JPH1195350A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material high in sensitivity and low in fog and capable of being processed at a low replenishing rate by incorporating epitaxial silver halide grains grown on the host flat silver halide grains in a silver halide emulsion layer and a phosazene compound. SOLUTION: This photosensitive silver halide emulsion layer formed on a support contains the epitaxial silver halide grains grown on the host flat silver halide grains having principal [111] faces and the phosphazene compound. The host silver halide grains have a corresponding circle diameter of 0.5-5.0 μm and a thickness of 0.07-0.70 μm and the epitaxial protuberances have face- centered cubic lattice structure and are, preferably, located on the circumferential edges of the flat grains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material having high sensitivity and low fog generation and a processing method therefor.

[0002]

2. Description of the Related Art In recent years, with regard to the development processing of silver halide photographic light-sensitive materials, it has been increasingly desired to reduce the processing time and the amount of processing waste liquid.

[0003] For example, in the medical field, the number of X-ray photography is rapidly increasing due to the spread of periodic medical examinations, medical checkups and the like, and the increase in diagnoses and examinations in general medical care. For this reason, at present, further speeding up of development processing and further reduction of processing waste liquid are increasing.

In order to speed up the processing of silver halide photographic light-sensitive materials, it is essential to shorten processing times such as development, fixing, washing and drying. However, for example, if the conventional photosensitive material is simply shortened by the development time, the image density and the sensitivity are greatly reduced and the gradation is deteriorated. Further, if the fixing time is shortened, the fixing becomes defective, which causes deterioration of the image quality. Therefore, it is basically necessary to increase the developing speed, fixing speed, drying speed, etc. of the silver halide photographic light-sensitive material.

[0005] Conventionally, to increase the developing speed and the fixing speed, it is necessary to reduce the content of silver iodide having low solubility, to use silver chlorobromide and silver chloride emulsions having high solubility, and to make silver halide grains fine. Flattening is believed to be advantageous.
However, it is known that a decrease in the silver iodide content and the use of silver chlorobromide and silver chloride cause a decrease in sensitivity.

JP-A-8-171164 discloses a sensitization technique using epitaxial grains. However, in this technique, the process in which the replenishing amount of the processing solution is reduced is not enough for practical use.

Further, sensitization techniques include reduction sensitization, Se,
Studies on chemical ripening, such as sensitization of Te, have been energetically conducted, but at present, the level of fogging increases, and further studies are required.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having high sensitivity and low fog and capable of low replenishment processing, and a processing method therefor.

[0009]

The above objects of the present invention have been attained by the following constitutions.

(1) In a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, host grains in the silver halide emulsion layer are composed of tabular silver halide grains. A silver halide photographic material comprising silver halide grains and a phosphazene compound.

(2) The host grains of the epitaxial silver halide grains are tabular grains having a (111) plane as a main plane, and have a circle-equivalent diameter of 0.5 to 5.0 μm and a thickness of 0.07.
.About.0.7 .mu.m, having epitaxially deposited silver halide projections of a face-centered cubic structure forming an epitaxy junction, wherein the silver halide projections are located at the periphery of host tabular grains. 2. The silver halide photographic light-sensitive material as described in 1 above, which is a silver particle.

(3) A processing method comprising the steps of developing, fixing and drying the silver halide light-sensitive material according to the above (1) or (2), wherein the total processing time is 30 seconds or less. Processing method of photosensitive material.

(4) A method of continuously processing the silver halide photographic light-sensitive material as described in 1 or 2 above in a processing step including development and fixing steps, wherein the processing solution in each processing step is solid-state processing. A method for processing a silver halide photographic light-sensitive material, characterized by using a processing solution prepared using an agent.

Hereinafter, the present invention will be described in detail. Conventional tabular silver halide grains in the present invention can be used without any particular limitation.

The epitaxial silver halide grains of the present invention have silver halide projections which are epitaxially grown after the tabular silver halide grains are prepared and then epitaxially adhered. The silver halide grains at the time of preparing the tabular silver halide grains before the epitaxial deposition is referred to as "host grains".

The halogen composition of the host tabular grains of the present invention is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When silver iodide is contained, the silver iodide content is preferably from 0.1 mol% to 10 mol%, more preferably 0.1 mol%.
-6 mol% is more preferable, and 0.1 mol%-2 mol% is particularly preferable. It is possible for tabular silver halide grains to contain small amounts of silver chloride, for example, US Pat.
No. 372,927 describes silver chlorobromide tabular grains having a silver chloride content of 0.4 to 20 mol%.

The average aspect ratio of the tabular silver halide grains of the present invention is preferably 2 or more and 10 or less, more preferably 7 or less, and most preferably 5 or less.

In the present invention, it is preferred that at least 50% of the total projected area of the silver halide grains contained in the emulsion is composed of tabular silver halide grains, but preferably at least 70%, more preferably at least 90%. This is the case of tabular silver halide grains having the (111) plane as the main plane. The fact that the main plane is the (111) plane can be confirmed by an X-ray diffraction method or the like.

The tabular silver halide grains of the present invention have two opposing parallel main planes, and the main plane is (1).
11) surface. The equivalent circle diameter is 0.5-3.0 μm,
Preferably it is 0.5 to 2.0 μm. 0.07 thickness
To 0.7 μm, preferably 0.1 to 0.7 μm. Here, the circle equivalent diameter means an average projected area diameter (hereinafter referred to as a particle diameter), and is a circle equivalent diameter of a projected area of the tabular silver halide grains (a circle having the same projected area as the silver halide grains). And the thickness indicates the distance between two parallel main planes forming tabular silver halide grains.

The particle size and thickness can be optimized to optimize speed and other photographic properties. Optimum particle size and optimum depending on other factors constituting the photosensitive material (sensitivity of hydrophilic colloid layer, hardness, chemical ripening conditions, sensitivity of photosensitive material, amount of silver coating, etc.) that affect sensitivity and other photographic characteristics The thickness is different.

The tabular silver halide grains of the present invention are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = width of grain size distribution (% ) Is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains of the present invention preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably 20% or less. And particularly preferably at most 15%.

The tabular silver halide grains of the present invention are crystallographically classified as twins. Twins are silver halide crystals having one or more twin planes in one grain, and the twins are classified according to a report by Klein and Moiser in Photograph Corspondents (Photograh).
phisher Korespondenz) 99 vol.9
The details are described on page 9, page 100, page 57.

In the tabular silver halide grains of the present invention, the silver halide projections are preferably formed at the periphery of the host tabular grains. Here, in the present invention, the peripheral portion of the host tabular grain refers to an outer periphery of the main plane of the tabular grain and a line segment represented by a set of points whose distance from the outer periphery is 10% of the equivalent circle diameter of the host tabular grain. Indicates the range enclosed by.

The halogen composition of the silver halide projections of the present invention is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When silver iodide is contained, the silver iodide content is preferably from 0.1 to 13 mol%, more preferably from 0.1 to 10 mol%.

When the silver halide projections are deposited on the host tabular grains, halide ions are introduced. When a plurality of halide ions are introduced, it is necessary to add them from the one having high solubility of silver salt. preferable.

