JPH07168323A - Method for developing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To stably process a black-and-white siver halide photographic sensitive material without using hydroquinone as the developing agent and with the liq. replenishment reduced. CONSTITUTION:At least one emulsion layer of this silver halide photographic sensitive material contains >=10mol% Cl<-> in >=50% of the total projected area of the silver halide grains and has a (100) principal plane. The thickness is controlled to <=0.35mum, and the material consists of the flat grains having <=2 aspect ratio. The material is developed with a developer contg. ascorbic acid and/or its derivative.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material. The present invention also relates to a developing method, and further relates to a processing method which makes it possible to reduce the amount of development replenisher per unit area of a photosensitive material by using the developing solution.

[0002]

2. Description of the Related Art Generally used black-and-white silver halide sensitizers (for X-ray, for plate making, for micro, for negative) are hydroquinone as a developing agent and 3-pyrazolidone type as an auxiliary developing agent. After being developed with an alkaline developing solution containing a compound or an aminophenol compound, an image is formed by a developing treatment including steps of fixing and washing (stabilizing) with water. Among them, the X-ray photographic light-sensitive material contains a relatively large amount of silver halide, and since it is processed rapidly, a highly active developer containing a large amount of hydroquinone as a developing agent is used. Has been done. Furthermore, this developer is characterized by containing glutaraldehyde as a hardener. In order to maintain high activity from such a developing solution, it has been replenished in a large amount against air oxidation. However, the toxicity and safety of hydroquinone is now becoming a problem. Sulfite, which is used for preventing the oxidation of hydroquinone, is a main cause of dissolving a silver halide salt in a developing solution and reducing it in the developing solution to cause so-called silver stain. Therefore, alternatives have become necessary. One of them is ascorbic acid known in U.S. Pat. No. 2,688,549 and JP-A-3-249756, and these compounds are hydrolyzed in an alkaline developer to generate an acid. It is a fatal problem to lose the developing activity more and more. Originally, ascorbic acids had low developing activity and did not have sufficient rapid processability.

Until now, no method has been known for avoiding the essential problems inherent in these ascorbic acids. Further, as a developer concentrated solution (treatment agent kit) until the developer is prepared and used, there is no practical problem in commercial value as long as its performance is guaranteed for about two years. If ascorbic acid is contained in the alkaline developer concentrate part during this period, the developing activity may have already been lost when it is used. Thus, even if ascorbic acid is used in place of hydroquinone, its usage is still unknown and is not put to practical use. Further, in order to bring this to a practical performance, various measures are required especially for stability. Black-and-white silver halide photographic light-sensitive materials are generally exposed, then developed, fixed, washed with water,
It is processed in a process called drying. Recently, most of them are processed by using an automatic processor (hereinafter, abbreviated as an automatic processor). At this time, the developing solution is placed in the developing tank of the developing machine in a state of being in contact with air, and the photosensitive material is appropriately processed. It has been desired that the developer has high stability when subjected to such processing. Furthermore, it has been desired to reduce the amount of replenisher required per unit area of the light-sensitive material. Conventionally, for example, X-
About 1 m ² of so-called sheet-shaped photographic light-sensitive material, such as light-sensitive material for ray photography and graphic arts, about 3 developer solution.
It was common to replenish over 30 ml. However, photographic developer waste has a high chemical oxygen demand (so-called C.O.
D) or a biological oxygen demand (so-called BOD), the developing waste liquid is chemically or biologically treated to be harmless and then discharged. A great economic burden is imposed on the treatment of these waste liquids.

On the other hand, regarding the performance of the light-sensitive material, development of a silver halide emulsion technique has been advanced which shows stable processing performance even with a low-activity processing solution and can withstand rapid processing. They are represented by many inventions of tabular grains having a low silver iodide content and tabular grains of silver chlorobromide system. For example, Japanese Patent Application No. 2-2
No. 25637, No. 3-135227, No. 3-1036.
No. 39 and No. 3-145164, it is described that the rapid processing property is improved by using tabular grains having a silver iodide content of 1 mol% or less. Also, for example, Japanese Patent Laid-Open No. 4-15
No. 5327, No. 1-92737, No. 4-6546,
JP-A 3-116133 describes that high silver chloride tabular grains have excellent photographic performance. Furthermore, JP-A-58-111936, JP-A-58-113930,
JP-A-62-123446 also describes silver chloride tabular grains. Especially European patent 0,534,395A1
No. 6 describes a high aspect ratio high silver chloride emulsion having a (100) plane as a principal plane. However, it cannot be expected that these emulsion techniques will provide particularly excellent performance in a developer containing ascorbic acid and its derivatives, let alone high-silver chloride having a (100) plane as the principal plane. It was unexpected that tabular grains exhibit the characteristics remarkably, and that a rapid processing system that is excellent in preservability and can reduce the amount of replenishment can be established.

[0005]

The problem to be solved by the present invention is to use ascorbic acid instead of hydroquinone as a developing agent for a black and white silver halide light-sensitive material, and to use a developing solution containing it. Another object is to improve the stability of a light-sensitive material system, and further to provide a method of processing with a small replenishing amount per unit area of a light-sensitive material.

[0006]

The present inventors have found that the above problems can be solved by the following method. (1) At least one of the emulsion layers has 50% or more of the total projected area of all silver halide grains with a Cl ^- content of 10 mol% or more, a main plane of {100} faces, and a thickness of 0.35 μm or less. A developing method in which a silver halide photographic light-sensitive material composed of tabular grains having a ratio of 2 or more is developed with a developer containing ascorbic acid and / or its derivative. (2) The developing method described in (1) above, wherein the developing solution containing ascorbic acid and / or its derivative contains 0.3 mol / liter or more of a carbonate. (3) To develop by the developing method described in (1) above, wherein the amount of the developer replenisher is 300 ml / m ² or less.

