JPH11218867A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material with high sensitivity, low fog and excellent treatment stability. SOLUTION: In this silver halide photographic sensitive material having at least one silver halide emulsion layer on a supporting body, at least one silver halide emulsion layer contains a cationic starch and is treated with a developer containing reductons. In the silver halide particles in the silver halide emulsion layer above described, >=70% of the projected area of the whole particles is occupied by flat plate-like particles having a (111) principal plane and the average aspect ratio of >=2 and <=10 and further, the silver halide emulsion contains a silver halide photographic emulsion subjected to reduction sensitization.

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 light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sensitivity, low fogging and excellent processing stability.

[0002]

2. Description of the Related Art In recent years, it has become an essential requirement to reduce development processing waste liquid for environmental protection.

[0003] Further, as for hydroquinones, which have been generally used as developing agents, conventionally, ascorbic acids and their derivatives (for example, reductones) are being studied as alternatives because of their insufficient safety.

[0004] However, ascorbic acids have the drawback of lowering the pH of the developing solution by air oxidation, thereby lowering the developing reaction and the developing activity. Therefore, it is technically difficult to maintain the pH to reduce the replenishment amount. Was included.

On the other hand, a developer is generally supplied as a concentrated solution or powder, and is prepared into a working solution by diluting or dissolving it in a certain amount of water before use. These concentrates or solid processing agents are easily oxidized by oxygen in the air during storage.

[0006] Oxidation lowers the concentration or pH of the developing agent or preservative, deteriorating the developability after storage over time. As described above, since the concentrated solution of the treating agent or the solid treating agent is deteriorated by long-term storage, there is a need for a technique that does not deteriorate the performance even after long-term storage. Further, there has been a demand for the development of a developer capable of obtaining stable photographic performance without processing fluctuation in a long-term running process.

Conventionally, techniques for preventing the oxidation of a developing solution include, for example, US Pat. No. 1,420,656 to which an amine compound is added as an antioxidant of a color developing agent, and Japanese Patent Application Laid-open No.
No. 3532 is disclosed.

However, a decrease in pH due to oxidation of a developer containing ascorbic acid (reductones) as a main agent is suppressed,
There was no disclosure of a technique for maintaining the development activity.

As a technique for maintaining the pH of the developer, it is known to use a large amount of a carbonate buffer. As a technique for maintaining the activity, it is conceivable to increase the amount of sulfite or add a preservative. However, these techniques are not preferable because the maintenance of the pH is insufficient and the salt concentration of the developer is increased to cause a decrease in developability.

On the other hand, for rapid processing of a silver halide photographic light-sensitive material, it is essential to shorten processing time 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.

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.

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.

In order to increase the developing speed, fixing speed or drying speed of a silver halide photographic light-sensitive material, a protective colloid of silver halide particles and a binder of another hydrophilic colloid layer are adjusted to the processing conditions. It is important to do things. Generally, gelatin is used as the protective colloid, but various studies have been made on other hydrophilic colloids. JP-A-9-
Nos. 120109 and 9-120110 describe a method for producing tabular silver halide grains using cationic starch as a peptizer. The use of cationic starch as a binder in the emulsion layer has been used to obtain cool images, indicating that the starch need not be cationic. However, by treating a silver halide photographic material using cationic starch as a binder with a developer containing reductones,
There is no disclosure or suggestion that the development processing stability is improved.

[0014]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, low fog, and excellent processing stability.

[0015]

The above object of the present invention has been attained by the following constitutions. It was a surprising discovery that the processing stability of a silver halide photographic material using a cationic starch as a binder according to the present invention was improved by processing with a developer containing reductones.

1. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers contains a cationic starch and is processed with a developer containing reductones. A silver halide photographic light-sensitive material comprising:

2. The silver halide grains in the silver halide emulsion layer are tabular grains in which at least 70% of the total projected area has a (111) major plane and an average aspect ratio of 2 to 10, and Contains a silver halide photographic emulsion which has been subjected to reduction sensitization.

3. 3. The silver halide photographic light-sensitive material according to 1 or 2, wherein the developer is prepared using a solid processing agent.

4. 4. The silver halide photographic light-sensitive material according to 3, wherein the photographic material is processed by an automatic processor having a total processing time of 10 to 30 seconds.

Hereinafter, the present invention will be described in detail.

{Silver Halide Grains} In the present invention, as the silver halide grains in the silver halide emulsion, conventional ones can be used without any particular limitation. Tabular silver halide grains having a high density).