Since the solubility of silver iodide is lower than that of silver bromide, and the solubility of silver bromide is lower than that of silver chloride, when halide ions are added in a preferred order,
Chloride ions are most likely to adhere near the joint. In some cases, the projections form a clear layer and can detect regions with high and low chloride ion concentrations, but sometimes cannot be detected when halides are added in a preferred order. This is because both bromide and iodide ions have the ability to replace the chloride of silver chloride deposited earlier to some extent.

In the present invention, the silver halide projection is
Closest to the periphery of the host tabular grains and less than 50% of the (111) faces of the tabular grains, preferably a much smaller percentage of the (111) faces of the tabular grains, preferably 25%
It is preferred to limit the fraction to less than 10%, most preferably less than 10%, optimally less than 5%. When the tabular grains include a central region having a low iodide concentration and a region disposed on a side portion having a high iodide concentration, silver halide projections are formed.
Typically, it is preferable to limit to tabular grains formed by regions arranged on the sides including edges and corners of the tabular grains.

In the practice of the present invention, it is preferred to limit the nominal amount of silver halide projections to less than 50 mole percent of total silver. In general, a silver halide projection concentration of 0.3 to 25 mol% is preferable, and a concentration of about 0.5 to 15 mol% is used for sensitization.
Is generally optimal.

When the halide ions are introduced, the temperature of the emulsion containing host tabular grains is introduced at an arbitrary temperature of 35 ° C. to 70 ° C. The pAg is 6.0 to 8.0.
5. The pH is preferably in the range of 4-9.

When the silver halide projections are formed on the periphery of the host tabular grains, a compound which acts as a site director when the silver halide projections are epitaxially attached before the introduction of halide ions (hereinafter referred to as a site director) Is required to be added. When the site director is not added, the silver halide projections are precipitated not only on the peripheral portion of the host tabular grain but also on the entire main plane.

The site director preferably used in the present invention may be any compound generally known in the art as a spectral sensitizing dye for silver halide grains, and specific examples thereof include cyanine, merocyanine, complex cyanine, and complex merocyanine. Compounds which form a J-aggregate with silver halide are preferred among dyes, such as, for example, holopolar, hemicyanine, styryl, and hemioxanol dyes. Particularly preferred are green and red absorbing cyanine dyes. Further, as a site director of the inorganic compound, iodide, thiocyanide, selenocyanide and the like can also be used.

When introducing the site director, the temperature of the emulsion containing host tabular grains is introduced at an arbitrary temperature of 35 to 70 ° C. Preferably it is 35-60 degreeC.

When the site director is introduced, the emulsion containing host tabular grains has a pAg of 6.0 to 8.5,
The pH is preferably in the range of 4-9.

The silver halide grains of the present invention may have dislocations. The dislocation is described, for example, in J. Mol. F. Hamilto
n, Photo. Sci. Eng. , 57 (1967)
And T. Shiozawa, J .; Soc. Photo. S
ci. Japan, 35, 213 (1972) and can be observed by a direct method using a low-temperature transmission electron microscope. In other words, the silver halide grains taken out so as not to apply enough pressure to cause dislocations in the grains from the emulsion are placed on a mesh for electron microscopic observation, and the sample is prepared so as to prevent damage (printout, etc.) by electron beams. Observation is performed by a transmission method in a state of cooling. At this time,
The thicker the particles, the more difficult it is for the electron beam to pass,
High pressure type (200 kV for 0.25 μm thick particles)
The above can be observed more clearly using an electron microscope.

The tabular silver halide grains of the present invention can be produced in the course of forming and / or growing grains by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts). Metal ions such as complex salts) and iron salts (including complex salts) can be added to make these metal elements contained inside and / or on the surface of the particles.

The phosphazene compound of the present invention is preferably a compound having a structural unit represented by the following general formula (1) or (2).

[0038]

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In the formula, R ₁ and R ₂ each represent a substituted or unsubstituted alkyl group, alkoxy group, aryl group, aryloxy group, alkenyl group, alkynyl group, amino group, alkylamino group, arylamino group, alkylthio group. , An arylthio group, an acyl group, an acyloxy group, a cyanide group, or an azide group, wherein R ₁ and R ₂ may be the same or different. n1 represents a positive integer of ₁ or more, and when n1 is plural, R ₁ or R ₂ may be the same or different.

[0040]

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In the formula, R ₃ and R ₄ are each represented by the general formula (1)
Represents a group having the same meaning as R ₁ and R _2, and R ₃ and R ₄ may be the same or different. n2 represents a positive integer of 2 or more, and R ₃ or R ₄ may be the same or different.

The above general formulas (1) and (2) are phosphazene derivatives whose basic skeleton is composed of a P = N bond. In the general formula (1), n1 is particularly limited as long as it is a positive integer of 1 or more. But not more preferably 1 or more and 30,000 or less, more preferably 1 or more and 10,000 or less,
More preferably, it is 1 or more and 5,000 or less. In the general formula (2), n2 is not particularly limited as long as it is a positive integer of 2 or more, but is preferably 2 or more and 10 or less, more preferably 2 or more and 8 or less, and further preferably 3 or 4.

These compounds include a high molecular weight compound having a linear P = N bond, a cyclic compound and a cyclic compound. The method of synthesizing these compounds is described in more detail as follows: (PNF ₂ ) ₃ , (PNF ₂ ) ₄ , (PNF ₂ ) n
And the like, in which the side group such as is a trimer, tetramer, or n-mer of an F atom, (PNCl ₂ ) ₃ , (PNCl ₂ ) ₄ , (PNCl ₂ )
Compounds in which the side group such as n (n <15) is a Cl atom trimer, tetramer, n-mer, (PNBr ₂ ) ₃ , (PNB
(Pr ₂ ) ₄ , (PNBr ₂ ) n, etc., a compound in which the side chain group is a Br atom trimer, tetramer, n-mer, (PNI ₂ ) ₃ , (PNI)
₂ ) ₄ , (PNI ₂ ) n or the like has a side chain group of a halogen atom of a trimer, tetramer, or n-mer compound of an I atom as C ₂ H ₅ ON.
a, CF ₂ HCF ₂ CH ₂ ONa, C ₂ H ₅ SNa, C ₆ H ₅
ONa, CH ₃ C ₆ H ₄ ONa, (C ₆ H ₅ O) ₂ Ca, CF
₃ reaction with metal salts of organic compounds such as CH ₂ ONa, C
An organic compound having a hydroxyl group such as ₆ H ₅ OH or C
P such as alcohol such as H ₂ (CH ₃ ) = C—COOCH ₂ CH ₂ OH, amines such as C ₆ H ₅ NH ₂ , etc.
An organic compound capable of nucleophilic substitution with a halogen atom on an atom,
Examples thereof include a method of mixing with amines such as aniline and halogen acceptor compounds such as sodium hydroxide and sodium carbonate.

The phosphazene derivative is generally synthesized in this manner.
There is no particular limitation.

Further, the combination of the side chain groups does not necessarily need to be composed of a single group, but may be a combination selected from a plurality of these groups. In addition, Chem. R
ev. , 1972, vol72, no. 4, 315-3
It may be a functional group contained in the compound shown in 56.

Next, specific examples of the compound represented by formula (1) or (2) will be shown, but the present invention is not limited to these. In the following specific examples, L is a chain compound, C
Represents a cyclic compound, and Hy represents a cyclic compound having a structure in which the cyclic compounds are further connected in a chain or network.