The tabular grains described in the present invention will be described in detail below. In a silver halide emulsion containing at least a dispersion medium and silver halide grains, 50% or more, preferably 60% or more of the total projected area of the silver halide grains.
To 100%, more preferably 70 to 100%, Cl ^- content is 10 mol% or more, preferably 20 mol% to 100%,
More preferably 30 to 100 mol%, and even more preferably 4
It is a tabular grain having 0 to 100 mol% and a main plane being a (100) plane. The principal plane refers to the maximum outer surface of tabular grains. The tabular grains have a thickness of 0.35 μm or less and 0.05 to
0.3 μm is more preferable, and 0.05 to 0.25 μm is still more preferable. The aspect ratio (diameter / thickness) is 2 or more, preferably 2 to 25, and more preferably 4 to 20. Here, the diameter refers to the diameter of a circle having an area equal to the projected area of the tabular grains, and the thickness refers to the distance between two principal planes. The main plane shape of the tabular grains is substantially a right-angled parallel four deformation. However, a mode in which the corners are slightly rounded is also allowed, but (volume of the defective portion of the corner / volume of the particle before the loss)
Is 0.2 or less, and in many cases is 0 to 0.1.
Here, the volume of the particles before deficiency refers to the volume of the particles when the straight part of the particles is extended to form a rectangular parallelepiped.

In the particles having a high AgCl content of the present invention, only one of the four corners may be rounded preferentially. Here, "preferentially" means that the volume of the defective portion is 2 times or more of the other volume, 4 times or more in many cases, and 8 times or more in more cases. (Total projected area of the tabular grains / total projected area of the tabular grains) = a ₇ , preferably 0.0
It is preferably 8 or more, more preferably 0.15 to 1.0, still more preferably 0.35 to 1.0.

The tabular grains have an average grain diameter of 0.2 to 1
0 μm is preferable, and 0.3 to 5 μm is more preferable. The I ⁻ content of the tabular grains is preferably 12 mol% or less, 6
It is more preferably not more than mol%, further preferably 0 to 3 mol%.

The AgX emulsion of the present invention is produced as follows.
can do. The tabular grains are preferential in the edge direction
To grow into tabular grains. Allow the preferential growth
In the present invention, the defect that enables the function is called a screw dislocation defect. The lack
One or more pits are formed at the time of nucleation, preferably 1 to 3, more preferably
In particular, one or two halogen composition gap surfaces should be formed.
It is formed by and. More preferably Ag with high solubility
X₁AgX on the layer₁AgX with lower solubility than the layer₂layer
Are formed by stacking. That is, halogen
Formation of Halogen Composition Gap Face with Inversion Reaction
Is effective. Solubility is AgCl> AgBr> AgI,
Therefore, Cl^-High content, Cl^-The lower the content, the more
It can be said that the resolution is high. More specifically, during nucleation
The halogen composition structure of the nucleus formed is, for example, (AgX₁
| AgX₂), Or (AgX₁| AgX_Four｜ Ag
X₃) Has a structure. The structure is, for example, a silver salt solution (hereinafter
Later "Ag⁺Liquid ”) and a halogen salt solution (hereinafter referred to as“ X ”).^-
Liquid "" is added at the same time, and X is added at the gap surface.
^-Shaped by changing the halogen composition of the liquid discontinuously.
Can be made. Or X in the dispersion medium solution^-Add liquid
Then Ag⁺Add liquid and add AgX₁Form and then another
X^-Liquid, then Ag⁺Add the solution, (AgX₁
| AgX₂) You can also create structures and their combinations
You can also make it by combining. AgX₁And AgX₂,
And AgX₁And AgX_Four, AgX_FourAnd AgX₃Is Cl^-
Content or Br^-Content is 25 to 100 mol%, preferred
50 to 100 mol%, more preferably 75 to 100
It differs by mol%. Further / or I ^-Content is 5-100
Mol%, preferably 10 to 100 mol%, more preferably
Differ by 30-100 mol%. Others, Cl^-Content rate
Difference or Br^-The content difference is I^-Content difference
Can be mentioned 0 to 5 mol%. Nuclear
The size is preferably 0.15 μm or less, and 0.01 to 0.
1 μm is more preferable.

Nucleation two-stage addition (AgX₁｜ A
gX₂) In case of AgX₁: AgX ₂Molar ratio of nuclei
Formation of three-stage addition (AgX₁| AgX_Four| AgX
₃) AgX₁: AgX₂: AgX₃The molar ratio of
The most preferable embodiment of the present invention can be obtained by variously changing the method of drawing.
It is possible to select and use the nuclear molar ratio. (AgX
₁| AgX₂), AgX₂Layer thickness is AgX₁layer
It is preferable to cover the surface of 1 layer or more on average with 3 lattices
Amount of layer covering ~ AgX₁10 layers^FourDouble molar amount is more preferable
Yes. (AgX₁| AgX_Four| AgX₃) The Ag
X_FourThe added molar amount of the layer is the AgX₁Of the added molar amount of the layer
0.02 to 10 times molar amount is preferable, 0.1 to 3 times molar amount
Amounts are more preferred. Normally, the gap difference becomes large
The more frequently the defect is formed, the higher the frequency.

The atmosphere of the dispersion medium solution during the nucleation is (10
0) It is necessary to create a surface forming atmosphere. In the case of nucleation carried out under Cl ⁻ excess concentration, most of the usual conditions (pCl0.
8 to 3.0, pH 2 to 9) is a (100) plane forming atmosphere. In the pH 1 to 7 range of the defect formation frequency, the higher the pH and the higher the pCl value, the higher the defect formation frequency. Here, pCl = -log [Cl ^- mol / liter]. When many defects are introduced into one grain, the frequency of thick grains in the finally obtained AgX emulsion increases. Therefore, it is not preferable that the amount of defects introduced is too large. It is necessary to select the defect forming conditions so that the finally obtained AgX emulsion is in the embodiment of the present invention. The aspect of the present invention can be obtained by uniformly forming the gap surface between the nuclei.

The dispersion medium concentration of the dispersion medium solution at the time of nucleation is 0.
1 to 10% by weight is preferable, and 0.3 to 5% by weight is more preferable. pH 1-10 is preferable and 2-8 is more preferable. The temperature is preferably 10 to 80 ° C, more preferably 30 to 60 ° C. In many cases, the lower the temperature at which the gap surface is formed is lower than 30 °, the lower the frequency of defect formation. This indicates that a certain temperature or higher is required for forming the defect. The excess Br ⁻ concentration is preferably 10 ⁻² mol / liter or less, more preferably 10 ^−2.5 mol / liter or less. The excess Cl ⁻ concentration is preferably pCl = 0.8 to 3.0, more preferably 1.2 to 2.8.