The halogen composition of the tabular silver halide grains is preferably any of silver bromide, silver iodobromide, silver chlorobromide and silver chloroiodobromide. When silver iodide is contained, the silver iodide content is preferably 0.1 mol% to 10 mol%, more preferably 0.2 mol%.
-6 mol% is more preferable, and 0.4 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%.

In the present invention, the average aspect ratio of the tabular silver halide grains is such that when the aspect ratio is smaller than 2, the covering power, which is an advantage of the tabular grains, is greatly reduced. It is preferably 2 or more and 10 or less, more preferably 2 or more and 7 or less, and most preferably 3 or more and 5 or less because the pressure resistance is easily deteriorated.

In the present invention, in order to make full use of the performance of the tabular grains, 70% or more of the total projected area of the silver halide grains contained in the silver halide emulsion has a (111) plane as a main plane. It is preferable that the silver halide grains are composed of silver halide grains, and more preferably 90% or more are composed of tabular silver halide grains having a (111) plane as a 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 in the present invention have two opposing parallel main planes, and the main plane is (1).
11) surface. The equivalent circle diameter is preferably 0.5 to 3.0 μm, more preferably 0.5 to 2.0 μm
It is. The thickness is preferably from 0.07 to 0.7 μm, more preferably from 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 the projected area of the tabular silver halide grains (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 in the present invention are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = broad grain size distribution (% ) Is preferably 25% or less, more preferably 20% or less, and particularly preferably 15% or less.

The tabular silver halide grains in 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 may be epitaxial grains formed on the host tabular grains. The halogen composition of the silver halide projections 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%,
0.1-10 mol% is more preferable.

The halogenated grains of the present invention may have dislocations. The dislocation is described, for example, in J. Mol. F. Hamilton,
Photo. Sci. Eng. , 57 (1967),
T. Shiozawa, J .; Soc. Photo. Sc
i. 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 particle, the more difficult it is for the electron beam to penetrate. Therefore, a sharper observation can be obtained by using a high-pressure electron microscope (200 kV or more for a particle having a thickness of 0.25 μm). it can.

The tabular silver halide grains of the present invention can be produced in the course of forming and / or growing grains by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt). 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.

In the present invention, the silver halide grains may be subjected to reduction sensitization in the grain forming step. Performing the reduction sensitization in the grain formation step of the silver halide emulsion means that it is performed during nucleation, ripening, and growth, and the reduction sensitization may be performed at any stage, but is most preferable. Is a method of reducing sensitization during the growth of silver halide grains.

Here, the term "growing" refers to a state in which the growth is temporarily stopped during the growth, even when the silver halide grains are grown simultaneously by physical ripening or by adding a water-soluble silver salt and a water-soluble alkali halide. The method may be any of the methods of growing further after performing the above.

Reduction sensitization has been known for a long time. For example, Journal of Photograph
hic Science, Vol. 25, pp. 19-27 (19
77) and Photographic Sciences
e and Engineering, Vol. 32, 113
Pp. 117 (1979) describe the sensitization mechanism using a photoreaction formula for silver nuclei.

The reduction sensitizer in the present invention is not particularly limited, and for example, thiourea dioxide, ascorbic acid and its derivatives, stannous salts and the like can be used. Other suitable reducing agents include borane compounds,
Examples include hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount of these reducing agents may be arbitrarily selected, but is usually preferably from 10 ^-2 to 10 ^-8 mol, particularly preferably from 10 ^-4 to 10 ^-6 mol, per mol of silver halide.

The timing of addition may be arbitrarily selected, but preferably during the growth of silver halide grains.

The silver halide photographic light-sensitive material of the present invention is characterized by containing a cationic starch.

The term "starch" includes both native starch and modified derivatives such as dextrinized, hydrodispersed, oxidized, alkylated, hydroxyalkylated, acetylated or fractionated starch.

The starch can be derived from corn starch, wheat starch, potato starch, tapioca starch, sago starch, rice starch, waxy corn starch or high amylose corn starch and the like. Starch generally comprises two structurally distinct polysaccharides, α-amylose and amylopectin. Both comprise α-D-glucopyranose units. In α-amylose, α-D-glucopyranose units form a 1,4-long chain polymer. The repeating unit takes the form (Equation 1):

[0042]

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In amylopectin, the repeating unit 1, 1
In addition to 4-linked, branched chain at position 6 (the -CH ₂ OH
Group) is also apparent, resulting in a branched polymer.
Starch and cellulose repeat units are diastereoisomers that confer different overall geometries to the molecule.
The α anomer found in starch and represented by (formula 1) above can be crystallized and has some degree of hydrogen bonding between repeating units in adjacent molecules (not to the same degree as the β anomer repeating units of cellulose and cellulose derivatives). The resulting polymer is obtained. The polymer molecules formed by the β anomer show strong hydrogen bonding between adjacent molecules, resulting in much higher crystallinity than a cluster of polymer molecules. Starches and starch derivatives that lack the alignment of substituents favoring the strong intermolecular bonds found in cellulose repeating units disperse in water much more readily.