L-1 [NP (NCS) ₂ ] _n L-2 [NP (NCO) ₂ ] _n L-3 [NP (COCH ₃ ) ₂ ] _n L-4 [NP (COC ₁₇ H ₃₅ ) ₂ ] _n L-5 [NP (CN) ₂ ] _n L-6 [NP (OMe) ₂ ] _n L-7 [NP (OEt) ₂ ] _n L-8 [NP (OCH ₂ CF ₃ ) ₂ ] _n L- 9 [NP (OCH ₂ C ₂ F ₅ ) ₂ ] _n L-10 [NP (OCH ₂ CF ₂ CF ₂ H) ₂ ] _n L-11 [NP (OCH ₂ C ₃ H ₇ ) ₂ ] _n L-12 [NP (OCH ₂ CF ₃ ) (OCH ₂ C
_{3 F 7)] n L-} 13 [NP (OCH 2 (CF 2) 6 CF 3) 2] n L-14 [NP (OCH 2 C 2 F 5) (OCH 2 C
_{3 F 7)] n L-} 15 [NP (OCH 2 CF 2 CF 2 H) (OCH 2 C
₆ F ₁₂ H)] _n L-16 [NP (OPh) ₂ ] _n L-17 [NP (OC ₆ H ₄ F-p) ₂ ] _n L-18 [NP (OC ₆ H ₄ CF ₃ -m) ₂ ] _n L-19 [NP (OC ₆ H ₄ Cl-p) ₂ ] _n L-20 [NP (OC ₆ H ₃ Cl ₂ -2, 4) ₂ ] _n L-21 [NP (OC ₆ H _{4 CH 3 -p) 2] n L} -22 [NP (OC 6 H 4 C 6 H 5 -p) 2] n L-23 [NP (NHMe) 2] n L-24 [NP (NHEt) 2] n L-25 [NP (NHPr-n) ₂ ] _n L-26 [NP (NHBu-n) ₂ ] _n L-27 [NP (NHPh) ₂ ] _n L-28 [NP (NMe ₂ ) ₂ ] _n L −29 [NP (NC ₅ H ₁₀ ) ₂ ] _n L-30 [NP (NEt ₂ ) Cl] _n L-31 [NP (NEt ₂ ) (NH ₂ )] _n L-32 [NP (NEt ₂ ) ( NHMe) _{n L-33 [NP (NEt} 2) (NHEt)] n L-34 [NP (NEt 2) (NHPr-n)] n L-35 [NP (NEt 2) (NHBu-n)] n L-36 (NPPh ₂ ) _n L-37 [NP (SEt) ₂ ] _n L-38 [NP (N ₃ ) ₂ ] _n L-39 [NP (NH ₂ ) ₂ ] _n

[0048]

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C-1 [NP (CF ₃ ) ₂ ] ₃ C-2 (NPPh ₂ ) ₃ C-3 (NPPh ₂ ) ₄ C-4 [NP (C ₆ H ₄ Cl-p) ₂ ] ₃ C- 5 [NP (OC ₆ H ₄ F-p) ₂ ] ₃ C-6 [NP (OC ₆ H ₄ F-p) ₂ ] ₄ C-7 (NPET ₂ ) ₃ C-8 (NPet ₂ ) ₄ C- 9 [NP (COCH ₃ ) ₂ ] ₃ C-10 [NP (COC ₁₇ H ₃₅ ) ₂ ] ₃ C-11 [NP (COCH ₃ ) ₂ ] ₄ C-12 [NP (COC ₁₇ H ₃₅ ) ₂ ] ₄ C-13 [NP (OCH ₂ CF ₃ ) ₂ ] ₃ C-14 [NP (OCH ₂ CF ₃ ) ₂ ] ₄ C-15 [NP (OMe ₂ ) ₂ ] ₃ C-16 [NP (OMe ₂ ) ₂ ] ₄ C-17 [NP (OEt ₂ ) ₂ ] ₃ C-18 [NP (OEt ₂ ) ₂ ] ₄ C-19 [NP (OPr-i) ₂ ] ₃ C-20 [NP (OPr-i) ₂ ] ₄ C-21 [N _{P (OBu-n) 2]} 3 C-22 [NP (OBu-n) 2] 4 C-23 [NP (OCH 2 Ph) 2] 3 C-24 [NP (OCH 2 Ph) 2] 4 C- 25 [NP (OPh) ₂ ] ₃ C-26 [NP (OPh) ₂ ] ₄ C-27 [NP (OC ₆ H ₄ CH ₃ -p) ₂ ] ₃ C-28 [NP (OC ₆ H ₄ CH ₃₎ -P) ₂ ] ₄ C-29 [NP (SEt) ₂ ] ₄ C-30 [NP (SPh) ₂ ] ₃ C-31 [NP (SPh) ₂ ] ₄ C-32 [NP (NHMe) ₂ ] ₃ C-33 [NP (NHMe) ₂ ] ₄ C-34 [NP (NHEt) ₂ ] ₃ C-35 [NP (NHEt) ₂ ] ₄ C-36 [NP (NHBu-n) ₂ ] ₃ C-37 [ NP (NHBu-n) ₂ ] ₄ C-38 [NP (NMe ₂ ) ₂ ] ₃ C-39 [NP (NMe ₂ ) ₂ ] ₄ C-40 [NP (NEt ₂ ) ₂ ] ₃ C-41 [NP (NEt ₂ ) ₂ ] ₄ C-42 [NP (NMePh) ₂ ] ₃ C-43 N ₃ P ₃ Ph ₃ (NHMe) ₃ (cis) C-44 N ₃ P ₃ Ph ₃ (NHMe) ₃ (trans) C-45 N ₃ P ₃ Ph ₃ (NHEt) ₃ (cis) C-46 N ₃ P ₃ Ph ₃ (NHEt) ₃ (trans) C-47 N ₃ P ₃ (NHEt) ) ₄ (OCH ₂ CF ₃ ) ₂ (g
em) C-48 N ₃ P ₃ (NHEt) ₄ (OCH ₂ CF ₃ ) ₂ (n
on-gem) C-49 N ₃ P ₃ (OC ₆ H ₅ ) ₄ (NH ₂ ) ₂ (gem) C-50 N ₃ P ₃ (OC ₆ H ₅ ) ₄ (NH ₂ ) ₂ (non-
gem) C-51 [NP (NCS) ₂ ] ₃ C-52 [NP (NCO) ₂ ] ₃ C-53 [NP (CN) ₂ ] ₃ C-54 [NP (N ₃ ) ₂ ] ₃ C-55 _{[NP (OPr-n) 2} ] 3 C-56 [NP (OCH 2 CF 3) 2] 3 C-57 [NP (SEt) 2] 3 C-58 [NP (NH 2) 2] 3 C-59 [NP (CF ₃ ) ₂ ] ₄ C-60 [NP (NCS) ₂ ] ₄ C-61 [NP (NCO) ₂ ] ₄ C-62 [NP (CN) ₂ ] ₄ C-63 [NP (OPr- n) ₂ ] ₄ C-64 [NP (NH ₂ ) ₂ ] ₄ C-65 [NP (OMe) ₂ ] ₅ C-66 [NP (NMe ₂ ) ₂ ] ₅ C-67 [NP (OPh) ₂ ] _{5 C-68 N 5 P 5} (OC 6 H 5) 8 (NH 2) 2 (gem) C-69 [NP (OMe) 2] 6 C-70 [NP (NMe 2) 2] 6 C-7 1 [NP (OPh) ₂ ] ₆ C-72 N ₆ P ₆ (OC ₆ H ₅ ) ₁₀ (NH ₂ ) ₂ (gem) C-73 [NP (OMe) ₂ ] ₈ C-74 [NP (NMe ₂ ) ₂ ] ₈ C-75 [NP (OPh) ₂ ] ₈ C-76 N ₈ P ₈ (OC ₆ H ₅ ) ₁₄ (NH ₂ ) ₂ (gem)

