 14, a maleic acid ester described in U.S. Pat. No. 3,236,653, and a copolymer of polyvinyl alcohol and polyvinyl pyrrolidone described in U.S. Pat.

(4) Polymer having a thioether group US Pat. Nos. 3,615,624, 3,860,428 and 370
6564. A polymer having a thioether group.

(5) Polyvinylimidazole A homopolymer of polyvinylimidazole, a copolymer of polyvinylimidazole and polyvinylamide,
3-7561, German Patents 2011095 and 2012
970. A terpolymer of acrylamide, acrylic acid, and vinylimidazole according to 970.

(6) Polyethyleneimine

(7) Acetal polymer: water-soluble polyvinyl acetal described in US Pat. No. 2,358,836, polyvinyl acetal having a carboxyl group described in US Pat. No. 3,0038,879, and polymer described in British Patent 771,155.

(8) Amino polymer US Pat. Nos. 3,345,346, 3,706,504 and 435
0759, aminopolymers described in German Patent 2,138,872, British Patent 1,413,125, U.S. Pat.
6. A polymer having a quaternary amine according to 6, US Pat.
A polymer having an amino group and a carboxyl group described in 1818, and a polymer described in US Pat.

(9) Polyacrylamide polymer Acrylamide homopolymer, US Pat. No. 25414
74. A copolymer of polyacrylamide and imidized polyacrylamide as described in 74.
Copolymers of acryl amide and methacryl amide described above, partially aminated acryl amide polymers described in US Pat. No. 3,284,207, JP-B-45-1403
1. The substituted acrylamide polymers described in U.S. Pat. Nos. 3,713,834 and 3,746,548 and British Patent 788,343.

(10) Polymer having hydroxyquinoline A polymer having hydroxyquinoline described in US Pat. Nos. 4,030,929 and 4,152,161.

(11) Others Vinyl polymers having an azaindene group described in JP-A-59-8604, polyalkylene oxide derivatives described in US Pat. No. 2,976,150, polyvinylamine imide polymers described in US Pat. No. 4,022,623, US Pat.
20, 4089688, US Pat.
Polyvinylpyridine described in 84456, US Pat.
No. 0857, a vinyl polymer having an imidazole group, a vinyl polymer having a triazole group described in JP-B-60-658, and water-soluble polyalkyleneaminotriazoles described in Zeitschrift-Bisenshaftrich Photography, Vol. 45, p. 43 (1950).

In the silver halide fine grain emulsion, excess water-soluble salts are removed by a known method. From the viewpoint of avoiding desorption of the dye adsorbed on the fine grains, ultrafiltration is particularly useful in the present invention. The specific device is described in, for example, JP-A-2-172816.

Benzimidazolocarboxy of the general formula [1]
The anine dye will be described in more detail. General formula [1]
Medium, R¹¹, R¹²Represents a substituted or unsubstituted alkyl group
You. Examples of the substituted alkyl group include R¹³, R¹⁴Out
And substituted alkyl groups. R ¹¹, R¹²Few of
At least one is an alkoxyalkyl group (having 2 to 2 carbon atoms)
20, preferably 2 to 8, more preferably 2 to 5
You. Specifically, methoxymethyl group, methoxypropyl
Group, ethoxymethyl group, ethoxyethyl group, etc.)
And at least one is preferably selected from the group consisting of
It is a toxic ethyl group. Also R¹¹, R¹²While remaining
Is preferably a methyl group or an ethyl group.

R ¹³ and R ^{14 each} represent a substituted or unsubstituted alkyl group, at least one of which is preferably a sulfoalkyl group having 1 to 7 carbon atoms, more preferably 1 to 4 carbon atoms. The remaining one of R ¹³ and R ¹⁴ has 1 to 18, preferably 1 to 7, more preferably 1 to 7 carbon atoms.
To 4 substituted alkyl groups or unsubstituted alkyl groups (methyl, ethyl, propyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl, etc.). Examples of the substituted alkyl group include a fluorine-substituted alkyl group (2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3 , 3,3-pentafluoropropyl group, etc.), hydroxyalkyl group (hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, etc.), aralkyl group (benzyl, 2-phenylethyl, etc.), carboxyalkyl group (carboxymethyl, -Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, etc.), an alkoxyalkyl group (2-methoxyethyl, 2
-(2-methoxyethoxy) ethyl, etc.), sulfoalkyl group (2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- (3-sulfopropoxy) ethyl, 2-hydroxy-3-sulfopropyl , 3-sulfopropoxyethoxyethyl, etc.) sulfatoalkyl groups (3-sulfatopropyl, 4-sulfatobutyl, etc.), hetero-substituted alkyl groups ((2-pyrrolidin-2-one-1-yl) ethyl, tetrahydrofur Furyl, 2-morpholinoethyl, etc.), 2-acetoxyethyl group, carboxymethoxymethyl group, 2-methanesulfonylaminoethyl group, and allyl group.

X ¹¹ , X ¹² , X ¹³ and X ¹⁴ may be the same or different, and each represents a hydrogen atom, a halogen atom (such as chlorine, bromine or fluorine), a cyano group, or a halogen-substituted alkyl group (trifluoromethyl). , 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,3
3-tetrafluoropropyl, etc.), and X
^At least one of ¹¹ and X ¹³ is preferably a hydrogen atom, and X ¹² and X ¹⁴ are preferably any of a cyano group, a haloalkyl group and a halogen atom. Z represents an ion necessary for neutralizing the charge, and n is 1 or 2. In addition, n is 1 when forming an intramolecular salt. Specific examples of the substituent in the compound of the general formula [1] are shown in Table 1, but the present invention is not limited to these compounds.

[0057]

[Table 1]

The benzimidazolocarbocyanine dye of the present invention represented by the general formula [1] is adsorbed on a silver halide surface to form a J-aggregate, and accordingly, 540 to 55.
Forming a sharp J-band absorption in the 0 nm wavelength range,
Thereby, the intensifying screen light emission can be efficiently absorbed. Also, due to its high basicity, by treating at a low pH during fixing, protons are instantaneously added and the color is erased, and with the addition of protons, the planarity of the dye molecules is lost and the J-aggregate is destroyed and the silver halide surface Since it is easily desorbed, fixing of the silver halide fine particles to which the dye has been adsorbed is not suppressed.

In particular, when the emulsion used for the photosensitive emulsion layer is a high silver chloride emulsion, its spectral sensitivity rapidly decreases as it deviates from the spectrally sensitized wavelength range. That is, of the crossover light at the time of exposure of the photosensitive material, only the crossover light in the spectrally sensitized wavelength region contributes to the deterioration of the sharpness of the image, and the adverse effect of the crossover light in other wavelength regions on the sharpness is relatively small. Will be small in size.
Therefore, the crossover cut layer by J-band absorption having a sharp spectral absorption profile as in the present invention efficiently and effectively cuts crossover light harmful to sharpness with a smaller amount of dye. Things are possible.

The silver halide grains used in the photosensitive silver halide emulsion layer of the present invention are silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide, chlorobromoiodide. Any silver halide may be used, but silver halide grains having a high silver chloride content are preferred from the viewpoint of processing speed. As described above, the crossover cut layer of the present invention has a crossover cut layer having sharp J band absorption. Therefore, a high silver chloride emulsion having a sharp spectral sensitivity distribution is preferable because crossover cut can be performed more efficiently, and its halogen composition has a silver chloride content of preferably 80 mol% or more and 100 mol% or less, more preferably. Is from 90 mol% to 100 mol%, particularly preferably from 95% to 100 mol%.