It can be included salt solution in the dispersion medium ^- [0014] silver salt solution and / or X during nucleation is added to allow for uniform nucleation. Dispersion medium concentration is 0.1% by weight
The above is preferable, 0.1 to 2% by weight is more preferable,
0.2 to 1% by weight is more preferable. Molecular weight 3000-6
10,000, preferably 8,000 to 40,000 low molecular weight gelatin is more preferable. Furthermore Ag ⁺ solution and X ^- liquid addition porosities 3
10 ^15, preferably through 30 to 10 ¹⁵ porous addition system, it is more preferably added directly to the liquid. The details are described in JP-A-3-21339 and 4-193336.
The description in Japanese Patent Application No. 4-240283 can be referred to. Gelatin having a lower methionine content has a higher frequency of defect formation. Methionine content is 1 to
From 60 μmol / g of gelatin, the most preferable gelatin can be selected and used according to each case.

Excess X ^- salt concentration during nucleation, or excess A
By lowering the g ⁺ salt concentration, the mixing ratio of twin grains can be reduced. In addition, the mixing ratio increases as the concentration of the dispersion medium decreases and the stirring level deteriorates. Therefore, the conditions may be selected by the try-and-error method so that the finally obtained particles fall within the aspect of the present invention. After forming a screw dislocation defect by the formation of the halogen composition gap surface during nucleation and the halogen conversion reaction at the interface, the temperature is then raised preferably by -10 ° C or higher, more preferably by 20 to 70 ° C. Let it mature. Aging is preferably performed in a (100) plane forming atmosphere. Aging conditions are preferably selected from the nucleation condition range. By the ripening, tabular grains are preferentially grown, non-tabular grains are extinguished, and the tabular grain ratio is increased. The ripening rate generally increases with increasing pH in the pH 1-6 region and with increasing Cl ^- concentration in the pCl 1-3 region.

After increasing the tabular grain ratio, a solute is then added to further grow the tabular grains. As a solute addition method, 1) an ion addition method (a method of adding an Ag ⁺ liquid and an X ⁻ liquid), 2) a method of previously forming AgX fine particles and adding the fine particles, 3) a combination method of both Can be mentioned. In order to preferentially grow the tabular grains in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range where Ostwald ripening is not performed. That is, it is necessary to control the concentration at a low supersaturation level with high accuracy. Method 2) is more preferable because it enables this. It is preferable because each tabular grain can be grown uniformly.

In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
Add an AgX fine grain emulsion having a diameter of 06 to 0.006 μm,
The tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or continuously. The fine grain emulsion can be continuously prepared by supplying the AgNO ₃ solution and the X ^- salt solution in a mixer provided in the vicinity of the reaction vessel, and immediately added to the reaction vessel immediately, or in advance in another vessel. It is also possible to add it continuously or intermittently after it is prepared in a batch manner.
The fine grain emulsion can be added in a liquid form or as a dry powder. It is also possible to mix the dry powder with water immediately before addition to liquefy it and add it.
The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. If the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that the fine particles are substantially free of twinned grains. Here, the multi-twin grain means a grain having two or more twin planes per grain. The term "substantially free" means that the ratio of multiple twin grains is 5%.
It is preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin crystal grains are contained. Furthermore, it is preferable that the screw dislocation is not substantially contained. Here, the term "substantially free" is in accordance with the above-mentioned rules.

The halogen composition of the fine particles is AgCl, Ag
Br, AgBrl (I ^- content is preferably 10 mol% or less, more preferably 5 mol% or less) and a mixed crystal of two or more thereof. For other details, see Japanese Patent Application No. 4-2141.
The description of No. 09 can be referred to.

As a dispersion medium for nucleation, ripening and growth, a conventionally known dispersion medium for an AgX emulsion can be used, but the methionine content is preferably 0 to 50 μmol / g, more preferably 0. -30 μmol / g gelatin can be preferably used. When the gelatin is used during ripening and growth, thinner tabular grains having a uniform diameter size distribution are formed, which is preferable. In addition, Japanese Patent Publication Sho 52
-16365, Journal of the Photographic Society of Japan, Volume 29 (1), 17,
22 (1966), Volume 30 (1), 10, 19 (19
67), Vol. 30 (2), 17 (1967), 33.
The synthetic polymer described in Volume (3), 24 (1967) can be preferably used as a dispersion medium. In addition, European patent 0
The crystal habit controlling agent described in No. 534395A1 can be used in combination. The concentration of the dispersion medium is preferably 0.1 to 10% by weight, and the control agent can be used preferably at 10 ^-1 to 10 ^-6 mol / liter, more preferably 10 ^-2 to 10 ^-5 mol / liter. . These can be added at any time from before nucleation to the end of growth. It can be added in the form of additional addition to the existing dispersion medium, or can be added after removing the existing dispersion medium by centrifugation or the like.

[0020] The aging, dispersing medium concentration at the time of growth, pH, X ^-
Regarding the range of salt concentration and the method of adding the Ag ⁺ liquid and the X ⁻ liquid (using a porous material addition system, containing a dispersion medium), the description of the nucleation can be referred to. The temperature is preferably 25 ° C or higher, more preferably 30 to 80 ° C.
The growth is also preferably performed in a (100) plane forming atmosphere.

Under the respective conditions, the atmosphere for forming the (100) plane is such that nucleation, ripening or growth is carried out, and 60% to 100%, preferably 80% to 100%, and more preferably 90% to 100% of the surface of the grain is formed. It refers to the condition for the (100) plane.
The surface ratio is T. Tani, Journal of Imaging Science. 29
Vol., 165 (1985).

In addition to the method for producing the AgX particles of the present invention, the following method can be mentioned. 1) Nucleation → Selectively grow tabular grains under low supersaturation concentration to increase size difference between tabular grains and non-tabular grains → Extinguish non-tabular grains by Ostwald ripening, 2) Nucleation → 10
Grow at a low supersaturation temperature at which the temperature is raised to ℃ or more and Ostwald ripening is performed. That is, the tabular grains are grown with the disappearance of fine particles other than the tabular grains. The particles of the present invention can be obtained by such careful examination.