[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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The preferred amount of the compound represented by formula (1) or (2) is 1 to 1 mol per mol of silver halide.
× 10 ^-6 mol to 1 × 10 ^-2 mol or less is preferably used. More preferably, 1 × 10 ⁻⁵ mol or more and 5 × 10 5
^-3 mol or less.

The silver halide emulsion according to the present invention may be spectrally sensitized with a spectral sensitizing dye. The spectral sensitizing dye refers to a dye that adsorbs to silver halide grains and contributes to sensitization. The spectral sensitizing dye used in the present invention is optional as long as it has a spectral sensitizing function. When adsorbed on silver halide emulsion grains and the reflection spectrum was measured,
It is preferable that the maximum absorption wavelength of the J aggregation band is 555 nm or less. In the application to X-ray medical light-sensitive materials using a phosphor emitting green light, a spectral sensitizing dye is adsorbed on silver halide emulsion grains, and when the reflection spectrum is measured, the green color from the phosphor is measured. J- in the same wavelength range as light
Preferably, a band is formed. That is,
It is preferable to select and combine spectral sensitizing dyes such that the J-band having the maximum absorption is preferably formed in the range of 520 nm to 555 nm. More preferably, it is 530-553 nm, most preferably 540-550 nm.

The addition of the spectral sensitizing dye according to the present invention can be carried out during the chemical ripening step, particularly preferably at the start of the chemical ripening. Also, the step of forming the silver halide projections of the silver halide emulsion according to the present invention is possible. By adding from time to the end of the desalting step, a high-sensitivity silver halide emulsion with excellent spectral sensitization efficiency can be obtained. The same or a different kind of spectral sensitizing dye according to the present invention may be additionally added to the dye added in the above-mentioned step (from the step of forming the silver halide projections to the end of the desalting step).

The silver halide solvent used for chemical sensitization according to the present invention is mixed with a sensitizer and added. The addition amount of the silver halide solvent is preferably 60 mg or more, more preferably 90 mg or more per mol of silver.

In the present invention, the conditions of the step of chemical sensitization,
For example, pAg, temperature, time and the like can be performed under conditions generally performed in the art. Sulfur sensitization using a compound containing sulfur or active gelatin that can react with silver ions for chemical sensitization, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, reduction using a reducing substance Sensitization, gold and other, noble metal sensitization using a noble metal and the like can be used alone or in combination, among them, selenium sensitization, tellurium sensitization, reduction sensitization, etc. are preferably used, particularly Sulfur sensitization, gold sensitization, and selenium sensitization are preferably used.

The chemical sensitization method used for the chemical sensitization according to the present invention can be referred to the sensitization method described in JP-A-7-114131.

The selenium sensitizer used for chemical sensitization according to the present invention contains a wide variety of selenium compounds. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylseleno). Urea, N, N,
N'-trimethyl-N'-heptafluoroselenourea,
N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4-nitrophenylcarbonylselenourea, etc., selenoketones (for example, selenoacetone, seleno Acetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophos Phates (eg, tri-
p-triselenophosphate, etc.) and selenides (diethyl selenide, diethyl diselenide, etc.). In particular, preferred selenium sensitizers are selenoureas,
Selenoamides and selenium ketones. However, in the present invention, the effect is increased by adding the selenium sensitizer as a dispersion of solid fine particles as compared with the case where the selenium sensitizer is added as a solution of an organic solvent.

Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-).
Dimethyltellurourea, N, N'-dimethyl-N'phenyltellurourea), phosphine tellurides (eg, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride,
Butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, telluroacetamide, N, N-dimethyltellurobenzamide), telluroketones, telluroesters, and isotellurocyanates. The technology for using the tellurium sensitizer is based on the technology for using the selenium sensitizer.

Examples of the gold sensitizer include chloroauric acid, gold thiosulfate, gold thiocyanate, and gold complexes of thioureas, rhodanines, and other various compounds.

The amounts of the sulfur sensitizer and the gold sensitizer are not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions and the like.
It is preferably from 1 × 10 ^-4 mol to 1 × 10 ^-9 mol per mol. Further, preferably 1 × 10 ⁻⁵ mol to 1 ×
10 ^-8 mol.

When at least one of the layer containing the photosensitive silver halide emulsion according to the present invention or any of the constituent layers other than the emulsion layer contains a dye capable of decoloring and / or flowing out during the development processing. A photosensitive material having high sensitivity, high sharpness, and low dye stain can be obtained. The dye used in the photosensitive material may be appropriately selected from dyes that can improve sharpness by absorbing a desired wavelength and removing the influence of the wavelength, depending on the photosensitive material. I can do it. It is preferable that the dye is decolorized or flows out during the development processing of the light-sensitive material, and that the coloring is not visible when the image is completed.

The dye used in the light-sensitive material according to the present invention is p
It is substantially insoluble in water at H7 or lower, has a pH of 8 or higher, and is substantially water-soluble. The amount added can be varied depending on the sharpness goal. Preferably 0.2 mg / m
^{2 ~20mg} / m ^2, more preferably 0.8 mg / m ² ~
15 mg / m ² .

Various photographic additives can be used in the silver halide photographic light-sensitive material according to the present invention. Known additives include, for example, Research Disclosure N
o. No. 17643 (December 1978); 187
16 (November 1979) and No. 16 308119
(December 1989).

The silver halide photographic material according to the present invention is prepared by adding a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone to an emulsion layer or other layers. Is also good.

The latex used in the present invention preferably has no or very little adverse effect on the following points even when used in a silver halide photographic element. That is, the latex surface is photographically inert and has very little interaction with various photographic additives. As an example, dyes and dyes are adsorbed and the photographic element is hardly stained with color. Further, it is difficult to adsorb a development accelerator, a development inhibitor, and the like, which affect the speed of development, and hardly affect sensitivity and fog.

It is considered that the fact that the latex which can be used in the present invention has the above-mentioned properties has a great influence on the monomer composition and properties of this latex. An index called a glass transition point is often used for latex. The higher the transition point is, the harder it becomes and cannot serve as a buffer. For this reason, considering the photographic characteristics, the selection of the composition and its use amount are not simple. Latexes using monomers such as styrene, butadiene, and vinylidene are well known. It is said that when a monomer having a carboxylic acid group such as acrylic acid, itaconic acid or maleic acid is introduced during the synthesis of latex, the influence on the photographic properties is reduced, and such synthesis is often attempted. The latex obtained by such a combination may contain a methacrylate unit to appropriately set the glass transition point according to the light-sensitive material.