The photosensitive silver halide grains may have a distribution or structure of a halogen composition in the grains, or may have a bonding structure. The photosensitive silver halide grains may be normal crystals containing no twin planes, parallel multiple twins containing two or more parallel twin planes, or non-parallel multiple twins containing two or more non-parallel twin planes. Good. The shape of the silver halide grains can be arbitrarily selected, but is preferably a tabular grain having a (111) plane as a main plane or a tabular grain having a (100) plane as a main plane. The size of the photosensitive silver halide grains can be arbitrarily selected from ultrafine grains having a sphere equivalent diameter of 0.01 μm or less to coarse grains having a sphere equivalent diameter of more than 10 μm, preferably from 0.1 μm to 3 μm. is there. The photosensitive silver halide of the present invention is preferably used in an amount of 0.1 g per m ² of the photosensitive material in terms of the amount of silver applied per side.
To 2.5 g, more preferably 0.1 g to 2.0 g, particularly preferably 0.3 g to 1.9 g.

The diaminostilbene type compound represented by the general formula [2] will be described in more detail. In the general formula [2], L ¹ ,
L ² is represented by -OR ¹ or ^{-NR 2 R 3, R 1,} R
² and R ³ each represent a hydrogen atom or an alkyl group, and may be the same or different. The alkyl group is a linear or branched alkyl group, and a hydrogen atom of the alkyl group may be substituted with another group. The group which can be substituted here is not particularly limited, but may be any of the above-mentioned general formula [A
Group] and [Group B], halogen atoms and the like. Examples of the group which can be substituted include those represented by the above general formula [Group A], [B
Group]. Also,
The alkyl group represented by R ¹ , R ² and R ³ preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The substituents of the general formulas [Group A] and [Group B] are generally known as hydrophilic groups, and particularly, the substituents of the general formula [Group A] are known as strongly hydrophilic groups.

In the present invention, the compound represented by the above general formula [2] has L ¹ and L ² satisfying at least one of the conditions (1) or (2). General formula [2]
Means that two triazine rings in the molecule are L ¹ and L, respectively.
Having ² has symmetry, and more specifically has symmetry belonging to the so-called C2h point group having two rotation axes outside the molecular plane at the center of the molecule (center point on the double bond).

Here, the condition (1) is a condition in which the four substituents L ¹ and L ² in the general formula [2] have a total of four or more substituents selected from the general formula [Group A]. When the condition (1) is satisfied, a total of six or more strongly hydrophilic groups in the molecule can be obtained by combining the number of the two sulfo groups of the benzene ring constituting the stilbene in the compound of the general formula [2]. It is equivalent to having. Here, the general formula [Group A]
Is preferably an even number, and the number is preferably 8 or less, more preferably 6 or less. As described above, if the number of the above-mentioned substituents is too large or too small, it is not preferable because the effect of preventing the residual color is reduced.

The condition (2) is a condition in which four substituents L ¹ and L ² in the general formula [2] are selected from a total of two [Group A] and two or more general formulas [Group B] ] Is a condition having a substituent selected from the above. When the condition (2) is satisfied, the compound represented by the general formula [2] is obtained by combining the number of the two sulfo groups on the benzene ring constituting stilbene with the following.
This corresponds to having a total of four strongly hydrophilic groups and a total of two or more hydrophilic groups in the molecule.

Here, the number of substituents selected from the general formula [Group B] is preferably an even number, and the number is preferably 10 or less, more preferably 4 or less. As described above, if the number of the above-mentioned substituents is too large or too small, it is not preferable because the effect of preventing the residual color is reduced.

Among the compounds represented by the general formula [2] according to the present invention, more preferable compounds are those described in the above condition (1).
Or, of (2), the condition (1) is satisfied. Under the above conditions (1) or (2), the compound represented by the general formula [2] having a strongly hydrophilic group has a structure known as a stilbene-based fluorescent whitening agent. However, for example, (I) described in JP-A-62-257154
-30) and (I-31), JP-A-4-249243.
Conventional optical brighteners having a total of four or more strongly hydrophilic substituents in the molecule, such as the compound (Comparative-1) described in the above publication, usually have two triazine rings in the molecule having an anilino group. There were features. Further, even with a conventional stilbene fluorescent brightener having a triazine ring having no anilino group, a specific compound satisfying any one of the above conditions (1) and (2) has not been known.

The stilbene compound represented by the general formula [2] of the present invention, which satisfies either the condition (1) or the condition (2), is characterized in that the triazine ring has an anilino group like the substituents L ¹ and L ^2. Having a feature of having a strong hydrophilic group without having any of the above, and having a symmetric structure as described above, which is different from the fluorescent brightener described in JP-A-4-249243.

In the compound of the general formula [2] in the present invention, the substituents L ¹ and L ² have the above-mentioned characteristics, and specific examples of L ¹ and L ² include a methoxy group,
Ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentyloxy, hexyloxy, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, 2- Hydroxyethoxy group, 3-hydroxypropoxy group, 4-hydroxybutoxy group, 2-
Hydroxyethylamino group, 3-hydroxypropylamino group, 4-hydroxybutylamino group, 2-hydroxyethylethylamino group, 3-hydroxypropylpropylamino group, 4-hydroxybutylbutylamino group,
Dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, di2-hydroxyethylamino group, di3-hydroxypropylamino group, dihydroxybutylamino group, 2-sulfoethoxy group A 3-sulfopropoxy group, a 4-sulfobutoxy group, a 2-sulfoethylamino group, a 3-sulfopropylamino group, a 4-sulfobutylamino group, a di-2-sulfoethylamino group, a di-3-sulfopropylamino group, Di-4-sulfobutylamino group,
2-sulfoethylmethylamino group, 3-sulfopropylmethylamino group, 4-sulfobutylmethylamino group, 2
-Sulfoethylethylamino group, 3-sulfopropylethylamino group, 4-sulfobutylethylamino group, 2-
Carboxyethoxy group, 3-carboxypropoxy group,
4-carboxybutoxy group, 2-carboxyethylamino group, 3-carboxypropylamino group, 4-carboxybutylamino group, di-2-carboxyethylamino group,
Di-3-carboxypropylamino group, di-4-carboxybutylamino group, 2-carboxyethylmethylamino group, 3-carboxypropylmethylamino group, 4-carboxybutylmethylamino group, 2-carboxyethylethylamino group, 3- Carboxypropylethylamino group, 4-carboxybutylethylamino group, 2-sulfoethoxy group, 3-sulfoxypropoxy group, 4-sulfoxybutoxy group, 2-sulfoxyethylamino group, 3-
A sulfoxypropylamino group, a 4-sulfoxybutylamino group, a di-2-sulfoxyethylamino group, a di3-sulfoxypropylamino group, a di-4-sulfoxybutylamino group, a 2-sulfoxyethylmethylamino group, 3-sulfoxypropylmethylamino group, 4-sulfoxybutylmethylamino group, 2-sulfoxyethylethylamino group, 3-sulfoxypropylethylamino group, 4-sulfoxybutylethylamino group, trimethylammoniomethylamino Group, trimethylammonioethylamino group,
Trimethylammoniopropylamino group, triethylammoniomethylamino group, triethylammonioethylamino group, triethylammoniopropylamino group and the like, more preferably, methoxy group, ethoxy group, 2-hydroxyethoxy group, 2- Hydroxyethylamino, 2-sulfoethylamino, di-2-sulfoethylamino, 2-carboxyethylamino, di-2-
Examples thereof include a carboxyethylamino group and a di-2-hydroxyethylamino group.

The preferred hydrophilicity of the compound of the general formula [2] in the present invention is that the log P value is -30 to -4, more preferably -18 to -7. Here, the log P value represents a value defined by a logarithmic value of a distribution ratio P (= [concentration in octanol] / [concentration in water]) of the compound in a binary system of octanol / water. If the logP value is -4 or more, crystallization of the processing solution during storage at low temperature becomes remarkable, and the reason is not clear.