The tabular grains are mainly composed of AgCl, but the grains can have various halogen composition structures. As a specific example, Japanese Patent Application No. 5-96250
The multi-structured particles described in No. 1 can be mentioned. That is, B
A mode in which the r ^- content and / or the I ^- content is high on the surface of the particle, a mode in which the edge portion of the particle is high, a mode in which the intermediate layer of the particle is high, and a mode in which the main plane of the particle is high Can be mentioned. In the present invention, it is preferable that the location and number (/ cm ² ) of chemically sensitized nuclei are controlled. Regarding this, JP-A-2-838 and 2-146.
No. 033, No. 1-120151, No. 3-121445.
Japanese Patent Application Laid-Open No. 62-74540, Japanese Patent Application No. 3-73266.
No. 3-140712 and No. 3-1155872 can be referred to. The AgX emulsion grains produced by the method of the present invention can also be used as a blend with one or more other AgX emulsions.

Additives that can be added to these emulsions from the grain formation to the coating step are not particularly limited, and any conventionally known photographic additives can be added. For example, AgX solvent, a dopant for AgX particles (for example, Group 8 noble metal compounds, other metal compounds, chalcogen compounds,
SCN compound, etc.), dispersion medium, antifoggant, sensitizing dye (for blue, green, red, infrared, panchromatic, ortho etc.), supersensitizer, chemical sensitizer (sulfur, selenium, tellurium, gold) And Group 8 noble metal compounds, phosphorus compounds, rhodan compounds, reduction sensitizers alone or in combination of two or more thereof), foggants, emulsion precipitants, surfactants, hardeners, dyes, color image-forming agents , Color photographic additives, soluble silver salts, latent image stabilizers, developers (hydroquinone compounds, etc.), pressure desensitizing agents,
Examples thereof include matting agents.

The black and white photographic light-sensitive material produced by using the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

As the support of the photographic light-sensitive material of the present invention,
It must have a thickness of 150-250 μm. This is essential from the viewpoint of handleability when observing on a medical Schaukasten. Further, the material is preferably a polyethylene terephthalate film, and particularly preferably colored blue. The support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment for improving the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex or the like may be provided, and a gelatin layer may be further provided thereon. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrocolloid layer can be further improved.

As various additives and the like used in the photographic light-sensitive material of the present invention, those described in the following relevant parts can be used.

Item 1) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035.

2) Antifoggant, Stabilization JP-A-2-68539, page 10, lower left column, line 17 to the same agent, page 11, upper left column, line 7 and page 3, lower left column, line 2 to 4 Lower left column of the page.

3) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, left lower column, line 20, JP-A-3-94249, page 6, lower left column, line 15 From page 11, upper right column, line 19

4) Surfactants and Antistatics JP-A-2-68539, page 11, upper left column, line 14 to the same antistatic agent, page 12, upper left column, line 9

5) Matting agent, slip agent, JP-A-2-68539, page 12, upper left column, line 10 to the same right plasticizer, upper column, line 10, page 14 left lower column, line 10 to the same lower right column 1 Line.

6) Hydrophilic Colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16

7) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6

8) Polyhydroxyben JP-A-3-39948, page 11, upper left column to page 12, left genus, lower column, EP Patent No. 452772A.

9) Layer Structure Japanese Patent Laid-Open No. 3-198041.

Ascorbic acid or its derivative used in the developing solution of the present invention is preferably a compound represented by the general formula (I).

General formula (I)

[Chemical 1]

In the formula, R ₁ and R ₂ each represent a hydroxy group, an amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonylamino group, a mercapto group and an alkylthio group, and X is a carbon atom or X constitutes a 5- or 6-membered ring in cooperation with two vinyl carbons which are composed of an oxygen atom or a nitrogen atom and are substituted by R ₁ and R ₂ and a carbonyl carbon. Hereinafter, the general formula (I) will be described in detail. In the formula, R ₁ and R ₂ are each a hydroxy group, an amino group (as a substituent, an alkyl group having 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, an n-butyl group, a hydroxyethyl group and the like as a substituent). ), Acylamino group, (acetylamino group, benzoylamino group, etc.),
Alkylsulfonylamino group, (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group, etc.), mercapto group, alkylthio group ( Methylthio group, ethylthio group, etc.). R ₁ , R
Preferred examples of ₂ include a hydroxy group, an amino group,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group. X is composed of a carbon atom, an oxygen atom, or a nitrogen atom, and X in combination with two vinyl carbons substituted by R ₁ and R ₂ and a carbonyl carbon.
Constitutes a 5- or 6-membered ring. As a specific example of X, -O-,
_{-C (R 3) (R 4} ) -, - C (R 5) =, - C (=
O) -, - N (R 6) -, - N =, constructed by combining. However, R ₃ , R ₄ , R ₅ , and R ₆ are hydrogen atoms, alkyl groups having 1 to 10 carbon atoms which may be substituted (such as a hydroxy group, a carboxy group, and a sulfo group) and carbon numbers. And 6 to 15 aryl groups which may be substituted (alkyl groups, halogen atoms, hydroxy groups, carboxy groups, sulfo groups can be mentioned as substituents), hydroxy groups and carboxy groups. Furthermore this 5
A saturated or unsaturated condensed ring may be formed in the to 6-membered ring. Examples of the 5- or 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Examples of the preferred 5- or 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring, and a uracil ring.

Specific examples of compounds are shown below.

[0041]

[Chemical 2]

[0042]

[Chemical 3]

[0043]

[Chemical 4]

[0044]

[Chemical 5]

[0045]

[Chemical 6]

Ascorbic acids used in the developing solution used in the present invention are endiol type (Endiol), enaminol type (Enaminol), endiamine type (Endiamin), thiol enol type (Thiol-Enol) and enamine-thiol type ( Enamin-Thiol) is generally known as a compound. Examples of these compounds are described in US Pat. No. 2,688,5
49 and JP-A-62-237443. Methods for synthesizing these ascorbic acids are also well known, and are described in, for example, Tsujio Nomura and Hirohisa Omura, "The Chemistry of Reductones" (Uchida Lao Tsukuba Shinsha 1969). The ascorbic acid used in the present invention can also be used in the form of an alkali metal salt such as lithium salt, sodium salt and potassium salt. These ascorbic acids are contained in an amount of 1 to 100 g, preferably 5 to 80 g per liter of the developing solution.
g is preferably used.