When a photographic element is produced, gelatin is advantageously used as a protective colloid used in the preparation of the emulsion according to the present invention and as a binder for other hydrophilic colloid layers. Hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sodium alginate,
Sugar derivatives such as starch derivatives; polyvinyl alcohol;
Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, using a variety of synthetic hydrophilic high-molecular substances such as copolymers such as polyvinylimidazole be able to.

As gelatin, lime-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Ph
oto. Japan. No. 16. P30 (1966)
Enzyme-treated gelatin as described in may be used,
In addition, a hydrolyzate or enzymatic decomposition product of gelatin can also be used.

The emulsion according to the present invention is washed with water for desalting,
It is preferable to use a newly prepared protective colloid dispersion. The temperature of washing can be selected according to the purpose, but 5 ℃ ～ 50 ℃
It is preferable to select within the range. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10. The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

A suitable support which can be used in the silver halide photographic light-sensitive material of the present invention is a plastic film or the like. The surface of the support is provided with an undercoat layer in order to improve the adhesion of the coating layer. Or corona discharge, ultraviolet irradiation, or the like. The undercoat layer preferably contains an antistatic improver such as a colloidal tin oxide sol.

The silver halide photographic light-sensitive material according to the present invention can be obtained by providing a silver halide emulsion layer and a crossover cut layer on both sides of a support to obtain a light-sensitive material having high sensitivity, high sharpness and excellent processability. Can be The amount of gelatin in the silver halide emulsion layer, surface protective layer, and other layers is preferably in the range of 0.5 to 3.5 g / m ² , particularly 1.5 to 3 g / m ² , on one side of the support. A range of 0 g / m ² is preferred.

The silver halide photographic material of the present invention can be processed with a processing solution prepared using a solid processing agent. The solid processing agent referred to in the present invention is a powder processing agent or tablet,
Pills, solid processing agents such as granules, etc., which have been subjected to moisture-proof treatment as required.

The term “powder” as used in the present invention means an aggregate of fine crystals. The term “granules” as used in the present invention refers to granules having a particle diameter of 50 to 5000 μm, which are obtained by adding a granulation step to powder. The tablet referred to in the present invention refers to a tablet obtained by compressing powder or granules into a certain shape.

The silver halide photographic light-sensitive material of the present invention can be supplied while continuously processing a solid processing agent. The solid processing agent referred to in the present invention is a powder processing agent, a solid processing agent such as a tablet, a pill, a granule, and the like. The powder refers to an aggregate of fine particle crystals. Granules are obtained by adding a granulation process to powder.
A tablet refers to a granular material having a particle size of 50 to 5000 μm, and a tablet refers to a product obtained by compression molding a powder or a granule into a predetermined shape.

In order to solidify the processing agent, a concentrated liquid, a fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the surface of the temporarily molded processing agent is sprayed with the water-soluble binder. Or any other means such as forming a coating layer.

A preferred method for producing a tablet is a method in which a solid processing agent in the form of powder is granulated and then subjected to a tableting step to form the tablet. There is an advantage that the solubility and storage stability are improved and the photographic performance becomes stable as compared with a solid processing agent formed by simply mixing a solid processing agent component and forming a tablet. As a granulation method for tablet formation, known methods such as tumbling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, and spray drying granulation can be used. For tablet formation, the average particle size of the obtained granules is 100 to 800 μm, because when mixing the granules and compressing and compressing, the components become non-uniform, so-called segregation hardly occurs. Is preferably used, and more preferably 200 to 750 μm.
Further, the particle size distribution is such that 60% or more of
Those with a deviation of 150 μm are preferred. Next, when the obtained granules are compressed under pressure, a known compressor, for example, a hydraulic press, a single-shot tableting machine, a rotary tableting machine, or a briquetting machine can be used. The solid processing agent obtained by pressurizing and compression can take any shape, but from the viewpoint of productivity, handling, or dust when used on the user side, a cylindrical type, so-called tablet, is preferable. .

Preferably, at the time of granulation, the above effect is further remarkable by separately granulating each component, for example, an alkali agent, a reducing agent, a preservative, and the like.

A method for producing a tablet processing agent is described in, for example,
Nos. 1-61837, 54-155038 and 52-
No. 88025, British Patent No. 1,213,808, etc., and can be produced by a general method. Further, granulating agents are described in, for example, JP-A Nos. 2-109042 and 2-109043.
And JP-A-3-39735, JP-A-3-39939, and the like. Further, powder processing agents are described, for example, in JP-A-54-133332 and British Patent 72.
5,892, 729,862 and German Patent 3,
It can be produced by a general method as described in the specification such as 733,861.

The bulk density of the above-mentioned solid processing agent is 1.0 g / cm ³ in the case of a tablet from the viewpoint of solubility and the effect.
To 2.5 g / cm ³ is in terms of the strength of preferably 1.0 g / cm ³ greater than the resulting solid, and more preferred in view of solubility of the solid product obtained as 2.5 g / cm ³ less than. When the solid processing agent is granules or powder, the bulk density is 0.
Those having 40 to 0.95 g / cm ³ are preferred.

The solid processing agent used in the present invention is a developer,
Although used for photographic processing agents such as fixing agents and rinsing agents, it is the developer that has a great effect of the present invention, especially an effect of stabilizing photographic performance.

Although the solid processing agent used in the present invention may fall within the scope of the present invention, it is within the scope of the present invention to solidify only one part of a certain processing agent. However, it is preferable that all the components of the processing agent are solidified. is there. It is desirable that each component is molded as a separate solid processing agent and is mounted in the same unit. It is also desirable that the separate components are packaged in the order in which they are periodically and repeatedly placed in a package.

It is preferable that all the processing agents to be replenished into each processing tank according to the processing amount information are charged as solid processing agents.
When replenishing water is required, replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishing water. That is, when two or more types of processing tanks need replenishment, only one tank is required to store the replenishing liquid by sharing the replenishing water, and the size of the automatic developing machine can be reduced. The replenishing water tank may be provided outside or externally, or may be built in an automatic developing machine.

In the case of solidifying the developer, it is preferable that all of the alkali agent and the reducing agent are solidified, and in the case of a tablet, at least three agents are used and most preferably one agent is used. It is a preferred embodiment of the agent. When the solid processing agent is divided into two or more agents, it is preferable that these tablets and granules are packaged in the same manner.

In the present invention, as a supply means for supplying the solid processing agent to the processing tank, for example, when the solid processing agent is a tablet, Japanese Unexamined Utility Model Publication No. 63-137783, 63-97
There are known methods such as Japanese Patent Application Laid-Open No. 522 and Japanese Utility Model Application Laid-Open No. 1-85732, but any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is in the form of granules or powder, it is disclosed in Japanese Utility Model Application Laid-Open No. 62-8196.
4, JP-A-63-84151, JP-A-1-292375
No., etc., and the gravity drop method described in
And a method using a screw or a screw described in JP-A-63-195345 are known methods, but are not limited thereto.