The compound of the general formula [2] in the present invention
The material has a diffusion coefficient in the gelatin film under various processing conditions.
A large number is desirable. For example, in an aqueous solution of pH5
Diffusion coefficient at 10 × 109cm^Two/ Sec. More than
Preferably, 20 × 109cm ^Two/ Sec. Above is better
Good. In an aqueous solution of pH 10, 20 × 1
09cm^Two/ Sec. More preferably, 50 × 109c
m^Two/ Sec. The above is more preferable. The diffusion coefficient is
Molecules of the compound in the aqueous solution of the
The transmission and diffusion into the water using a spectrophotometer
It is possible to measure by
rnal of Polymer Science, V
ol. 30, 2075 (1985).
You.

The diaminostilbene compound of the general formula [2] used in the present invention has a specific structure in which L ¹ and L ² are represented by the atomic groups shown in Tables 2 to 7. However, the present invention is not limited to these.

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

[Table 4]

[0076]

[Table 5]

[0077]

[Table 6]

[0078]

[Table 7]

When the diaminostilbene type compound of the present invention represented by the general formula [2] is contained in a processing solution, the residual color of the photographic material after processing can be improved. The diaminostilbene type compound can be contained in any of the processing solutions in each of the development, fixing, and washing steps of the processing step.
It is preferable to add to the previous treatment bath as much as possible,
In particular, it is preferable to use it by adding it to a developing solution, and more preferably to include it in a processing solution of a plurality of steps. The concentration of the diaminostilbene-type compound in the processing solution is 5 × 10 ⁻⁵ to 1 × 10 ⁻² mol / L in the running solution, and more preferably 1 × 10 ^{−4 to} 5 × 10 ⁻³ mol / L. And the concentration in the replenisher is preferably the concentration required to keep the set concentration in the running solution constant, specifically 1.5 × 10 ^{−4 to} 1.5 × 10 ⁻² mol / l.

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention.
9 described in the following applicable places can be used.

(1) Silver halide emulsion and method for preparing the same: From page 8, lower right column, lower line 6, page 10 to upper right column, line 12, line 8. (2) Chemical sensitization method, page 10, upper right column, line 13 to lower left column, line 16; (3) Antifoggants and stabilizers, page 17, lower left column, line 17 to page 11, upper left column, line 7, and page 3, lower left column, line 2, page 4 lower left column. (4) Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. (5) Surfactant and antistatic agent, page 11, upper left column, line 14 to page 12, upper left column, line 9. (6) Matting agent, slip agent, and plasticizer: page 12, upper left column, line 10 to upper right column, line 10 and page 14, lower left column, line 10 to lower right column, line 1. (7) hydrophilic colloid, page 12, upper right column, line 11 to lower left column, line 16; (8) Hardener page 12, lower left column, line 17 to page 13, upper right column, line 6 (9) Support: page 13, upper right column, lines 7 to 20. (10) Dyes and mordants, page 13, lower left column, line 1 to page 14, lower left column, line 9.

Any layer of the silver halide photographic light-sensitive material of the present invention may contain a polymer latex obtained by polymerizing a monomer which is hardly soluble in water. The monomer is preferably an acrylate compound, more preferably both an acrylate compound and a methacrylate compound. The particle size of the polymer latex is preferably 300 nm or less. The polymer latex is preferably polymerized in the presence of a water-soluble polymer and / or a surfactant.

At least one of the monomers forming the polymer latex has a solubility in water at 25 ° C. of not more than 0.025% by weight, preferably 0.025% by weight.
15% by weight or less. The solubility of the monomer forming the polymer latex in water at 25 ° C. can be measured, for example, by the method described in New Experimental Chemistry Course Basic Operation 1 (Maruzen Chemical, 1975).

As the surfactant used in the polymerization of the polymer latex, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used. Preferred are anionic surfactants and / or nonionic surfactants, and particularly preferred are anionic surfactants. As the water-soluble polymer used in the polymerization of the polymer latex, any of a synthetic water-soluble polymer and a natural water-soluble polymer is preferably used.

Among the above synthetic water-soluble polymers and natural water-soluble polymers, those having a nonionic group in the molecule, those having an anionic group, those having a cationic group, those having a nonionic group and an anionic group ,
Any of those having a nonionic group and a cationic group, those having an anionic group and a cationic group are preferably used, and particularly preferably those having an anionic group and / or having a nonionic group and an anionic group. Things are used.

The water-soluble polymer is water at 20 ° C.
It is sufficient to dissolve 0.05 g or more per 0 g, and preferably 0.1 g or more. The polymer latex can be easily produced by various methods. For example, there is an emulsion polymerization method, a method of redispersing a polymer obtained by solution polymerization, bulk polymerization, or the like.

Regarding the polymer latex and a method for synthesizing the same, US Pat. No. 2,852,386 and US Pat.
No. 3,457, No. 3,411,911, No. 3,41
Nos. 1,912 and 4,197,127,
No. 5331, JP-A-60-18540 and JP-A-51-13.
No. 0217, No. 58-137831, No. 55-502
No. 40 and the like. The average particle size of the polymer latex is preferably from 0.5 to 250 nm, more preferably from 30 to 250 nm. The particle size of the polymer latex can be measured by an electron micrograph, a soap droplet method, a light scattering method, a centrifugal sedimentation method and the like described in “Chemistry of Polymer Latex” (Polymer Publishing Association, 1973).

The total molecular weight of the polymer latex is preferably from 1,000 to 1,000,000, more preferably from 20 to 100,000.
00 to 500,000. The polymer latex can be contained in the photographic component layer as it is or after being dispersed in water. The polymer latex may be added to any layer of the silver halide photographic light-sensitive material of the present invention, or may be added only to one of the silver halide emulsion layer and another hydrophilic colloid layer. It is preferably added to both, more preferably to both the silver halide emulsion layer and the hydrophilic colloid layer furthest from the support.

The amount of the polymer latex added is preferably 5 to 70% by weight based on the amount of the binder in the photographic constituent layer.
Is added within the range. When the polymer latex is added to both the emulsion layer and the protective layer, the ratio of the added amount of the protective layer / the added amount of the emulsion layer is preferably 0.3 to 0.4.

The silver halide photographic light-sensitive material of the present invention may contain colloidal silica in the silver halide emulsion layer. The colloidal silica is mainly composed of silicon dioxide,
It may contain small amounts of other components such as alumina and sodium aluminate, and may contain inorganic or organic salts as stabilizers. The average particle size of the colloidal silica is preferably 0.005 to 1 μm, and more preferably 0.005 to 0.5 μm.

These colloidal silicas are known and can be easily produced by known methods. Colloidal silica is also commercially available. I. Du
Ludox AM, Ludox AS, Ludox L made by Pont de Neouvs & Co (USA)
S, Ludox TM, Ludox HS, etc., Snowtex 20 and Snowtex 3 manufactured by Nissan Chemical Industries, Ltd.
0, Snowtex C, Snowtex O, etc., Mons
Syston C-3 manufactured by anto Co (USA)
0, Syston ZO, Nalco Chem
Nalcoag-1060, Nalcoag-
These are readily available under trade names such as ID 21-64. The amount of colloidal silica added is preferably large as long as the photographic performance is not adversely affected, but the upper limit is limited in relation to the photographic performance. When gelatin is used as a binder, the amount of colloidal silica is preferably 0.01 to 2.0, more preferably 0.05 to 1.0, and particularly preferably 0.1 to 2.0 in terms of dry weight of gelatin per 1 gelatin. 0
5 to 0.5.