The developer of the present invention contains a development inhibitor such as potassium bromide or potassium iodide; an organic solvent such as dimethylformamide, methyl cellosolve, hexylene glycol, ethanol or methanol; 5-methylbenz as a benztriazole derivative. There are triazole, 5-bromobenztriazole, 5-chlorobenztriazole, 5-butylbenztriazole, benztriazole and the like, but 5-methylbenztriazole is particularly preferable. Nitroindazole is preferably 5 nitroindazole, 6 nitroindazole, 4 nitroindazole. , 7 nitroindazole, 3 cyano-5-nitroindazole, etc., but 5-nitroindazole is particularly preferable. Particularly when a compound such as 5-nitroindazole is used, it is dissolved in advance in a part different from the part containing the dihydroxybenzene type developing agent or the sulfite preservative, and both parts are mixed and water is added at the time of use. Is common. Further, if necessary, a color tone agent, a surfactant, a water softener, a hardener and the like may be contained.

As the chelating agent in the developing solution, ethylenediaminedioltohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, Diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, 1,3-diaminopropanoltetraacetic acid, triethylenetetraminehexaacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylene Phosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1- Phosphonoethane-2-carboxylic acid, 1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphono-1,3,
Examples thereof include 3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate, and particularly preferably, for example, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diaminopropanol. Tetraacetic acid, glycol ether diamine tetraacetic acid, hydroxyethyl ethylenediamine triacetic acid, 2-phosphonobutane-
1,2,4-tricarboxylic acid, 1,1-diphosphonoethane-2-carboxylic acid, nitrilotrimethylenephosphonic acid, ethylenediaminetetraphosphonic acid, diethylenetriaminepentaphosphonic acid, 1-hydroxypropylidene-1,1-diphosphonic acid, 1- Aminoethylidene
1,1-diphosphonic acid, 1-hydroxyethylidene-
There are 1,1-diphosphonic acids and their salts.

In the present invention, as a silver stain preventing agent in a developing solution, JP-B-56-46585 and JP-B-62-4702 are used.
Japanese Patent Publication No. 62-4703, US Pat. No. 4,254,
215, 3,318,701, JP-A-58-20.
No. 3439, No. 62-56959, No. 62-1782.
47, Japanese Patent Application Laid-Open No. 1-20249, Japanese Patent Application No. 3-949.
The compounds described in No. 55, No. 3-112275 and No. 3-233718 can be used.

In the present invention, it is particularly preferable to use 1-phenyl-3-pyrazolidones or p-aminophenols together with ascorbic acids. 3 used in the present invention
-Pyrazolidone-based developing agents include 1-phenyl-3
-Pyrazolidone, 1-phenyl-4,4-dimethyl-3
-Pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,
4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-
p-tolyl-4,4-dimethyl-3-pyrazolidone, 1
-P-tolyl-4-methyl-4-hydroxymethyl-3
-Such as pyrazolidone. Developing agent is usually 0.001
It is preferably used in an amount of mol / liter to 1.2 mol / liter. Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol and N- (4-hydroxyphenyl). Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like are available, but N-methyl-p-aminophenol is preferred.

A dialdehyde hardener can be used in the developer of the present invention. Examples of the dialdehyde compound include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succinaldehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β.
-Ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde, α, α
-Diethylsuccindialdehyde, butyl maleic dialdehyde, bisulfite adducts thereof, and the like. The most preferred of these is glutaraldehyde or its bisulfite adduct. The amount of the dialdehyde compound in the developing solution is preferably 0.5 to 100 g, particularly 0.5 to 30 g per liter. Since the above-mentioned nitroindazoles and dialdehyde compounds gradually deteriorate in the developing solution (use solution), the form of the pretreatment kit before preparing the use solution contains ascorbic acids. It should be stored separately from the alkaline part in neutral and acidic solutions. The pH of the developer of the present invention is preferably in the range of 8.5 to 12. More preferably pH 9 to 1
The range is up to 2.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
Includes pH adjusting agents such as potassium carbonate, sodium triphosphate, potassium triphosphate. Examples of the sulfite preservative used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite and potassium metabisulfite. The sulfite content is preferably 0.01 mol / liter or more, particularly preferably 0.02 mol / liter or more. Further, the upper limit is preferably up to 2.5 mol / liter. In addition, 22 of "Photographic Processing Chemistry" by LFA Mason, published by Focal Press (1966)
6 to 229, U.S. Pat. Nos. 2,193,015, 2,592,364, and JP-A-48-64933 may be used.

In general, a boric acid compound (for example, boric acid, borax) is often used as a pH buffering agent in the developing solution, but the boric acid compound is used in the ascorbic acid-containing developing solution of the present invention. It is preferable not to contain substantially.
When the ascorbic acid-containing developer contains a boric acid compound, the effect of the present invention cannot be obtained even in combination with the packaging material of the present invention having a low oxygen transmission rate. The relationship between the presence or absence of the boric acid compound and the effect in the system of the present invention was completely unexpected.

A method for preparing a treating agent used in the present invention is described in JP-A-61-177132 and JP-A-3-134666.
The method described in JP-A-3-67258 can be used. As the method of replenishing the developing solution as the processing method of the present invention, the method described in Japanese Patent Application No. 54131/1992 can be used.

In addition, "Chemistry of antibacterial and antifungal" by Hiroshi Horiguchi,
Compounds such as those described in Sankyo Publishing (Showa 57), "Handbook of Antibacterial and Antibacterial Technology", Japan Society for Antibacterial and Antibacterial Agent, Hakuhodo (Showa 61) may be included. The developed, fixed and washed (or stabilized) photographic material is dried by squeezing washing water, that is, squeeze rollers.
Drying is performed at about 40 ° C to about 100 ° C, and the drying time is appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 seconds.
Minutes, particularly preferably at 40-80 ° C. for about 5 seconds
2 minutes.

When a dry-to-dry development process for 100 seconds or less is performed, a roller made of a rubber material as described in JP-A-63-151943 is developed in order to prevent development unevenness peculiar to rapid processing. It is applied to a roller at the tank outlet, and as described in JP-A-63-151944, the discharge flow rate for stirring the developing solution in the developing solution tank is set to 10 m / min or more. As described in JP-A No. 63-264758, it is more preferable to stir more strongly than during standby at least during the development processing.

There are no particular restrictions on the photographic light-sensitive material used in the development processing method of the light-sensitive material of the present invention, and general black-and-white light-sensitive materials are mainly used. In particular, it is used for photographic materials for laser light sources, printing sensitive materials, medical direct photographing X-ray sensitive materials, medical indirect photographing X-ray sensitive materials, CRT image recording sensitive materials, microfilm, general photographing sensitive materials and the like. You can also The present invention will be specifically described below with reference to examples.