However, in a preferred method, the supply means for supplying the solid processing agent to the processing tank includes, for example, a predetermined amount of the solid processing agent weighed in advance and divided and packaged, and the package is opened in accordance with the processing amount of the photosensitive material. There is a way to take it out. Specifically, the solid processing agent is sandwiched and stored in a predetermined amount, preferably in a single replenishment amount, in a package composed of at least two packaging materials. The part is opened so that it can be removed. The solid processing agent in a removable state can be easily supplied to a processing tank having a filtering means by natural fall. Since a predetermined amount of the solid processing agent is stored in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is shut off, the moisture proof is guaranteed unless opened.

As an embodiment, a configuration is conceivable in which a package made of at least two packaging materials sandwiches the solid processing agent and is closely adhered or adhered to each other so that the periphery of the solid processing agent can be separated. . By pulling each packaging material sandwiching the solid processing agent in a different direction, the contact surfaces adhered or adhered are separated, and the solid processing agent can be taken out.

As another embodiment, a configuration is conceivable in which at least one of the packages composed of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term “opening” as used herein refers to a cut or break that leaves a part of the packaging material. As an opening method, the solid processing agent is forcibly extruded by applying a compressive force from the non-opening side package to the openable package through the solid processing agent, or the package is opened. It is conceivable that the solid processing agent can be taken out by making a cut with a sharp member.

The supply start signal is obtained by detecting information on the processing amount. The supply stop signal is obtained by detecting information indicating that a predetermined amount of supply has been completed. Also, when the processing agent is packaged and needs to be opened, the driving means for separating or opening operates based on the obtained supply start signal, and the driving means for separating or opening based on the supply stop signal stops. Can be controlled.

The supply means of the solid processing agent may have a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the photosensitive material. That is, in an automatic developing machine, it is necessary to keep the component concentration in each processing tank constant and to stabilize photographic performance.

The processing amount information of the photographic light-sensitive material means the processing amount of the silver halide photographic light-sensitive material processed with the processing solution or
It is a value proportional to the processing amount of the processed silver halide photographic light-sensitive material or the processing amount of the silver halide photographic light-sensitive material being processed, and indicates indirectly or directly the reduction amount of the processing agent in the processing solution. Before the photosensitive material is carried into the processing solution,
It may be detected at any time after or during immersion in the processing solution. Further, physical parameters such as the concentration of the composition in the processing solution, a change in the concentration, pH, and specific gravity may be used. Alternatively, the amount of the treatment liquid that has come out after drying may be used.

The place where the solid processing agent according to the present invention is charged may be in a processing tank, but is preferably in communication with a processing section for processing a photosensitive material, and a processing liquid flows between the processing section and the processing section. It is preferable to use a structure in which the processing component is circulated and the processing component has a fixed circulation amount between the processing unit and the dissolved component moves to the processing unit. The solid processing agent is preferably introduced into a processing liquid whose temperature is controlled.

It is preferable that the developer in the processing method according to the present invention does not substantially contain a dihydroxybenzene-based developing agent.

In the processing solution of the present invention, an organic reducing agent can be used as a preservative in addition to sulfite as a preservative. In addition, bisulfite adducts of chelating agents and hardeners can be used. It is also preferable to add a silver sludge inhibitor. Addition of a cyclodextrin compound is also preferable, and compounds described in JP-A-1-124852 are particularly preferable.

The processing temperature of the developer is preferably 25 to 5
At 0 ° C, more preferably 30 to 40 ° C. The development time is 3 to 15 seconds, more preferably 3 to 10 seconds. The total processing time in the present invention is Dry to Dry
For 30 seconds or less, and preferably 25 seconds or less. The term "total processing time" as used herein refers to the total processing time including the steps of developing, fixing, washing and drying the photosensitive material.

The replenishment of the treating agent replenishes the amount corresponding to the treating agent fatigue and oxidative fatigue. The replenishment method is disclosed in
No. 43, replenishment by width and feed speed.
No. 104946, refilling area, JP-A-1-149915
Area replenishment controlled by the number of continuous processing described in No. 6 may be used, and a preferable (development) replenishment amount is 14 ml / 4.
It is below the cut. More preferably, it is 7 ml / 4 cut or less.

The fixing temperature and time are more preferably from 20 ° C. to 50 ° C. for 2 seconds to 8 seconds. Preferred fixing solutions include fixing materials generally used in the art, and the iodine content is preferably 0.3 g / liter or less, more preferably 0.1 g / liter or less. Fixer pH is 3.8
As mentioned above, it is preferably 4.2 to 5.5. A preferred replenishment rate of the fixing solution is 14 ml / 4 cut or less, more preferably 7 ml / 4 cut or less. The fixing solution may be one that forms an acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferable to add in the form of aluminum sulfate, aluminum chloride, potassium alum and the like.

The fixing solution may optionally contain a preservative such as sulfite or bisulfite, a pH buffer such as acetic acid or boric acid, a mineral acid (sulfuric acid, nitric acid) or an organic acid (citric acid, oxalic acid, malic acid, etc.). PH adjusting agents such as various acids such as hydrochloric acid, metal hydroxides (potassium hydroxide and sodium), and chelating agents having a water softening ability.

As the fixing accelerator, for example, JP-B-45-3
No. 5754, No. 58-122535, No. 58-122
No. 536, US Pat. No. 4,126,
And the thioethers described in JP-A No. 459.

[0105]

EXAMPLES The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.
The invention can be better understood by reference to the following examples of emulsion preparation, emulsion and photographic elements that satisfy the requirements of the invention.

Example 1 (Preparation of seed emulsion) Seed emulsion 1 was prepared as follows.

A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% ethanol aqueous solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2.5N silver nitrate aqueous solution 2825 ml C1 bromide 841 g of potassium 2825 ml of water D1 1.75 N aqueous solution of potassium bromide The following silver potential control amount: 42 ° C, JP-B-58-58288, 58-5828
The solution B1 was added to the solution A1 using the mixing stirrer shown in No. 9.
Then, 464.3 ml of each of the solution C1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 60 ° C. for 60 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution was again cooled. The B1 and the solution C1 were each mixed with 55.4 by a simultaneous mixing method.
It was added at a flow rate of ml / min for 42 minutes. The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase from 42 ° C. to 60 ° C. and the re-simultaneous mixing with the solutions B1 and C1 was measured using the solution D1.
It was controlled to be 8 mV and +16 mV.

After the addition was completed, the pH was adjusted to 6 with 3% KOH.
It was desalted and washed immediately with 0. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.064 μm. It was confirmed with an electron microscope that the diameter (in terms of circular diameter) was 0.595 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Em-1) A tabular silver halide emulsion Em-1 was prepared using Seed Emulsion 1 and the following four kinds of solutions.

A2 Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous ethanol solution) 2.25 ml Seed emulsion 1 1.722 mol equivalent Equivalent to 3150 ml with water B2 1734 g potassium bromide 3644 ml with water Finish C2 2478 g of silver nitrate Finish to 4165 ml with water D2 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average particle size: 0.05μ) Equivalent to 0.080 mol * 0.06 mol of potassium iodide To 6.64 liters of a 5.0% by weight aqueous gelatin solution containing the above, 2 liters of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added over 10 minutes. During the formation of the fine particles, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

In the reaction vessel, the solution A2 was vigorously stirred while being kept at 60 ° C., and a part of the solution B2, a part of the solution C2 and half of the solution D2 were added thereto by a double jet method over 5 minutes. Then, half of the remaining amount of the solution B2 and the solution C2 are added over a period of 37 minutes, and a part of the solution B2, a part of the solution C2, and the entire remaining amount of the solution D2 are added over 15 minutes. The total amount of the remaining solutions B2 and C2 was added thereto over 33 minutes. During this time, the pH was 5.8 and the pAg was
It was kept at 8.8 throughout. Here, the addition rates of the solution B2 and the solution C2 were changed as a function of time in accordance with the critical growth rate.