When the colloidal silica is added to the emulsion, a solution appropriately diluted with water or a hydrophilic solvent may be added. The timing of addition to the emulsion is not particularly limited. It is good to add to the step.

The silver halide photographic light-sensitive material of the present invention may contain a polyhydric alcohol in the silver halide emulsion layer. The amount of the polyhydric alcohol to be added is preferably 1.0 × 10 ^{−3 to} 5.0 × 10 ⁻¹ mol, more preferably 5.0 × 10 ^{−2 to} 2.0 × 10 ⁻ mol per mol of silver. ¹ mole. As the polyhydric alcohol, a hydroxyl group in a molecule is 2-1.
An alcohol containing 2 to 2 carbon atoms, in which the hydroxyl group is not conjugated to the hydroxyl group by a conjugated chain, that is, an oxidized form is not preferable, and the melting point is 50 to 300
° C is preferred.

The silver halide photographic light-sensitive material of the present invention may contain a dye dispersed in solid fine particles in the hydrophilic colloid layer. The solid fine particle dispersion of the dye will be described in detail. Examples of the dye include known dyes and pigments, for example, “Dye Handbook” (pages 315 to 1109, edited by The Society of Synthetic Organic Chemistry, 1970) and “Color Material Engineering Handbook” (pages 225 to 417, Color Material Association). Hen, 19
1989) may be used, but a dye represented by the following formula (FA) is preferably used.

Formula (FA) D- (X) _{y In} Formula (FA), D represents a compound having a chromophore, and X represents a dissociable proton or a dissociative proton bonded to D directly or via a divalent linking group. Represents a group having a neutral proton, and y is 1
Represents an integer of to 7.

The compound having a chromophore represented by D can be selected from many well-known dye compounds. Examples of these compounds include oxonol dyes, merocyanine dyes, cyanine dyes, arylidene dyes, azomethine dyes, triphenylmethane dyes, azo dyes, anthraquinone dyes, and indoaniline dyes.

The dissociable proton represented by X or a group having a dissociable proton is in a non-dissociated state when the compound represented by the formula (FA) is added to the silver halide photographic material of the present invention. The compound has the property of making the compound of formula (FA) substantially water-insoluble, and has the property of dissociating to make the compound of formula (FA) substantially water-soluble in the step of developing the material. Have. Examples of these groups include a carboxylic acid group, a sulfonamide group, an arylsulfamoyl group, a sulfonylcarbamoyl group, a carbonylsulfamoyl group, an enol group of an oxonol dye, and a phenolic hydroxyl group. Among the compounds represented by the formula (FA), more preferred are compounds represented by the following formula (FA1):
It is a compound represented by (FA2) or (FA3), particularly preferably a compound of (FA1).

[0098] Formula _{(FA1) A 1 = L 1} - (L 2 = L 3) m -Q formula _{(FA2) A 1 = L 1} - (L 2 = L 3) n -A 2 Formula (FA3 ) a ₁ = (L in ₁ -L _{2) n} = B ₁ equation, a ₁ and a ₂ each represent an acidic nucleus. B ₁ represents a basic nucleus. Q represents an aryl group or a heterocyclic group,
L ₁ , L ₂ and L ₃ each represent a methine group. m is
0, 1, and 2, and n and p represent 0, 1, 2, and 3, respectively. However, the compounds of formulas (FA1) to (FA3)
In the molecule, a carboxylic acid group, a sulfonamide group, an arylsulfamoyl group, a sulfonylcarbamoyl group, a carbonylsulfamoyl group, an enol group of an oxonol dye, and at least one group selected from the group consisting of a phenolic hydroxyl group. And no other water-soluble groups (for example, sulfonic acid groups and phosphoric acid groups).

The acidic nucleus represented by A ₁ and A ₂ is preferably a cyclic ketomethylene compound or a compound having a methylene group sandwiched between electron-withdrawing groups. Examples of cyclic ketomethylene compounds include 2-pyrazolin-5-one,
Rhodanin, hydantoin, thiohydantoin, 2,4-
Oxazolidinedione, isoxazolone, barbituric acid, thiobarbituric acid, indandione, dioxopyrazolopyridine, hydroxypyridone, pyrazolidinedione, and 2,5-dihydrofuran-2-one. These may have a substituent. A compound having a methylene group sandwiched between electron-withdrawing groups can be represented as Z ₁ CH ₂ Z ₂ . Here, Z ₁ and Z ₂ are —CN, —SO ₂ R ₁ , —COR ₁ ,
_{-COOR 2, -CONHR 2, -SO 2} NHR 2, -
C [= C (CN) _2] R _1, or -C [= C (C
N) ₂ ] NHR ₁ . R ₁ represents an alkyl group, an aryl group, or a heterocyclic group, R ₂ represents a hydrogen atom, a group represented by R ₁ , and each of these may have a substituent.

Examples of the basic nucleus represented by B ₁ include pyridine, quinoline, indolenine, oxazole, imidazole, thiazole, benzoxazole, benzimidazole, benzothiazole, oxazoline, naphthoxazole and pyrrole. . Each of these may have a substituent.

Examples of the aryl group represented by Q include a phenyl group and a naphthyl group. Each of these may have a substituent. Examples of the heterocyclic group represented by Q include pyrrole, indole, furan, thiophene, imidazole, pyrazole, indolizine,
Quinoline, carbazole, phenothiazine, phenoxazine, indoline, thiazole, pyridine, pyridazine, thiadiazine, pyran, thiopyran, oxadiazole, benzoquinoline, thiadiazole, pyrrolothiazole, pyrrolopyridazine, tetrazole, oxazole, coumarin, and cumarone. . Each of these may have a substituent.

The methine groups represented by L ₁ , L ₂ and L ₃ may have a substituent, and the substituents are connected to each other to form a 5- or 6-membered ring (for example, cyclopentene, cyclohexene). It may be formed.

The substituent which each of the above-mentioned groups may have is a substituent which substantially dissolves the compound of the formula (FA) and the compounds of the formulas (FA1) to (FA3) in water at pH 5 to pH 7. If not, there is no particular limitation. For example, the following substituents can be mentioned. Carboxylic acid group, having 1 to 1 carbon atoms
0 sulfonamide groups (eg, methanesulfonamide, benzenesulfonamide, butanesulfonamide,
n-octanesulfonamide), a sulfamoyl group having 0 to 10 carbon atoms (eg, unsubstituted sulfamoyl, methylsulfamoyl, phenylsulfamoyl, butylsulfamoyl), a sulfonylcarbamoyl group having 2 to 10 carbon atoms (eg, Methanesulfonylcarbamoyl, propanesulfonylcarbamoyl, benzenesulfonylcarbamoyl), acylsulfamoyl groups having 1 to 10 carbon atoms (eg, acetylsulfamoyl, propionylsulfamoyl, pivaloylsulfamoyl, benzoylsulfamoyl), A chain or cyclic alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, isopropyl, butyl, hexyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxy Chill, benzyl, Feninechiru,
4-carboxybenzyl, 2-diethylaminoethyl), an alkenyl group having 2 to 8 carbon atoms (for example, vinyl,
Allyl), an alkoxy group having 1 to 8 carbon atoms (eg, methoxy, ethoxy, butoxy), a halogen atom (eg,
F, Cl, Br), an amino group having 0 to 10 carbon atoms (eg, unsubstituted amino, dimethylamino, diethylamino, carboxyethylamino), an alkoxycarbonyl group having 2 to 10 carbon atoms (eg, methoxycarbonyl),
An amide group having 1 to 10 carbon atoms (for example, acetylamino,
Benzamide), a carbamoyl group having 1 to 10 carbon atoms (eg, unsubstituted carbamoyl, methylcarbamoyl, ethylcarbamoyl), an aryl group having 6 to 10 carbon atoms (eg, phenyl, naphthyl, 4-carboxyphenyl,
3-carboxyphenyl, 3,5-dicarboxyphenyl, 4-methanesulfonamidophenyl, 4-butanesulfonamidophenyl), an aryloxy group having 6 to 10 carbon atoms (for example, phenoxy, 4-carboxyphenoxy, 3-methylphenoxy) , Naphthoxy), having 1 to 1 carbon atoms
8 alkylthio groups (e.g., methylthio, ethylthio, octylthio), C6-C10 arylthio groups (e.g., phenylthio, naphthylthio), 1-carbon atoms
10 acyl groups (for example, acetyl, benzoyl, propanoyl), and a sulfonyl group having 1 to 10 carbon atoms (for example,
Methanesulfonyl, benzenesulfonyl), having 1 to 1 carbon atoms
10 ureido groups (for example, ureido, methylureide), urethane groups having 2 to 10 carbon atoms (for example, methoxycarbonylamino, ethoxycarbonylamino), cyano group, hydroxyl group, nitro group, heterocyclic group (for example, 5-carboxy) Examples include a benzoxazole ring, a pyridine ring, a sulfolane ring, a pyrrole ring, a pyrrolidine ring, a morpholine ring, a piperazine ring, a pyrimidine ring, and a furan ring.