The water-dispersible starch used in the practice of this invention is cationic, that is, contains an overall net positive charge when dispersed in water. Starch is usually cationized by attaching a cation substituent to the α-D-glucopyranose unit, usually by esterification or etherification at one or more free hydroxyl sites. The reactive cation-providing reagent is typically
It contains a primary, secondary or tertiary amino group (which can subsequently be protonated to a cationic form under the intended use conditions) or a quaternary ammonium, sulfonium or phosphonium group.

To be useful as a peptizer, the cationic starch must be water-dispersible. Many starches disperse in water when heated to a temperature below boiling for a short time (eg, 5 to 30 minutes). High shear mixing also facilitates starch dispersion. The presence of a cationic substituent increases the polarity of the starch molecule and facilitates dispersion. For starch molecules, they are preferably dispersed at least at the colloid level, and ideally at the molecular level, ie
Dissolve.

The following patents describe water-dispersible cationic starches within the intended scope of the present invention: * US Pat. No. 2,989,520 (Rutenb)
erg et al.), US Patent No. 3,017,294 (Mei).
sel), U.S. Pat. No. 3,051,700 (Eliz)
er et al.), U.S. Patent No. 3,077,469 (Aszo).
los), U.S. Pat. No. 3,136,646 (Eliz)
er et al.) * U.S. Patent No. 3,219,518 (Bar
ber et al.) * U.S. Pat. No. 3,320,080 (Mz
Zarella et al.), U.S. Pat. No. 3,320,118 (Black et al.), U.S. Pat. No. 3,243,426 (Caesar et al.), U.S. Pat. No. 3,336,292 (Kirby), U.S. Pat. 354,034 (J
US Patent No. 3,422,087 (Caesar), * US Patent No. 3,467,608 (Dishburger et al.), * US Patent No. 3,46.
7,647 (Beaninga et al.), U.S. Pat.
671,310 (Brown et al.); U.S. Pat.
06,584 (Cescato et al.); U.S. Pat.
737,370 (Jarowenko et al.), * U.S. Pat. No. 3,770,472 (Jarowenko), U.S. Pat. No. 3,842,005 (Moser et al.), U.S. Pat. No. 4,060,683 (Tessler), U.S. Pat. No. 4,127,563 (Rakin et al.), U.S. Pat. No. 4,613,407 (Huchette et al.),
U.S. Pat. No. 4,964,915 (Blix et al.) *
U.S. Patent No. 5,227,481 (Tsai et al.) And *
U.S. Patent No. 5,349,089 (Tsai et al.).

Oxidized ones before or after the addition of the cation substituent (patents marked with * above) are also preferred. This oxidation is achieved by treating the starch with a strong oxidizing agent. Hypochlorite (ClO ⁻ ) or periodate (IO ₄
^- both) it is widely used in the manufacture of commercial starch derivatives are and studied, preferred. While any convenient counterion can be used, preferred counterions are those that are well compatible with the preparation of silver halide emulsions, such as alkali and alkaline earth cations, most commonly sodium, potassium Or calcium.

In the developer of the present invention, reductones are preferably used as a developing agent. Examples of the reductones include enediol type, enaminol type, enediamine type, thiol enol type and enamine thiol type,
Preferred are compounds represented by the following general formula (A).

[0049]

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(Wherein R ¹ and R ² are each a hydroxy group,
Represents an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group or an alkylthio group.
P and Q each represent a hydroxy group, a carboxyl group, an alkoxy group, a hydroxyalkyl group, a carboxyalkyl group, a sulfo group, a sulfoalkyl group, an amino group, an aminoalkyl group, an alkyl group or an aryl group, or A non-metal atom group forming a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ¹ and R ² and a carbon atom substituted by Y. Y represents ＝ O or ＮＲNR ³ , and R ³ represents a hydrogen atom, a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group. In the general formula (A), R ¹ and R ² each represent a hydroxy group, an amino group (which may have an alkyl group such as ethyl, butyl, or hydroxyethyl as a substituent), or an acylamino group (acetylamino, benzoyl). Amino), alkylsulfonylamino group (methanesulfonylamino, butanesulfonylamino, etc.), arylsulfonylamino group (benzenesulfonylamino, p-toluenesulfonylamino, etc.), alkoxycarbonylamino group (methoxycarbonylamino, etc.), mercapto group or Represents an alkylthio group (methylthio, ethylthio, etc.), wherein R ¹ and R ²
Preferred examples include a hydroxy group, an amino group, an alkylsulfonylamino group, and an arylsulfonylamino group.