After the addition was completed, the emulsion was cooled to 40 ° C., subjected to ultrafiltration desalting by a known method, added with a 10% gelatin solution, stirred at 50 ° C. for 30 minutes, and redispersed. After the redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.984 μm and the average thickness was 0.1 mm.
Tabular silver halide grains having a size of 22 μm, an average aspect ratio of about 4.5, and a particle size distribution of 18.1% were obtained. Also,
The average of the twin plane distance is 0.020 μm, and grains having a twin plane distance to thickness ratio of 5 or more are 97% (number) of all tabular silver halide grains and 10 or more grains are 49 or more. %, 15
These particles accounted for 17%.

(Preparation of Em-2) Em-1 at 40 ° C.
And the pAg was adjusted to 7.5 by simultaneously adding a silver nitrate solution and a potassium iodide solution. At this time, the silver nitrate solution and the potassium iodide solution were added in such a ratio that the silver iodide content of silver halide precipitated in a small amount during this preparation was 12 mol%.

Next, 2 mol% based on the first amount of Em-1
Was added, calcium chloride, sodium bromide, silver iodide fine grain emulsion (the same as used in the preparation of Em-1), and silver nitrate solution were added in this order. The amount of silver nitrate added was 6 mol% based on the total silver amount of the silver halide grains. After all this Em-2
The composition ratio (mol%) of the halide added in the preparation of
l: Br: I = 42: 42: 16 was added.

When the obtained Em-2 was observed with an electron microscope, a large number of silver halide projections epitaxially adhered were observed not only on the periphery but also on the entire main plane ((111) plane).

(Preparation of Em-3) In the preparation of Em-2, between the addition of sodium chloride and the addition of calcium chloride, 0.6 mmol of the sensitizing dye (A) per mole of silver and the sensitizing dye (B Em-3 was prepared in the same manner as in the preparation of Em-2, except that 0.006 mmol (all per mol of silver) was added as a dispersion in the form of solid fine particles.

A dispersion of the spectral sensitizing dye in the form of solid fine particles is prepared by adding a predetermined amount of the spectral sensitizing dye to water previously adjusted to 27 ° C. and using a high-speed stirrer (dissolver) at 3,500 rpm for 30 minutes.
Obtained by stirring for ~ 120 min.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine-sodium salt sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl- 3,3'-Di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride The obtained Em-3 was observed with an electron microscope, and found to be epitaxially attached to the periphery of the main plane ((111) plane). Silver halide protrusions were observed.

(Chemical sensitization of Em-1)
After the addition of the sensitizing dyes (A) and (B) in the following amounts in the form of fine solid particles, a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and A dispersion of phenylphosphine selenide was added, and after 30 minutes, a silver iodide fine grain emulsion was added, followed by ripening for a total of 2 hours. At the end of ripening, 4-hydroxy-6-methyl-1,3,3 is used as a stabilizer.
An appropriate amount of a, 7-tetrazaindene (TAI) was added. The above additives and their amounts (per mole of silver) are shown below.

Sensitizing dye (A) 0.6 mol Sensitizing dye (B) 0.006 mol Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.2 mg Stabilizer ( TAI) 500 mg The above dispersion of triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 kg of ethyl acetate at 50 ° C., stirred and completely dissolved. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and 93 g of a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate was added thereto.
Was added. Next, these two liquids are mixed to obtain a diameter of 10c.
m with a high-speed stirring type disperser having a dissolver of 50 m.
Dispersion was performed at a dispersion blade peripheral speed of 40 m / sec at 30 ° C. for 30 minutes. Thereafter, ethyl acetate was removed while stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

(Chemical sensitization of Em-2 and Em-3) The sensitizing dyes (A) and (B) were not added. , Em-3 were chemically sensitized.

To the emulsion thus obtained, the kind and amount of the compound represented by the general formula (1) or (2) shown in Table 1 and the additives described below were added to prepare an emulsion layer coating solution. At the same time, a coating solution for a protective layer described below was prepared. Using both coating solutions, the coating amount was 1.6 g / m ^{2 of} silver per side, and the amount of gelatin was 2.5
g / m ² was applied simultaneously on both sides of the support at a speed of 80 m / min using two slide hopper coaters so as to obtain g / m ^2, and dried for 2 minutes and 20 seconds to obtain a sample. As a support, a copolymer aqueous dispersion obtained by diluting a copolymer composed of three monomers of 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate, and 40 wt% of butyl methacrylate so as to have a concentration of 10 wt% was placed below. A polyethylene terephthalate film base colored blue with a concentration of 0.13 for an X-ray film of 175 μm as an eluate was used.

The additives used in the emulsion are as follows.
The amount of addition is shown in an amount per mole of silver halide.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 180 mg / m ² Gelatin 0.2 g / m ² Sodium dodecylbenzenesulfonate 5 mg / m ² Compound (I) 5 mg / m ² 2, 4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μ) 10 mg / m ² Second layer (emulsion layer) For each of the emulsions obtained above, The following various additives were added.

Compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone ( 35 mg / m ² Styrene-maleic anhydride copolymer 80 mg / m ² Sodium polystyrene sulfonate 80 mg / m ² Trimethylolpropane 350 mg / m ² Diethylene glycol 50 mg / m ² Nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3 ammonium dihydroxybenzene-4-sulfonic acid 500 mg / m ² 2-mercaptobenzimidazole-5-sulfonate sodium 5 mg / ^{m 2} compound ^{(H) 0.5mg / m 2 n} -C 4 H 9 _{OCH 2 CH (OH) CH 2} N _{CH 2 COOH) 2 350mg / m} 2 Compound (M) 5 mg / m ² Compound (N) 5 mg / m ² Colloidal silica 0.5 g / m ² Latex (L) 0.2 g / m ² Dextrin (average molecular weight 1000) 0 1.2 g / m ² Gelatin 1.2 g / m ² Third layer (protective layer) Gelatin 0.8 g / m ² Matting agent composed of polymethyl methacrylate (area average particle size 7.0 μ) 50 mg / m ² Formaldehyde 20 mg / m ² 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² bis-vinylsulfonylmethyl ether 36 mg / m ² latex (L) 0.2 g / m ² polyacrylamide (average molecular weight 10,000 ) 0.1 g / m ² sodium polyacrylate 30 mg / m ² compound (SI) 20mg / m ² compound (I) 12 mg / ² Compound (J) 2mg / m ² Compound (S-1) 7mg / m 2 Compound (K) 15mg / m ² Compound (O) 50mg / m ² Compound (S-2) 5mg / m 2 C 9 F 19 - O- (CH ₂ CH ₂ O) ₁₁ -H 3 mg / m ² C ₈ F ₁₇ SO ₂ N- (C ₃ H ₇ ) (CH ₂ CH ₂ O) ₁₅ -H 2 mg / m ² C ₈ F ₁₇ SO _{2 N- (C 3 H 7) (} CH 2 CH 2 O) 4 - (CH 2) 4 SO 3 Na 1mg / m 2

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Next, the photographic characteristics were evaluated using the obtained coated sample. First, the sample was sandwiched between two fluorescent intensifying screens XG-S (manufactured by Konica Corporation), and a tube voltage of 8 was applied through an aluminum wedge.
X-rays were irradiated at 0 kVp and a tube current of 100 mA for 0.05 seconds, and exposure was performed.