Preferably, dye-A represented by the following general formula
It is. Dye-A

[0105]

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In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group. Group, acylamino group, ureido group, amino group, acyl group, alkoxy group, aryloxy group, hydroxy group, carboxy group, cyano group, sulfamoyl group, sulfonamide group, and B is a 5- or 6-membered oxygen-containing heterocyclic ring Group or 6
L _{1 to} L ₃ each represents a methine group; n represents 0 or 1; and the dye contains at least one of a carboxyl group, a sulfonamide group, and a sulfamoyl group. .

Hereinafter, specific examples of the solid disperse dye which can be used in the present invention will be described.

[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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[0113]

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[0114]

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In addition, specific examples of the formula (FA1) include (II-2) to (II-24) described in JP-A-7-152112.
As a specific example of (FA2).
(III-5) to (III-18) described in JP-A-7-152112 are described as specific examples of (FA3).
(IV-7).

In addition, dyes which can be used in the present invention include solid fine particle dispersed dyes which are decolorized at the time of treatment, such as cyanine dyes, pyrylium dyes and aminium dyes described in JP-A-3-138640. As dyes not used, cyanine dyes having a carboxyl group described in Japanese Patent Application No. 6-279297, and Japanese Patent Application No. 7-54.
No. 026, a cyanine dye containing no acidic group, a lake type cyanine dye described in JP-A-7-135118, a cyanine dye described in JP-A-1-266536,
Solid fine particle dispersions of a horopora type cyanine dye described in 136038, a pyrilium dye described in JP-A-62-299959, a polymer type cyanine dye described in Japanese Patent Application No. 6-45473, and an oxonol dye described in JP-A-2-282244. And light scattering particles described in JP-A-63-131135, Yb3 + compounds described in Japanese Patent Application No. 7-151380, and ITO powders described in JP-A-7-113072. Further, dyes represented by formulas (F1) and (F2) described in Japanese Patent Application No. 7-350753, and specifically, compounds F35 to F112 described in the same publication are also preferably used.

The dyes used in the present invention are described in International Patent WO
88/04794, European Patent EP 027472
Nos. 3A1, 276566, 299435, JP-A-52-92716, 55-155350, and 5
Nos. 5-155351, 61-205934, 48
-68623, U.S. Pat.
No. 6897, No. 3746539, No. 3933798
Nos. 4,130,429 and 4,408,411, JP-A-2-282244, JP-A-3-7931, and JP-A-3-167.
No. 546, JP-A-1-266536 and 3-1360.
No. 38, No. 3-226736, No. 3-138640
No. 3-21542, Japanese Patent Application No. 6-227982
Nos. 6-227983, 6-279297, 7-54026, 7-101968, and 7-13
5118, JP-A-2-282244, JP-A-7-1
No. 13072, JP-A-7-53946 and the like, or a method described in the gazette or a method according to the method.

The dye of the present invention may be non-eluting (the dye or a reaction product of the dye and the processing solution does not elute during the development processing) or may be eluting. As long as no harmful absorption remains after the development processing, a non-eluting compound that can be used in a development processing system with a small amount of replenisher and that can cope with rapid processing is preferable.

The above-mentioned method for converting the dye into solid fine particles is carried out by using known fine means (for example, ball mill, vibrating ball mill, planetary ball mill, sand mill, colloid mill, jet mill, roller mill) in the presence of a dispersing agent. Can be dispersed mechanically. As the dispersing aid to be used, the above-mentioned polymer compounds are used, and if necessary, two or more kinds may be used in combination. At the same time, a known anionic / nonionic / cationic surfactant or a polymer may be used in combination, but it is preferable to use only the above-mentioned polymer compound. The dispersing aid is generally mixed with the dye powder or wet cake before dispersion and sent to a dispersing machine as a slurry.However, in a state where the dispersion aid is mixed with the dye in advance, heat treatment or treatment with a solvent is performed. It may be a dye powder or a wet cake. During the dispersion, as the fine particles are formed, they can be added to the dispersion. Further, it can be added to the dispersion liquid for stabilizing the physical properties after dispersion. In any case, a solvent (eg, water / alcohol) is commonly used. Before, during or after dispersion, the pH may be controlled with a suitable pH adjuster. In addition to mechanical dispersing, fine particles may be formed by dissolving in a solvent by controlling the pH and then changing the pH in the presence of a dispersing agent. At this time,
An organic solvent may be used as a solvent used for dissolution, and the organic solvent is usually removed after the completion of the micronization. The prepared dispersion may be stored with stirring or in a highly viscous state by a hydrophilic colloid (for example, gelatinized to a jelly state) in order to suppress sedimentation of fine particles during storage.
And can also be saved. It is preferable to add a preservative for the purpose of preventing propagation of various bacteria during storage.

The solid fine particles of the dye thus prepared are:
Average particle diameter 0.005 μm to 10 μm, preferably,
0.01 μm to 3 μm, and in some cases 0.05
It is preferably about 0.5 μm.

The solid fine particle dispersion of the present invention may be added to any layer (back layer, emulsion layer, protective layer, undercoat layer, intermediate layer, etc.) in the hydrophilic colloid layer of the photosensitive material.
Preferably, it is used for a hydrophilic colloid layer other than the emulsion layer. Two or more dyes may be used in the same layer, or one type of dye may be contained in a plurality of layers. The hydrophilic colloid is not particularly limited, but usually gelatin is preferred. The amount of the dye of the present invention used as a solid content depends on the required absorbance and the extinction coefficient of the dispersion.
It is used by being applied in the range of 001 to 5 g / m ² . Preferably, it is used at 0.005 to ² g / m ² , more preferably 0.005 to 1 g / m ² . At this time, when the photosensitive material is coated on both sides, it can be added to only one side. In addition to the solid fine particle dispersion of the dye of the present invention, known dyes can be used in the light-sensitive material of the present invention as needed. Examples of such dyes are described on page 17 of JP-A-2-103536.

The method for developing a light-sensitive material of the present invention is not particularly limited as a photographic light-sensitive material. It can be preferably used for a laser light source photographic material, a medical direct imaging X-ray material, a medical indirect imaging X-ray material, a CRT image recording material, and a microfilm. X-ray material for direct shooting. Hereinafter, the present invention will be described in detail with reference to examples.