P and Q are hydroxy, carboxyl, alkoxy (methoxy, ethoxy, butoxy, etc.), hydroxyalkyl (hydroxymethyl, hydroxyethyl, etc.), carboxyalkyl (carboxymethyl, carboxyethyl, etc.), Sulfo group (including salt), sulfoalkyl group (sulfoethyl, sulfopropyl, etc.), amino group (including alkyl substitution), aminoalkyl group (aminoethyl, aminopropyl, etc.), alkyl group (methyl, ethyl, propyl, butyl) , Pentyl, etc.)
Or an aryl group (phenyl, p-tolyl, naphthyl, etc.)
Or a non-metallic atomic group bonded to each other to form a 5- to 8-membered ring together with two vinyl carbon atoms substituted by R ¹ and R ² and a carbon atom substituted by Y. These 5-8
The membered rings may form a saturated or unsaturated fused ring.

Examples of the 5- to 8-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring,
Examples thereof include an azacyclohexenone ring, a uracil ring, a cycloheptenone ring, a cyclohexanone ring, an azepine ring, and a cyclooctenone ring, and a 5- to 6-membered ring is preferable. Among them, preferred examples of the 5- to 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexanone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

When Y represents ＮＲNR ³ , R ³ is a hydrogen atom,
It represents a hydroxy group, an alkyl group, an acyl group, a hydroxyalkyl group, a sulfoalkyl group or a carboxyalkyl group, and specific examples of each substituent are the same groups as those described above for R ¹ , R ² , P and Q. Can be mentioned.

Hereinafter, specific examples of the compound represented by formula (A) are shown, but the present invention is not limited thereto.

[0055]

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[0056]

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[0057]

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The reductone salts include, for example, lithium, sodium, potassium and ammonium salts.

Of these, preferred are ascorbic acid and erythorbic acid (stereoisomer) (A-1)
It is.

The amount of these reductones to be added to the developing solution is not particularly limited, but is practically 0.1 to 100 g, preferably 0.5 to 60 g, more preferably 1 to 30 g per liter of the processing solution. Is desirable in order to obtain the effect of suppressing the formation of a white precipitate.

The reductones may contain only one kind or two or more kinds.

In the present invention, it is preferable to use a compound represented by the following general formula (1) together with the above reductones.

[0063]

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(Wherein R ¹¹ represents a hydrogen atom or a methyl group; R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, a carboxyalkyl Represents a group, a sulfoalkyl group or a carboxyl group.) In the general formula (1), R ¹¹ in the formula is selected from a hydrogen atom or a methyl group. R ¹² , R ¹³ , and R ¹⁴ are each independently selected from a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, a carboxyalkyl group, a sulfoalkyl group, or a carboxyl group.

When R ¹² , R ¹³ and R ¹⁴ are alkyl groups, there is no --SH group as a substituent. R ¹² , R ¹³ , R
It is preferable that ¹⁴ is substituted with a hydroxyalkyl group, a carboxyalkyl group, or a sulfoalkyl group, respectively, in order to reduce odor. In order to exhibit the effects of the present invention, R ¹¹ is more preferably a hydrogen atom.

In the present invention, it is more preferable that the compound represented by the general formula (1) is a compound represented by the following general formula (2).

[0067]

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(Wherein, R ¹⁵ and R ¹⁶ represent a hydrogen atom or a methyl group. However, when one or both of R ¹⁵ and R ¹⁶ are a methyl group, the methyl group is substituted with a hydroxy group or a carboxyl group. M represents a hydrogen atom, an alkali metal atom or an ammonium group, and n represents 0, 1 or 2.) In the general formula (2), R ¹⁵ and R ¹⁶ represent a methyl group, a hydroxyalkyl group, a carboxy group. Selected from alkyl groups. Note that R ¹⁵ and R ¹⁶ in the general formula (2) are not substituted with a —SH group. M can take a hydrogen atom, an alkali metal atom, or an ammonium salt, but is actually a carboxylic acid, and is considered to be dissociated in a developing solution to form an anion. Although n can take 0, 1, or 2, 0 is the highest effect of the present invention, and the effect is reduced as the number increases.

The above general formula (1) used in the present invention,
Specific examples of the compound represented by (2) are shown below, but the present invention is not limited thereto.