(Processing 1) Automatic developing machine (S manufactured by Konica Corporation)
Processing 1 was performed using RX-701) with a developing solution and a fixing solution having the following formulations. Note that tablets were prepared according to the following operations (A to D).

Operation (A) 3000 g of hydroquinone as a developing agent is ground in a commercially available bantam mill until the average particle size becomes 10 μm. 3000 g of sodium sulfite and 2 parts of potassium sulfite were added to the fine powder.
000 g and 1000 g of Dimaison S were added and mixed in a mill for 30 minutes, and then at room temperature for about 10 minutes in a commercially available stirring granulator.
After granulating by adding 30 ml of water, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to remove almost completely the moisture of the granulated material. 25 g of 100 g of polyethylene glycol 6000 was added to the granules thus prepared.
After mixing uniformly for 10 minutes using a mixer in a room humidified at 40 ° C. and below 40% RH, one tablet of the obtained mixture was obtained using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. The tablet A for development replenishment was prepared by compression tableting with the filling amount per unit being 3.84 g.

Operation (B) 100 g of DTPA, 4000 g of potassium carbonate, 10 g of 5-methylbenzotriazole, 7 g of 1-phenyl-5-mercaptotetrazole, 5 g of 2-mercaptohypoxanthine, 200 g of KOH, 5 g of N-acetyl-D, L-penicillamine, Is pulverized and granulated in the same manner as in the operation (A).
The amount of water added was 30.0 ml, and after granulation,
After drying for a minute, the water content of the granules is almost completely removed. The mixture thus obtained was compressed and tableted using the same tableting machine as described above with a filling amount per tablet of 1.73 g to prepare a tablet B for development replenishment.

Next, a fixing replenishing tablet was prepared in the following manner.

Operation (C) Ammonium thiosulfate / sodium thiosulfate (70/3
0 weight ratio) 14000 g, sodium sulfite 1500 g
Is ground in the same manner as in (A), and then uniformly mixed with a commercially available mixer. Next, in the same manner as in (A), the amount of water added was 500 m
and perform granulation. After the granulation, the granules are dried at 60 ° C. for 30 minutes to almost completely remove the moisture of the granules. 4 g of sodium N-lauroylalanine is added to the granules thus prepared and mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the obtained mixture was subjected to compression tableting using a tableting machine similar to the above with a filling amount per tablet of 6.202 g, and tablets for fixing replenishment C were prepared.
A preparation was made.

Operation (D) Boric acid 1000 g, aluminum sulfate / 18-hydrate 150
0 g, sodium hydrogen acetate (3,000 g of glacial acetic acid and sodium acetate mixed and dried), tartaric acid 200
g is ground and granulated in the same manner as in the operation (A). The amount of water to be added is 100 ml, and after granulation, the mixture is dried at 50 ° C. for 30 minutes to almost completely remove water from the granulated product. 4 g of sodium N-lauroylalanine was added to the thus-prepared product, and after mixing for 3 minutes, the obtained mixture was compressed to a filling amount of 4.562 g per tablet using the same tableting machine as described above. Tableting was performed to prepare a fixing replenishing tablet D preparation.

Developer Starter Glacial acetic acid 2.98 g KBr 4.0 g Water was added to make up to 1 liter.

At the start of developing solution processing (running start), developing solution 1 prepared by diluting developing tablets A and B with diluting water was used.
The processing was started by filling the developing tank with a liquid obtained by adding 330 ml of the starter to 6.5 liters as a starting liquid.
The pH of the developer to which the starter was added was 10.45.

The photosensitive material prepared above was exposed to light so that the optical density after development processing was 1.0, and running was performed. For the running, an automatic developing machine SRX-701 (manufactured by Konica Corp.) equipped with a charging member for a solid processing agent and modified so as to be able to process at a processing speed of 15 seconds was used. During the running, the above-mentioned ^two agents A and B and 0.6 ml of water were added to the developer per 0.62 m ² of the photosensitive material.
When each of A and B was dissolved in 38 ml of water, the pH was 10.
70. To the fixing solution, ^two C agents, one D agent and 74 ml of water were added per 0.62 m ² of the photosensitive material. The rate of addition of water to each processing agent was started almost simultaneously with the addition of the processing agent, and was added at a constant speed for 10 minutes in approximately proportion to the dissolution rate of the processing agent.

[0141] The processing stability was evaluated by uniformly exposing the prepared sample with tungsten light so that the transmitted light blackening concentration was 1.0, and then until the processing level reached an equilibrium state in processing 1 (four cuts). (2000 sheets in size), sensitometry was performed at the initial level and the level after running, and the sensitivity difference was compared. The closer the sensitivity difference ΔS between the initial level and the level after running to 0, the more excellent the processing stability.

(Process 2) SRX701 automatic machine and DF-7
Processing 2 was performed using a 1-30 processing liquid (both manufactured by Konica Corporation) for a processing time of 30 seconds.

Fogging of the samples obtained in the treatments 1 and 2
The sensitivity and gamma were measured. Sensitivity is the sample No. The sensitivity in the processing 2 of 1 was set to 100 and expressed as a relative sensitivity. Also,
Gamma was determined by measuring the slope of the logarithm of the amount of exposure that gives densities of 1.0 and 2.0.

The results are shown in Table 1.

[0145]

[Table 1]

As is clear from Table 1, the sample of the present invention has high sensitivity and low fog, but the samples other than the present invention have low sensitivity and have a problem with fog. Further, the sample of the present invention has excellent processing stability.

[0147]

According to the present invention, a silver halide photographic material having high sensitivity and low fog and capable of low replenishment processing and a processing method thereof can be provided.

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein the host halide grains in the silver halide emulsion layer are tabular silver halide grains. A silver halide photographic material comprising silver halide grains and a phosphazene compound. 2. The host grains of the epitaxial silver halide grains are tabular grains having a (111) plane as a main plane, having an equivalent circle diameter of 0.5 to 5.0 μm and a thickness of 0.07 to 0.
7 μm, having epitaxially deposited silver halide projections of a face-centered cubic structure forming an epitaxy junction, and the silver halide projections are silver halide grains located at the periphery of host tabular grains. 2. The silver halide photographic light-sensitive material according to claim 1, wherein 3. A processing method comprising the steps of developing, fixing and drying the silver halide light-sensitive material according to claim 1 or 2, wherein the total processing time is 30 seconds or less. Processing method of photosensitive material. 4. A method for continuously processing the silver halide photographic light-sensitive material according to claim 1 or 2 in a processing step including a developing step and a fixing step, wherein the processing liquid in each processing step is solid-state processing. A method for processing a silver halide photographic light-sensitive material, characterized by using a processing solution prepared using an agent.