[0058]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the practical embodiments of the present invention are not limited to these. Example 1 Inventive Emulsion A 1200 ml of an aqueous gelatin solution (containing 18 g of deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g, pH 4.3) was placed in a reaction vessel, and the temperature was maintained at 43 ° C. and Ag- 1 solution (20 ml of AgNO _{3 in} 100 ml)
g, 0.8 g of the gelatin, 0.2 ml of HNO ₃ 1N solution) and X-1 solution (6.9 g of NaCl in 100 ml, 0.8 g of the gelatin, 0.3 ml of NaCH 1N solution).
Simultaneous addition of only 12 ml at 4 ml / min. After stirring for 2 minutes, Ag-2 solution (containing 2 g of AgNO ₃ in 100 ml, 0.8 g of the gelatin and 0.2 ml of HNO ₃ 1N solution) and X-2 solution (1.4 g of KBr in 100 ml, 31 ml of containing 0.8 g of gelatin and 0.2 ml of NaOH 1N solution)
Only 19 ml of the mixture was added at the same time. After stirring for 2 minutes,
The Ag-1 solution and the X-1 solution were simultaneously mixed and added at 36 ml at 48 ml / min. NaCl-1 solution (100 ml of NaCl
20 ml (including 10 g) was added to adjust the pH to 4.8 and the temperature was raised to 75 ° C. After aging for 20 minutes, the temperature is adjusted to 60
After lowering the temperature to ℃ and adjusting the pH to 5.0, A at a silver potential of 130 mV
g-3 solution (containing 10 g of AgNO _{3 in} 100 ml) and X
-3 solution (containing 3.6 g of NaCl in 100 ml) by C.
DJ (controlled double jet) was added. The flow rate at the start of addition was 7 ml / min, and the flow rate was accelerated at 0.1 ml / min per minute, and 400 ml of Ag-3 solution was added.

A precipitating agent was added and the temperature was lowered to 30 ° C.
After washing with precipitation, an aqueous gelatin solution was added, and the pH was adjusted to 6.
2, adjusted to pCl 3.0. Collect a part of the emulsion
Then, a transmission electron micrograph image of a replica of the particle (hereinafter
The "TEM image" is observed. Shape characteristic value of the particle
Was as follows: ((100) flat with aspect ratio 2 or more
Total projected area of plate-like particles / sum of projected areas of all AgX particles) =
a₁= 0.91, aspect ratio 2 or more (100) tabular grains
Average aspect ratio of child (average diameter / average thickness) = a ₂=
3.4, average of (100) tabular grains with aspect ratio of 2 or more
Diameter = a₃= 1.0 μm, (total projected area of twin grains /
(Total projected area of (100) tabular grains with a spectral ratio of 2 or more) =
a_Four= 0, (with an aspect ratio of 2 or more, an edge ratio of 1 to 1.4
Of (100) tabular grain total projected area / total AgX grain projection
Sum of shadow areas) = a_Five= 0.86, (aspect ratio 2 or more
70% of the total projected area from the largest of (100) tabular grains
Coefficient of variation of the diameter distribution of the particles when taken out)
= A₆= 0.059, average thickness = a₇= 0.29 μm

Thereafter, this emulsion was heated to 60 ° C., sodium thiosulfate was added, 2 minutes after that, chloroauric acid and potassium thiocyanate were added, and 65 minutes later, 4-hydroxy-
Emulsion A was prepared by adding methyl-1,3,3a, 7-tetrazaindene and then rapidly cooling to solidify. Emulsion A is AgB
It is a high silver chloride (100) tabular emulsion containing 0.76 mol% of r.

1. Comparative Example Emulsion B Preparation 32 g of gelatin was dissolved in 1 liter of water, and 0.3 g of potassium bromide and 5 g of sodium chloride were placed in a container heated at 60 ° C.
g and compound [I]

[0062]

[Chemical 7]

After adding 46 mg, 444 ml of an aqueous solution containing 80 g of silver nitrate and 452 ml of an aqueous solution containing 45 g of potassium bromide and 5.5 g of sodium chloride were added by the double jet method over about 30 minutes, and then 80 g of silver nitrate was added. An aqueous solution containing 400 ml of an aqueous solution, 46.4 g of potassium bromide, 5.7 g of sodium chloride and potassium hexachloroiridium (III) (10 ^-7 mol / mol silver), 415 ml of an aqueous solution.
And were added by the double jet method over about 25 minutes to give cubic monodispersed silver chlorobromide grains having an average grain size (projected area diameter) of 0.67 μm (variation coefficient of projected area diameter: 10
%) Was prepared.

This emulsion was desalted by a coagulation method, and then 62 g of gelatin and 1.75 g of phenoxyethanol were added,
It was adjusted to pH 6.5 and pAg 8.5. After that, 65 ℃
The temperature was raised to, 2 mg of sodium thiosulfate was added, 2 minutes after that, 5 mg of chloroauric acid was added, and 80 minutes later, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene was added to 5
After adding 12 mg, it was rapidly cooled and solidified to obtain Emulsion B.

2. Preparation of emulsion coating solution The following chemicals were added to emulsions A and B per mol of silver halide to prepare emulsion coating solutions.

B. Spectral sensitizing dye [I] 138 mg b. Spectral sensitizing dye [II] 42.5 mg c. Polyacrylamide (molecular weight 40,000) 8.54 g d. Trimethylolpropane 1.2 g e. Sodium polystyrene sulfonate (average molecular weight 600,000) 0.46 g f. Latex of poly (ethyl acrylate / metal acrylic acid) 32.8 g. 1,2-bis (hinylsulfonylacetamide) ethane 2 g

Spectral sensitizing dye [I]

[0068]

[Chemical 8]

Spectral sensitizing dye [II]

[0070]

[Chemical 9]

3. Preparation of Surface Protective Coating Solution for Emulsion Layer The container was heated to 40 ° C. and the following chemicals were added to prepare a coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (average molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. Sodium t-octylphenoxyethoxyethane sulfonate 1.5 g. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.3 g h. C ₈ H ₁₇ SO ₃ K 84 mg Re. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. 0.2 g of NaOH. Methanol 78cc. 1,2-Bis (vinylsulfonylacetamide) ethane Adjustment so that the swelling amount shown in Table 1 was obtained. Compound [II] 52 mg

[0072]

[Chemical 10]

4. Preparation of Back Layer Coating Liquid The container was heated to 40 ° C., and the chemicals shown below were added to prepare a back layer coating liquid. I. Gelatin amount 100 g b. Dye [I] 2.39 g

[0074]

[Chemical 11]

C. Sodium polystyrene sulfonate 1.1 g d. Phosphoric acid 0.55 g E. Poly (ethyl acrylate / methacrylic acid) latex 2.9 g f. Compound [II] 46 mg g. Oil dispersion of dye [II] described in JP-A-61-285445 246 mg as dye itself [II]

[0076]

[Chemical 12]

H. Oil dispersion of dye [III] described in JP-A-61-285445 46 mg as dye itself [III]

[0078]

[Chemical 13]

5. Preparation of Back Surface Protective Coating Solution The container was heated to 40 ° C. and the following chemicals were added to prepare a coating solution.