[0070]

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[0071]

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[0072]

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Each of these compounds is a known compound, and can be easily obtained by synthesis, extraction, and the like. Among these, compounds (2-1), (2-2) and (2-5) are particularly preferred for the present invention.

The above general formula (1) used in the present invention,
The amount of the compound represented by formula (2) to be added to the developer is not particularly limited, but may be practically 0.01 to 1.5 mol per liter of the actually used developer, and is more preferably. It is used at 0.05 mol to 1 mol.

In the developer of the present invention, the compound represented by the general formula (1) or (2) may be used alone, or the compound represented by the general formula (1) and the compound represented by the general formula (2) May be used in combination.

The silver halide photographic material of the present invention is preferably processed using 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, or the like, which is subjected to moisture proof processing as required.

The powder as used in the present invention refers to 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 or fine powder or 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 (Japanese Patent Application Nos. 2-135887 and 2-2031).
No. 65, 2-203166, 2-203167
No. 2-203168 and No. 2-300409).

A preferred tablet production method is a method of granulating a powdery solid processing agent and then performing 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 such as 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, for example, US Pat.

The bulk density of the above solid processing agent is 1.0 g / cm ³ in the case of a tablet from the viewpoint of its 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 possible 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 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,
JP-A-3-137783, JP-A-63-97522,
There is a known method such as Japanese Utility Model 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 powders, Japanese Utility Model Application Laid-Open No.
No. 84151, JP-A-1-292375, and the gravity drop method described in JP-A-1-259375 and JP-A-63-105159 and 63-19.
There is a known method using a screw or a screw described in No. 5345 or the like, but the method is not limited thereto.

However, in a preferred method, as a supply means for supplying the solid processing agent to the processing tank, for example, a predetermined amount of the solid processing agent weighed in advance and divided and packaged is opened according to 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 in close contact with 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, it is conceivable that at least one of the packages made 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 according to 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 material is the processing amount of the silver halide photographic 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 of 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. And a structure in which there is a constant processing solution circulation amount with the processing unit and the dissolved components move 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 of the present invention does not substantially contain a dihydroxybenzene-based developing agent.

In the developer in the processing method of the present invention, an organic reducing agent can be used as a preservative in addition to the sulfite described in Japanese Patent Application No. 4-286232 as a preservative. In addition, a chelating agent described in Japanese Patent Application No. 4-586323 (p. 20) or a bisulfite adduct of a hardener described in the same (p. 21) can be used. It is also preferable to add compounds described in Japanese Patent Application Nos. 4-92947 and 5-96118 (general formulas [4-a] and [4-b]) as silver sludge inhibitors. 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 from 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
And 30 seconds or less, and preferably 25 seconds or less from the viewpoint of realizing rapid processing. 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, Japanese Patent Publication No. 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.

Examples of the support which can be used in the light-sensitive material of the present invention include, for example, Research Disclosure N
o. No. 17643, p. 308 119 of 10
And those described on page 09.

A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The undercoat layer preferably contains an antistatic improver such as a colloidal tin oxide sol.

When the silver halide emulsion layer and the crossover cut layer are provided on both sides of the support of the photographic material of the present invention, a photographic material having high sensitivity, high sharpness and excellent processability can be obtained. The amount of gelatin in the silver halide emulsion layer, surface protective layer and other layers is 0.5 to 0.5 in total on one side of the support.
It is preferably in the range of 3.5 g / m ² , especially 1.
The range is preferably from 5 to 3.0 g / m ² .

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.

In producing a photographic element, gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers. Sex colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, albumin, proteins such as casein; hydroxyethyl cellulose,
Carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl Various kinds of synthetic hydrophilic polymer substances such as a single or copolymer such as imidazole and polyvinyl virazole can be used. As gelatin, besides lime-processed gelatin, acid-processed gelatin and Bul
l. Soc. Sci. Photo. Japan. No.
16. Enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or enzymatic degradation product of gelatin can also be used.

The emulsion of the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The temperature of water washing can be selected according to the purpose, but is preferably selected in the range of 5 ° C to 50 ° C. 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. Noodle washing method, dialysis method using semi-permeable membrane,
It can be selected from centrifugation, 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. In some cases, a method of adding a chalcogenide compound during preparation of an emulsion as described in US Pat. No. 3,772,031 is also useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanic acid, carbonate, phosphate, and acetate may be present.

The silver halide emulsion of the present invention may be spectrally sensitized with a spectral sensitizing dye.

The spectral sensitizing dye refers to a dye which 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. The photosensitive dye is adsorbed on silver halide emulsion grains,
When the reflection spectrum is 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. It is preferable that the J-band is formed in the same wavelength region as the light. That is, it is preferable to select and combine spectral sensitizing dyes so that the J-band having the maximum absorption is preferably formed in the range of 520 nm to 555 nm. More preferably, 5
30-553 nm, most preferably 540-550 n
m.