[0123]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. (1) Preparation of Fine Particle Emulsion Preparation of Fine Particle Emulsion (1-1) (Invention) In this example, the pipeline mixer shown in FIG. 1 is used. The mixing container of the pipeline mixer has an internal volume of 8 m
This is a cylindrical closed container having a stirring blade that can rotate at high speed in the opposite direction to the top and bottom inside. A 0.5N silver nitrate aqueous solution and a 0.5N sodium chloride aqueous solution are added to the mixing vessel at 25 ml / min and 30 ml / min, respectively, and simultaneously, a benzimidazolocarbocyanine dye (dye-1)

[0124]

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An aqueous solution of the protonated product (0.002 mol / l, pH 5) and an aqueous solution of sodium hydroxide at a concentration sufficient to completely neutralize the solution were added at 200 ml / min. In the aqueous solution of the dye protonated product, low molecular weight gelatin having an average molecular weight of 30,000 or less as a protective colloid,
15 g per liter of aqueous solution is dissolved and contained.

The above solution was vigorously stirred in the mixing vessel at a stirring rotation speed of 2,000 rpm and rapidly and uniformly mixed to obtain an emulsion of silver halide fine particles having a dye adsorbed on the surface. The emulsion is retained in the mixing container for about 1 second, immediately discharged out of the container, introduced directly into an ultrafiltration membrane, to remove excess water-soluble salts and to have a concentration suitable for preparing a coating solution. Concentrated. The concentrated emulsion was redispersed in an aqueous gelatin solution to obtain a silver halide fine grain emulsion having a silver amount of 45 g per 1000 g of the emulsion. The fine particle size was 0.018 μm.

Preparation of Fine Particle Emulsion (1-2) (Invention) In the same mixing vessel used for the preparation of the above (1-1),
The stirring rotation speed was set to 2,000 rpm, and a 0.1 N aqueous solution of silver nitrate and a 0.1 N aqueous solution of sodium hydroxide were added thereto at 125 ml / min and 150 ml / min, respectively. Of low molecular weight gelatin dissolved in 25 g per liter of aqueous solution. The emulsion stays in the mixing container for about 2 seconds and is immediately discharged out of the container to obtain benzimidazole carbocyanine (dye-2).

[0128]

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Was added to a methanol solution of The concentration of the dye methanol solution is 0.0015 mol / L,
The volume was 3 liters, and the emulsion was continued to be added thereto for 10 minutes. The dye was adsorbed on the surface of the silver halide fine particles in the methanol solution, gelatin was aggregated, and the emulsion precipitated. After allowing the emulsion to settle completely, the supernatant was decanted to remove excess water-soluble salts and concentrated. The concentrated emulsion was redispersed in an aqueous gelatin solution, resulting in an emulsion of 1000
A silver halide fine grain emulsion having a silver amount of 45 g per g was obtained.
The particle size was 0.020 μm.

Preparation of Fine Particle Emulsion (1-3) (Invention) A stirring device similar to that used in the preparation of the above (1-1) was used.
However, the one with an internal volume of 2 ml was used, and the stirring rotation speed was 20
00 rpm. Here, 0.5N silver nitrate aqueous solution,
0.5N aqueous sodium chloride solution was added at 25ml /
Min and 30 ml / min, and simultaneously an aqueous protective colloid solution was added at 50 ml / min. The aqueous sodium chloride solution contains a benzimidazole carbocyanine dye (dye-3)

[0131]

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0.02 mol per liter of the solution is dissolved therein, and the aqueous protective colloid solution further contains 50 g per liter of a solution of PVA (polyvinyl alcohol) having a degree of polymerization of 500 and a degree of fighting of 100%. . The emulsion stayed in the mixing container for about 1 second, was immediately discharged out of the container, and was introduced into the second stirring device as described above. Here, 0.1N potassium iodide aqueous solution
Added at 5 ml / min. Approximately 1 emulsion was placed in a second mixing vessel.
After standing for 2 seconds, the mixture was immediately discharged out of the container and introduced into an ultrafiltration membrane to remove excess water-soluble salts and concentrate the emulsion. The emulsion was redispersed in an aqueous gelatin solution to obtain a silver halide fine grain emulsion having a silver amount of 45 g per 1000 g of the emulsion. Fine particle size is 0.015μm
Met.

Preparation of Fine Particle Emulsion (1-4) (Comparative Example) A fine particle emulsion is prepared in the same manner as in the above (1-2). However, the aqueous halogen solution is a mixture of potassium bromide and potassium iodide so that the prepared fine particles have a halogen composition of silver iodobromide having a silver bromide / silver iodide ratio of 95/5. After the preparation, the emulsion was changed to Dye-4.

[0134]

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Was added to a methanol solution of The fine grain size of the resulting fine grain emulsion was 0.060 μm. Preparation of Fine Particle Emulsion (1-5) (Comparative Example) A fine particle emulsion is prepared in the same manner as in the above (1-4). However, the aqueous solution of halogen is an aqueous solution of potassium bromide, and after preparation, the emulsion is dye-5.

[0136]

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Was added to a methanol solution of The fine grain size of the resulting fine grain emulsion was 0.020 μm.

(2) Preparation of silver halide emulsion for photosensitive layer Preparation of silver chloride tabular emulsion (2-1) 1582 ml of an aqueous gelatin solution (gelatin-1) was placed in a reaction vessel.
(Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 19.5 g, 1N aqueous silver nitrate solution 7.
8 ml, pH 4.3) and 13 m aqueous sodium chloride solution (containing 10 g sodium chloride in 100 ml)
1 was added. Here, while maintaining the temperature at 40 ° C., Ag
-1 solution (containing 20 g of silver nitrate in 100 ml) and X-1
15.6 ml of the liquid (containing 7.05 g of sodium chloride in 100 ml) was added simultaneously at 62.4 ml / min.

After stirring for 3 minutes, 28.2 ml of the Ag-2 solution (containing 2 g of silver nitrate in 100 ml) and the X-2 solution (containing 1.4 g of potassium bromide in 100 ml) were simultaneously mixed at 80.6 ml / min. Was added. After stirring for 3 minutes, Ag-
Solution 1 and solution X-1 at 62.4 ml / min each.
8 ml was added simultaneously. After stirring for 2 minutes, 203 ml of an aqueous gelatin solution (13 g of gelatin-1 and 1.1 g of NaCl).
Containing 3 g, adjusted to pH 6.5 with 1N NaOH)
Was added to adjust the pCl to 1.75, the temperature was adjusted to 63 ° C., and aqueous hydrogen peroxide was added to 6 × 10 6 g of gelatin per 1 g of gelatin.
^-4 mol was added to adjust the pCl to 1.70, followed by aging for 3 minutes. Then, a silver chloride fine grain emulsion (average grain diameter 0.1 μm)
m) was added at 2.68 × 10 ⁻² mol / min for 20 minutes.

After completion of the addition, the mixture was aged for 40 minutes, and then a sedimentation agent was added to the mixture to adjust the temperature to 35 ° C. and to wash it by settling. An aqueous gelatin solution was added, and the pH was adjusted to 6.0 at a temperature of 60 ° C. As a result, the average diameter is 1.40 μm, the average thickness is 0.13 μm,
Silver chloride containing 0.44 mol% of bromine with respect to silver ｛1
A 00 ° tabular grain emulsion was obtained.

Preparation of silver bromide tabular emulsion (2-2) 6.52 g of potassium chloride and 11.6 g of low molecular weight gelatin (average molecular weight: 15,000) were placed in 1.11 liter of water, and the mixture was kept at 74 ° C. While stirring, 21.6 ml of an aqueous solution of silver nitrate (2.40 g of silver nitrate) and 38.5 ml of an aqueous solution of potassium bromide (5.9 g of potassium bromide) were added by a double jet method over 37 seconds.