B. Gelatin 100 g b. Sodium polystyrene sulfonate 0.3 g c. Polymethylmethacrylate fine particles (average particle size 3.5 μm) 4.3 g d. Sodium t-octylphenoxyethoxyethane sulfonate 1.8 g e. Sodium polyacrylate 1.7 g f. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.6 g g. C ₈ H ₁₇ SO ₃ K 268 mg Chi. _{C 8 F 17 SO 2 N (} C 3 H 7) 8 CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 45mg Li. NaOH 0.3 g Nu. 131 mg of methanol Prepare so that the amount of 1,2-bis (vinylsulfonylacetamide) ethane back layer and its surface protective layer is 2.2% by weight based on the total amount of gelatin. Compound [II] 45 mg 6. Preparation of coating sample The coating solution for the back layer described above was coated with the coating solution for the surface protective layer of the back layer on one side of the polyethylene terephthalate support colored in blue, and the gelatin coating amount of the back layer was 2.6.
9 g / m ^2, a gelatin coating amount of the surface protective layer of the back layer was coated to a 1.3 g / m ^2. Following this, the opposite aforementioned emulsion coating solution side and the surface protective layer coating solution of the support, the coating amount of Ag is 2.4 g / m ² of emulsion coating solution, the amount of gelatin 1.85 g / m ² and The surface protective layer was coated such that the amount of gelatin was 1.2 g / m ² to obtain a coated sample.

7. Sensitometry Method The coated sample thus prepared was subjected to sensitometry by the following method to measure the photographic sensitivity. The coated sample at 25 ° C,
The coating was kept at 60% temperature and humidity for 7 days after coating, and exposed using a 633 nm He-Ne laser exposure unit of AC-1 manufactured by Fuji Photo Film Co., Ltd. In addition, the 780 nm semiconductor laser exposure unit of FCR-7000 manufactured by Fuji Photo Film Co., Ltd. was modified to produce AlGaInP 5 mW manufactured by NEC Corporation.
Exposure was carried out using a 678 nm semiconductor laser equipped with a light emitting portion.

8. Development Method Next, development was carried out by an automatic processor by the following method. The drive motor gear of the automatic developing machine CEPROS-M manufactured by Fuji Photo Film Co., Ltd. was modified to set the dry to dry processing time to 30, 45 and 90 seconds.

Developer composition Diethylenetriaminepentaacetic acid 4.0 g Potassium carbonate 55.2 g (0.4 mol / liter) Sodium sulfite 15.0 g Ascorbic acid 40.0 g 1-Phenyl-4-methyl-4-hydroxymethyl-3- Pyrazolidone 5.0 g 5-Methyl-benztriazole 0.06 g 2-Mercaptobenzimidazole-5-sulfonic acid 2,3,5,6,7,8-hexahydro-2-thioxo-4- (1H) .quinazolinone 0. 05 g Potassium bromide 2.0 g Water was added to 1 liter (pH is adjusted to 10.00 with potassium hydroxide.)

Fixer composition Ammonium thiosulfate 140 g Sodium sulfite 15 g Disodium ethylenediaminetetraacetate / dihydrate 25 mg Sodium hydroxide 6 g upto 1000 ml pH 5.10

Processing speed: Dry to Dry 30 ″ 45 ″ 90 ″ Development temperature: 35 ° C. (8 ″ 13 ″ 25 ″) Fixing temperature: 32 ° C. Drying temperature: 55 ° C. Replenishment amount ………… Developer 15 ml / 10 × 12 inches Fixer 15 ml / 10 × 12 inches

The sensitivity is expressed by the reciprocal of the exposure amount which gives a density of Fog + 1.0.
It was set to 0. The results are shown in Table 1.

[0087]

[Table 1]

As is apparent from Table 1, the light-sensitive material of the present invention and the developer exhibit good photographic performance.

Example 2 Inventive Emulsion C To a reaction vessel was placed 1200 ml of an aqueous gelatin solution (containing 20 g of deionized alkali-treated gelatin, pH 4.3),
While maintaining the temperature at 41 ° C., the Ag-1 liquid of Example 1 and X
Solution-1 was co-mixed with 12 ml at 50 ml / min. Two
After stirring for a minute, the Ag-2 solution and the X-2 solution were simultaneously mixed and added in an amount of 22 ml at 62 ml / min. After stirring for 2 minutes, Ag
Solution-1 and Solution X-1 were simultaneously mixed and added at 38 ml at 50 ml / min. 23 ml of NaCl-1 solution was added to adjust the pH to 5.0 and the temperature was raised to 75 ° C. After aging for 20 minutes, the temperature was lowered to 65 ° C., AgCl fine grain emulsion (average particle diameter 0.08 μm) was added at a rate of 4 × 10 ⁻³ mol / min AgCl addition, and after 10 minutes addition, AgCl 10 ^{−. It} added for 70 minutes by the accelerated addition method of ⁴ mol / min. After the addition, the mixture was aged for 8 minutes, a precipitating agent was added, the temperature was lowered to 30 ° C., and the precipitate was washed with water. An aqueous gelatin solution was added, and the pH was adjusted to 6.
2, adjusted to pCl 3.0. When a part of the emulsion was sampled and a transmission electron micrograph image of a replica of AgX grains was observed, the shape characteristic values of the grains were as follows.
a ₁ = 0.92, a ₂ = 4.5, a ₃ = 1.0 μm, a
_{4 = 0, a 5 = 0.82} , a 6 = 0.077, a 7 =
0.22 μm, silver chloride content 98.26 mol%

After that, soluble salts were removed by the coagulation sedimentation method. The temperature was raised again to 40 ° C., 7.5 g of gelatin, 0.6 g of phenoxyethanol and 0.2 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted to 6.2 and pCl3.0 with caustic soda. To the emulsion thus prepared, 1 × 10 ⁻⁵ mol / mol Ag of thiosulfonic acid compound-I was added while maintaining the temperature at 58 ° C. with stirring, and then 8 × 10 5 of sensitizing dye-I was added. ^-Four
Mol / mol Ag and sensitizing dye-II were added at 3 × 10 ⁻⁶ mol / mol Ag.