The spectral sensitizing dye according to the present invention can be added at the time of the chemical ripening step, particularly preferably at the start of the chemical ripening step. Further, the step of forming the silver halide projections of the silver halide emulsion according to the present invention can be carried out. 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 in the chemical sensitization of 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.

As for the chemical sensitization method used for the chemical sensitization of the present invention, the sensitization method described in Japanese Patent Application No. 5-261264 can be referred to.

The selenium sensitizer used in the chemical sensitization of the present invention contains a wide variety of selenium compounds. For example, US Pat. Nos. 1,574,944 and 1,60.
No. 2,592, No. 1,623,499;
150046, JP-A-4-25832, 4-10
No. 9240 and No. 4-147250. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), and 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 (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids And selenoesters (eg, 2-selenopropionic acid, methyl-3-selenobutyrate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), and selenides (diethylselenide, diethyldiethyl) Selenide). Particularly preferred selenium sensitizers are selenoureas, selenamides, 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.

Regarding tellurium sensitizers and sensitization methods, see US Pat. Nos. 1,623,499 and 3,320,069.
Nos. 3,772,031 and 3,531,289
No. 3,655,394, UK Patent No. 235,21
No. 1, No. 1, 121, 496, No. 1, 295, 462
No. 1,396,696, Canadian Patent No. 800,9
No. 58, JP-A-4-204640, JP-A-4-3330
No. 43 and the like. Examples of useful tellurium sensitizers include telluroureas (e.g., N, N-dimethyltellurourea, tetramethyltellurourea, N-carboxyethyl-N, N'-dimethyltellurourea, N, N'-dimethyl). -N'-phenyltellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluramides ( For example, telluroacetamide, N, N-dimethyltellurobenzamide), telluro ketones, telluro esters, isotellurocyanates, and the like.

The technique for using the tellurium sensitizer is the same as the technique 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 to be used and the ripening conditions.
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 any one of the layer containing the photosensitive silver halide emulsion of the present invention or a constituent layer other than the emulsion layer contains a dye capable of decoloring and / or flowing out during development processing, A photosensitive material having high sensitivity, high sharpness, and little 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 of the present invention is p
It is substantially insoluble in water at H7 or less and substantially water-soluble at pH 8 or more. 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 light-sensitive material of the present invention. Known additives include, for example, Research Disclosure No. 17
No. 643 (December 1978); 18716 (1
No. 997) and the same No. 308119 (1989
(December, 2000). The types of compounds and the locations described in these three research disclosures are listed below.

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[Table 1]

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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.

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 odor 841 g of potassium bromide 2825 ml of water D1 1.75 N aqueous solution of potassium bromide
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 stopping the addition of the solution B1 and the solution C1, it takes 60 minutes to raise the temperature of the solution A1 to 60 ° C., adjust the pH to 5.0 with 3% KOH, and then again 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 Make up to 3644 ml with 1734 g water potassium bromide.

C2 Silver nitrate 2478 g Make up to 4165 ml with water.

D2 Fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) Equivalent to 0.080 moles * 5.0 containing 0.06 moles of potassium iodide To 6.64 liters of a 6% by weight aqueous gelatin solution, 2 liters each 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 sodium carbonate solution.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 70 ° 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 completion of the addition, 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.

(Preparation of Em-2) In the preparation of Em-1, 100 mg of thiourea dioxide (reduction sensitizer) was added to the A2 solution.
And stirred at 70 ° C. for 30 minutes before starting addition of solution B2 and solution C2 in the same manner as Em-1.
-2 was prepared.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 1.023 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 4.6, and a particle size distribution of 14.8% were obtained.

A dispersion of solid fine particles of a spectral sensitizing dye was prepared by a method according to the method described in Japanese Patent Application No. 4-99437. That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been previously adjusted to 27 ° C., and a high-speed stirrer (dissolver) is used to add 3,5,5.
Obtained by stirring at 00 rpm for 30-120 minutes.

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 (chemical sensitization of Em-1,2)
After the temperature was reduced to 0 ° C., the sensitizing dyes (A) and (B) were added in the following amounts in the form of solid fine particle dispersion, and then a mixed aqueous solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate, and triphenyl A dispersion of phosphine 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-1,3,3a, 7-
An appropriate amount of tetrazaindene (TAI) was added.

The above-mentioned 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.