Next, an aqueous gelatin solution (26 g of gelatin) was added, and then 104.1 ml of an aqueous silver nitrate solution (silver nitrate 1 g) was added.
1.5 g) was added over 11.5 minutes. Where 25
After adding 18 ml of an aqueous solution of ammonia at 10% for 10 minutes at the same temperature, 15% aqueous solution of acetic acid was added.
7 ml was added. Subsequently, an aqueous solution of silver nitrate (187.7 g of silver nitrate) and an aqueous solution of potassium bromide were added to pAg8.
While maintaining at 5, control double jet method 75
Added over minutes. At this time, the flow rate was accelerated at the end of the addition to be 3.2 times that at the start. After completion of addition, 2N
44 ml of aqueous potassium thiocyanate solution were added.

After completion of the addition, the mixture was aged for 5 minutes, and a sedimentation agent was added to the mixture to adjust the temperature to 35 ° C. and to wash it by settling. Gelatin 63.
3 g, 2.9 g of phenoxyethanol and 1.4 g of sodium polystyrenesulfonate as a thickener were added.
The pH was adjusted to 6.05 and pAg to 8.70. As a result, a pure silver bromide {111} tabular grain emulsion having an average diameter of 1.80 μm and an average thickness of 0.32 μm was obtained.

Chemical sensitization The emulsions (2-1) and (2-2) were chemically sensitized as follows. The emulsion was kept at a temperature of 56 ° C. while stirring, and the thiosulfonic acid compound-1 was first added.

[0145]

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3.1 × 10 ⁻⁵ mol / silver mol was added, and then 0.11 mol% of silver iodide fine particles having a diameter of 0.03 μm were added.
Add silver mole and add 0.036 mg of thiourea dioxide
/ Silver mole was added and held for 22 minutes to effect reduction sensitization. Next, 4-hydroxy-6-methyl-1,3,3
3a, 7-tetraazaindene (16.9 mg / silver mole) and the dispersion of dye-4 were used as a dye-4 in an amount of 476 m
g / silver mole, dye-6

[0147]

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Was added in an amount of 2.2 mg. Further, 0.64 g / mol of silver of calcium chloride was added, followed by 0.24 mg / mol of silver of sodium thiosulfate and selenium compound-1.

[0149]

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Was converted to 0.62 mg / silver mole and 1.5 parts of chloroauric acid.
mg / silver mole and potassium thiocyanate 72 mg / silver mole were added and aged for 58 minutes. Thereafter, sodium sulphite 21.1 mg / silver mole was added to further ripen, and 105 minutes after the addition of chloroauric acid, compound-1

[0151]

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Was added at a temperature of 35 ° C. after 4 minutes. Thus, the preparation of the silver halide emulsion for the photosensitive layer was completed.

(3) Preparation of Support Preparation of Support (3-1) A corona discharge was carried out on a biaxially stretched 175 μm thick blue-colored polyethylene terephthalate film.
The coating amount of the first undercoating liquid having the following composition is 4.9 ml /
m ² with a wire converter,
Dry at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. Dye-1 was used in the polyethylene terephthalate used.

[0154]

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Used was 0.04% by weight. First undercoat layer • Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158 ml • 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41 ml -Distilled water 801 ml The above latex solution contains an emulsifying dispersant-1.

[0156]

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Is contained in an amount of 0.04% based on the solid content of the latex.

Preparation of Support (3-2) Preparation of Dye Dispersion for Second Undercoat Layer Dye-2

[0159]

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Was subjected to a ball mill treatment by the method described in JP-A-63-197943. 434 ml of water and Trit
791 ml of a 6.7% aqueous solution of on-X200® surfactant was placed in a 2 liter ball mill. 20 g of Dye-2 were added to this solution. 400 ml (2 mm diameter) beads of zirconium oxide (ZrO ₂ ) were added, and the contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added. After defoaming, Zr is filtered
O ₂ beads were removed. Observation of the obtained dye dispersion showed that the particle size of the crushed dye was 0.05 to 1.15 μm.
m, with an average particle size of 0.3
It was 7 μm. Furthermore, the pigment particles having a size of 0.9 μm or more were removed by centrifugation. Thus, Dye Dispersion-1 was obtained.

Preparation of Support A support was prepared in the same manner as in the support (3-1), and a second undercoat layer having the following composition was coated on the first undercoat layer on both surfaces described above. Each side so that the amount described below,
Both surfaces were coated and dried at 155 ° C. by a wire bar coder method.・ Gelatin 80 mg / m ²・ Dye dispersion-1 (as dye solid content) 8 mg / m ²・ Coating aid-1 1.8 mg / m ²

[0162]

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Proxel 0.27 mg / m ² Matting agent (polymethyl methacrylate having an average particle size of 2.5 μm) 2.5 mg / m ²

(4) Preparation of Photographic Material Preparation of Coating Solution for Photosensitive Layer A coating solution for the photosensitive layer was prepared so that each component to be added to the emulsion had the following coating amount per one side of the support. 2,6-bis (hydroxyamino) -4-diethylamino - 1,3,5-triazine 1.7 mg / m ² · Dextran (average molecular weight 39000) 0.45 g / m Sodium ^{2-polystyrene} sulfonate 33 mg / m ² (Average molecular weight 600,000) (Including emulsion addition) Gelatin 1.1 g / m ² (Including emulsion addition) Hardener 1,2-bis (vinylsulfonylacetamide) ethane 55 mg / m ² Hydroquinone monosulfone Sodium acid 0.11 g / m ² · Dye-1 emulsion (as dye solids) 4.0 mg / m ² · Dye-3 emulsion (as dye solids) 4.0 mg / m ² Dye-3

[0165]

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Polymer latex-1 0.4 g / m ²

[0167]

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• Colloidal silica (Ludox AM from Du Pont) 0.6 g / m ² • Polyhydric alcohol 2,2-dimethyl-1,3-pentanediol 0.3 g / m ²

Preparation of Coating Solution for Surface Protective Layer A coating solution for the surface protective layer was prepared such that each component of the surface protective layer had the following coating amount.・ Gelatin 0.60 g / m ²・ Benzoisothiazolone 1.4 mg / m ²・ Sodium polyacrylate (average molecular weight 41000) 17 mg / m ²・ Additive-1 35 mg / m ²

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Additive-2 5.4 mg / m ²

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Additive-3 22.5 mg / m ²

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Additive-4 0.5 mg / m ²

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Matting agent-1 (average particle size: 3.7 μm) 72.5 mg / m ²

[0178]

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The coating solutions for the fine grain emulsion layer, photosensitive emulsion layer and surface protective layer prepared above were simultaneously coated on both sides of the support by the simultaneous extrusion method under the same conditions. The amount of gelatin in the emulsion layer and the amount of each chemical in the emulsion layer were adjusted so that the coating amount was constant. The silver coating amount of the fine grain emulsion layer and the photosensitive emulsion layer of each photographic material was 0.2 g / m 2 per side.
² and 1.75 g / m ² .

[0180]

[Table 8]

(5) Preparation of Developing Solution Preparation of Developing Solution (5-1) Preparation of Concentrated Developing Solution A concentrated developing solution containing sodium erythorbate having the following formulation as a developing agent was prepared. -Diethylenetriaminepentaacetic acid 8.0 g-Sodium sulfite 20.0 g-Sodium carbonate monohydrate 52.0 g-Potassium carbonate 55.0 g-Sodium erythorbate 60.0 g-4-hydroxymethyl-4-methyl-1-phenyl-3 -Pyrazolidone 13.2 g-3,3'-diphenyl-3,3'-dithiopropionic acid 1.44 g-diethylene glycol 50.0 g Add water to 1 liter or more to make 1 liter and p with sodium hydroxide.
Adjusted to H10.1.

Preparation of Development Replenisher The above concentrated developer was diluted 2-fold and used as a development replenisher.

Preparation of Developing Mother Solution 2 liters of the above concentrated developing solution was diluted to 4 liters with water, and a starter solution having the following composition was added in an amount of 55 ml per liter of diluted developing solution. A developing solution having a pH of 9.5 was used as a developing mother solution.

Starter liquid Potassium bromide 11.1 g Acetic acid 10.8 g Water was added to above to make 55 ml.

Preparation of Developer (5-2) A developer is prepared in the same manner as in the developer (5-1).
However, a diaminostilbene type compound (diaminostilbene type compound-1) is contained in the concentrated developer.

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Is dissolved and contained in an amount of 5 g per liter.

(6) Preparation of Fixing Solution Preparation of Fixing Solution (6-1) Preparation of Concentrated Fixing Solution A concentrated fixing solution having the following formulation was prepared. Water 500 ml Ethylenediaminetetraacetic acid dihydrate 0.05 g Sodium thiosulfate 200 g Sodium bisulfite 98.0 g Sodium hydroxide 2.9 g Adjust the pH to 5.2 with sodium hydroxide and add water. It was 1 liter.

Preparation of Fixing Replenisher The concentrated fixing solution was diluted 2-fold and used as a fixing replenisher. Preparation of fixing mother liquor Dilute 2000 ml of the above concentrated fixing solution with water to 4000 ml
And pH was 5.4.

Preparation of Fixing Solution (6-2) A fixing solution is prepared in the same manner as in the fixing solution (6-1).
However, a diaminostilbene type compound (diaminostilbene type compound-2) is contained in the concentrated fixing solution.

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Is dissolved and contained in an amount of 5 g per liter.

(7) Evaluation of Crossover Cut and Residual Color For the double-sided coated photographic material, a fluorescent intensifying screen was brought into close contact with only one emulsion layer, and a black paper was applied to the other side, followed by X-ray exposure. Sensitometry was performed. The screen used was an HGM screen manufactured by Fuji Photo Film Co., Ltd. The light-sensitive material exposed as described above was processed by an automatic processor. The automatic processor is an automatic processor CEPR manufactured by Fuji Photo Film Co., Ltd. with an improved drive system and an aperture ratio of 0.02.
Using the OS 30 and the developing mother liquor and the fixing mother liquor, processing was performed while replenishing the developing replenisher and the fixing replenisher with 50 ml per 1 m ² of the light-sensitive material.

Process Temperature Processing Time Developing 35 ° C about 8 seconds Fixing 35 ° C about 8 seconds Washing 25 ° C about 7 seconds Drying 55 ° C about 6 seconds

Either the exposed surface (front surface) or the unexposed surface (back surface) of the processed photosensitive material was removed, and a sensitometric curve was prepared. The sensitivity difference Δlog E was measured at the linear part between the foot and shoulder of one of the sensitometric curves, and the crossover% was evaluated by the following equation. Crossover% = 100 / (antilog (Δlo
gE) +1)

[0196]

[Table 9]

The residual color was evaluated on a scale of 1 to 5, with 5 being the best and 1 being the best.
Is the worst. Thus, the present invention has significantly reduced or virtually negligible residual color after processing, while significantly reducing crossover. That is, it is possible to achieve both crossover cut and residual color after processing at a high level that cannot be achieved by the conventional technology.

[0198]

According to the present invention, it is possible to significantly reduce the crossover and to reduce the residual color after the processing to a level which is extremely small or practically negligible. It can be compatible with the remaining color.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a schematic configuration of a stirring device used in Examples.

[Explanation of symbols]

 Reference Signs List 10 Stirring device 11, 12, 13 Liquid supply port 16 Liquid discharge port 19 Stirring tank 20 Seal plate 21, 22 Stirring blade 26 External magnet 28, 29 Motor

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/26 G03C 5/26

Claims (6)

[Claims] 1. A radiographic element comprising a transparent support and at least one coated on at least one side of the support.
A light-sensitive silver halide emulsion layer and at least one substantially light-insensitive silver halide emulsion layer coated between the support and the emulsion layer. Silver halide emulsion layer contains non-photosensitive silver halide fine particles having at least one spectral sensitizing dye adsorbed on the surface thereof,
At least one of the spectral sensitizing dyes is a benzimidazolocarbocyanine dye represented by the general formula [1], and the substantially light-insensitive silver halide emulsion layer has a responsivity of the radiographic element. A radiographic element absorbing light in the spectral region and having a crossover of less than 10%. General formula [1] In the general formula (1), R ^11, R ^12, R ^13, R ¹⁴ represents a substituted or unsubstituted alkyl group, at least one of R ^11, R ¹² represents an alkoxyalkyl group, the R ^13, R ¹⁴ At least one represents a sulfoalkyl group. X ¹¹ , X ¹² ,
X ¹³ and X ¹⁴ may be the same or different and each represent a hydrogen atom, a cyano group, a halogen-substituted alkyl group or a halogen atom, and at least one of X ¹¹ and X ¹³ represents a hydrogen atom. Z represents an ion necessary to balance the charge, n is 1 or 2, and n = 1 when an internal salt is formed. 2. A radiographic element according to claim 1, wherein said non-photosensitive silver halide fine grains have an average grain size of 0.005 to 0.1 μm. 3. The radiographic element according to claim 1, wherein the non-photosensitive silver halide fine particles are non-photosensitive silver halide fine particles having an epitaxial portion, and the epitaxial portion has a high iodine content. A radiographic element characterized by silver iodobromide or silver iodochloride, or high bromo silver chlorobromide. 4. The radiographic element according to claim 1, wherein the silver halide fine particles have a predetermined number of liquid supply ports through which the liquid to be stirred flows, and discharge the liquid after the stirring processing. A stirring tank provided with a liquid discharge port and a pair of stirring blades which are arranged at least at two places in the stirring tank and which are rotationally driven in opposite directions to each other to control the stirring state of the liquid in the stirring tank; A radiographic element manufactured using the apparatus. 5. The radiographic element according to claim 1, wherein the silver halide emulsion used in at least one of the light-sensitive silver halide emulsion layers has a silver chloride content of 90 mol%. A radiographic element comprising a silver halide emulsion of at least 100 mol%. 6. An image forming method wherein the radiographic element according to claim 1 is subjected to image exposure, development, fixing and washing, followed by drying, wherein at least one of the processing steps is performed. An image forming method for a radiographic element, wherein the two processing steps are performed in the presence of a diaminostilbene compound represented by the general formula [2]. General formula [2] In the general formula [2], L ¹ and L ² may be the same or different, and —OR ¹ or —NR ² R ³ (R ¹ , R ² , R ³
Represents a hydrogen atom or an alkyl group, respectively. ) And satisfies at least one of the following conditions (1) and (2). (1) The four substituents L ¹ and L ² in the general formula [ ² ] have a total of four or more substituents selected from the general formula [Group A]. (2) The four substituents L ¹ and L ² in the general formula [ ² ] have a total of two substituents selected from the general formula [Group A], and the substituents selected from the general formula [Group B] It has a total of two or more groups. General formula [Group A] General formula [Group B] In the general formula [Group A], X represents a halogen atom, and R represents an alkyl group. In the general formulas [2] and [Group A], M represents a hydrogen atom, an alkali metal, tetraalkylammonium or pyridinium.