The obtained emulsion was added with the kind and amount of cationic starch or gelatin shown in Table 2 and the additives described below 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, two slide hopper type coaters were used to simultaneously coat both sides of the support at a speed of 80 m / min so that the amount of silver per side was 1.4 g / m ² . Drying was performed for 2 minutes and 20 seconds to obtain a photosensitive material.

As a support, an aqueous dispersion of a copolymer obtained by diluting a copolymer composed of three monomers of 50% by weight of glycidyl methacrylate, 10% by weight of methyl acrylate and 40% by weight of butyl methacrylate so as to have a concentration of 10% by weight. Was used as an undercoating liquid, and a polyethylene terephthalate film base colored blue with a concentration of 0.13 for an X-ray film of 175 μm 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 (Dye 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 μm) 10 mg / m ² Second layer (emulsion layer) For each of the emulsions obtained above, The following various additives were added.

Cationic starch described in Table 2 Gelatin described in Table 2 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 (molecular weight 10,000) 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 Ammonium 1,3-dihydroxybenzene-4-sulfonate 500 mg / m ² Sodium ² -mercaptobenzimidazole-5-sulfonate 5 mg / m ² Compound (H) 0. 5 mg / m ² _{n-C 4 H 9 OCH 2} CH (OH) CH 2 N (CH 2 COOH) 2 350mg / m 2 Compound (M) 5mg / m ² Compound (N) 5mg / m ² Colloidal silica 0.5 g / m ² latex (L) 0.2 g / m ² Third layer (protective layer) Cationic starch described in Table 2 Gelatin described in Table 2 Matting agent composed of polymethyl methacrylate (area average particle size 7.0 μm) 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 10000) 0.1g / m ² sodium polyacrylate 30 mg / m ² compound (SI) (polysiloxane) 20 mg / m ² compound ( ) 12 mg / m 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 3mg / m 2 C 8 F 17 SO 2 N- (C 3 H 7) (CH 2 CH 2 O) 15 -H 2mg / 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, photographic characteristics were evaluated using the obtained coated sample (photosensitive material sample). First, a light-sensitive material sample was placed on two fluorescent intensifying screens X.
GS (manufactured by Konica Corporation), X-rays were irradiated through an aluminum wedge at a tube voltage of 80 kVp and a tube current of 100 mA for 0.05 seconds to perform exposure, and treatments 1, 2 and 3 were performed. .

(Preparation of Developer and Processing Agent According to the Present Invention) A developer and a fixer having the following compositions were prepared, and photographic performance was evaluated.

(Treatment 1) <Preparation of Developing Concentrate> Diethylenetriaminepentaacetic acid 5g Sodium sulfite 24g Sodium carbonate monohydrate 87.5g Potassium carbonate 97.5g Sodium erythorbate (reductones) 120g N-acetyl-D, L- Penicylamine 0.1 g 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 16.0 g 5-methylbenzotriazole 0.15 g Glutaraldehyde (50 wt% aqueous solution) 8.0 g Add water to finish to 1 liter KOH Adjust the pH to 10.20 with.

The preparation of the working solution was performed by adding 600 ml of water to 400 ml of the developing concentrated solution to make 1 liter of the working solution.
Let it be 1.

<Preparation of Fixing Concentrate> Ammonium thiosulfate (70 wt / vol%) 400 ml Sodium sulfite 40 g Boric acid 16 g β-alanine 36 g Glacial acetic acid 60 g Tartaric acid 5 g Aluminum sulfate 20 g Add water to make up to 1 liter. Adjust to

The preparation of the working solution was performed by adding 500 ml of water to 500 ml of the fixing concentrate to make 1 liter of the working solution, and fixing solution-1
And

(Process 2) <Preparation of solid developer> Granules (A) 500 g of 1-phenyl-3-pyrazolidone, 10 g of N-acetyl-D, L-penicillamine, 500 g of boric acid, sodium glutaraldehyde bisulfite Addition 1000g
Are ground in a commercially available bantam mill to an average of 10 μm.

To this fine powder, 300 g of DTPA · 5Na (diethylenetriaminepentaacetic acid · pentasodium), 300 g of dimezone S (1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone), 4000 g of ascorbic acid (reductones), sulfurous acid 1600 g of sodium,
7.0 g of 1-phenyl-5-mercaptotetrazole,
400 g of the binder mannitol and 500 g of the compound 2-1 represented by the general formula (2) of the present invention are added, and mixed in a mill for 30 minutes.
After granulating by adding 30 ml of water for 0 minutes, the granulated material is dried at 40 ° C. for 2 hours in a fluidized bed drier to almost completely remove the moisture of the granulated material.

Granulated product (B) 11000 g of potassium carbonate, 2000 of sodium bicarbonate
g are each ground in a commercially available bantam mill to an average of 10 μm. 800 g of binder mannitol was added to each fine powder, mixed in a mill for 30 minutes, and granulated by adding 30 ml of water at room temperature for about 15 minutes in a commercial stirring granulator. The material is dried in a fluidized drier at 40 ° C. for 2 hours to almost completely remove the water content of the granulated material.

The granules (A) and (B) thus obtained were mixed with 100 g of sodium lauryl sulfate at 25 ° C.
Using a mixer in a room conditioned to 40% RH or less
After uniformly mixing for 1 minute, the obtained mixture was subjected to compression tableting with a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU to a filling amount of 10 g per tablet,
21,000 ascorbic acid-based developing tablets were prepared.

The method of preparing the working solution is to add water to 24 solid developers to make 1 liter of working solution.

<Preparation of Solid Fixing Agent> Granulated product (C) Ammonium thiosulfate / sodium thiosulfate (90/1
15000 g), 1500 g of β-alanine, and 4000 g of sodium acetate are pulverized in a commercially available bantam mill to an average of 10 μm.

To this fine powder were added 500 g of sodium sulfite, 750 g of sodium persulfate, and 1300 mannitol binder.
g, adding water to 50 ml and performing stirring granulation,
The granulate is dried at 40 ° C. in a fluidized bed drier to remove water almost completely.

Granulated product (D) 700 g of boric acid, aluminum sulfate / 18-hydrate 1500
g, 1200 g of succinic acid are ground as in (A). 200 g of sodium hydrogen sulfate was added to this fine powder, and the amount of water added was 3
The mixture is stirred at 0 ml to carry out stirring granulation, and the granulated product is dried at 40 ° C. in a fluidized bed drier to completely remove water.

The granules (C) and (D) thus obtained were mixed with 150 g of sodium lauryl sulfate at 25 ° C.
Using a mixer in a room conditioned to 40% RH or less
After uniformly mixing for 1 minute, the obtained mixture was subjected to compression tableting with a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU to a filling amount of 10 g per tablet,
26000 fixing tablets were produced. The working solution was prepared by adding water to 28 solid fixing agents to make 1 liter of working solution.

(Treatment 3) A DF-71-30 treatment solution (manufactured by Konica Corporation) is used. The processing solution does not contain ascorbic acid (reductones) in the developing solution.

<< Evaluation Method >> The photographic performance was evaluated by treating the above processing agents (Processing 1) to (Processing 3) with SRX of an automatic developing machine.
-701 (manufactured by Konica Corporation) and developed in a 30-second mode under the following conditions. Both the developing temperature and the fixing temperature were 35 ° C.

The sensitivities in the table are those of Sample No. in the developer immediately after the preparation in (Process 3). The reciprocal of the exposure amount that gives an optical density of fog density +1.0 to 1 is shown as a relative value with 100 being the reciprocal. The fog indicates the optical density including the unexposed portion of the support, and D
m indicates the maximum concentration. The gamma is 1.0 or 2.
The slope of the logarithm of the exposure amount giving 0 was measured and found. The capacity of the developing tank was adjusted to 13.5 liters.

The processing stability was evaluated by uniformly exposing the prepared sample with tungsten light so that the transmitted light darkening concentration was 1.0 until the processing level reached an equilibrium state in processing 1 ( This was performed by performing sensitometry at the initial level and the level after running, and comparing the sensitivity difference. The closer the sensitivity difference ΔS between the initial level and the level after running to 0, the more excellent the processing stability.

Tables 2 and 3 show the above results.

[0170]

[Table 2]

[0171]

[Table 3]

As is clear from Tables 2 and 3, the present invention has high sensitivity and low fog, and the sensitivity difference between the initial level and the level after running is small, and the processing stability is excellent.

[0173]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and low fog and excellent processing stability can be provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 5/26 520 G03C 5/26 520 5/30 5/30

Claims (4)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic material characterized in that at least one of the silver halide emulsion layers contains cationic starch and is processed with a developer containing reductones. 2. The silver halide grains in the silver halide emulsion layer are tabular grains having 70% or more of the total projected area having a (111) major plane, and having an average aspect ratio of 2 or more and 10 or less, and 2. The silver halide photographic material according to claim 1, wherein said silver halide emulsion contains a reduction-sensitized silver halide photographic emulsion. 3. The silver halide photographic light-sensitive material according to claim 1, wherein said developer is prepared by using a solid processing agent. 4. The silver halide photographic material according to claim 3, wherein the photographic material is processed by an automatic processor having a total processing time of 10 to 30 seconds.