[0091]

[Chemical 14]

[0092]

[Chemical 15]

Sodium thiosulfate, selenium compound-I, chloroauric acid and potassium thiocyanate were added, and after optimal chemical sensitization, the mixture was cooled to 35 ° C. to prepare Emulsion C of the present invention.

[0094]

[Chemical 16]

40 g of gelatin was dissolved in 2000 ml of distilled water and the solution was kept at 40 ° C. with stirring in a reaction vessel. After adjusting the pH to 3.00 with nitric acid, 33.0 ml of 1 molar silver nitrate aqueous solution and 34.0 ml of 1 molar potassium bromide aqueous solution were added to this solution in 20 seconds.
After the addition was completed, pAg was adjusted to 6.5 with an aqueous silver nitrate solution, and p
Adjust H to 6.00 with aqueous sodium hydroxide solution to 75
The temperature was raised to ° C. Immediately after the temperature was raised, pAg was adjusted to 5.79 and physical ripening was carried out for 3 hours. Continuously 30 minutes later.
18.7 ml of a 01 molar silver nitrate aqueous solution and a 0.01 molar aqueous potassium iodide solution were added by the control double jet method while keeping pAg at 5.79. The obtained emulsion was centrifuged at 6000 rpm for 10 minutes and concentrated to 200 ml. After repeating the above operation 5 times, the concentrated emulsion was mixed and 5 g of gelatin was added. In the obtained emulsion B, tabular silver halide grains substantially composed of silver iodobromide having two parallel main planes (100) planes and an aspect ratio of 2 or more were all projections of silver halide grains. It occupies 84% of the area and the average edge length is 1.12 μm.
The thickness between the principal planes was 0.18 μm, and the silver iodide content relative to silver bromide was 0.6 mol%. After this, soluble salts were removed by the coagulation sedimentation method. The temperature was raised to 40 ° C again, and 30 g of gelatin and 2.35 of phenoxyethanol were used.
g and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and the pH was adjusted with caustic soda and silver nitrate solution.
It was adjusted to 5.90 and pAg 8.00. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, thiosulfonic acid compound-I

[0096]

[Chemical 17]

1 × 10 ^-5 mol / mol Ag was added, and then 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene 20mg and Sensitizing Dye-I

[0098]

[Chemical 18]

80 mg of was added. Subsequently, 0.25 mg of sodium thiosulfate, 0.3 mg of selenium compound-I, 0.5 mg of chloroauric acid and 20 mg of potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of comparative tabular grain D was completed.

[0100]

[Chemical 19]

Preparation of Coating Sample A coating sample was prepared by adding the following chemicals to 1 mol of silver halide of Emulsions C and D to prepare a coating solution. -Gelatin (including Gel in emulsion) The film thickness was adjusted by changing this amount.・ Trimethylolpropane 9g ・ Dextran (average molecular weight 39,000) 18.5g ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8g ・ Hardener 1,2-bis (vinylsulfonylacetamide) ethane Depending on this amount The amount of swelling was adjusted. -Compound-I 34 mg-Compound-II 4.8 g-Compound-III 15 mg

[0102]

[Chemical 20]

[0103]

[Chemical 21]

Dye Emulsion A was added to the above coating solution so that the amount of Dye-I was 10 mg / m ² per side.

[0105]

[Chemical formula 22]

(1) Preparation of Dye Emulsion A 60 g of the above dye-I and the following high boiling organic solvent-I
62.8 g, -II 62.8 g and ethyl acetate 333
g was melted at 60 ° C. Next, 65 cc of 5% aqueous solution of sodium dodecyl sulfonate, 94 g of gelatin and 581 of water.
cc was added, and the mixture was emulsified and dispersed at 60 ° C. for 30 minutes with a dissolver. Next, 2 g of the following compound-IV and 6 liters of water were added, and the temperature was lowered to 40 ° C. Next, using Asahi Kasei's ultrafiltration lab module ACP1050,
The mixture was concentrated to kg, and 1 g of the compound-IV was added to prepare a dye emulsion A.

[0107]

[Chemical formula 23]

The surface protective layer was prepared and prepared so that each component had the following coating amount. -Gelatin The film thickness was adjusted by changing this amount.・ Sodium polyacrylate (average molecular weight 400,000) 0.080 g / m ²・ 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.015 g / m ²・ Coating aid-I 0.013 g / m ²・ Coating aid-II 0.045 g / m ²・ Coating aid-III 0.0065 g / m ²・ Coating aid-IV 0.003 g / m ²・ Coating aid-V 0.001 g / m ²・ Compound-V 1.7 mg / m ² · Compound-VI 100 mg / m ² · Polymethylmethacrylate (average particle size 3.7 μm) 0.087 g / m ² · Proxel (adjusted to pH 7.4 with NaOH) 0.0005 g / m ²

[0109]

[Chemical formula 24]

Preparation of Support (1) Preparation of Dye Dispersion B for Undercoat Layer The following Dye-II was ball milled by the method described in JP-A-63-197943.

[0111]

[Chemical 25]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO ₂ ) beads 4
00 ml (2 mm diameter) was added and the contents were milled for 4 days.
After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO ₂ beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the crushed dye had a wide range of diameters from 0.05 to 1.15 .mu.m, and the average particle size was 0.37 .mu.m. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D was obtained. (2) Preparation of support Corona discharge treatment was performed on a biaxially stretched 175 μm thick polyethylene terephthalate film, and the first undercoat liquid having the following composition was applied so that the coating amount was 4.9 cc / m ^2. It was applied with a wire bar coater and dried at 185 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used had a dye-I content of 0.04 wt%. * Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 158cc * 2,4-dichloro-6-hydroxy-s-triazine sodium salt 4% solution 41cc * Distilled water 801cc * The latex solution contains the following compounds as emulsifying dispersants in an amount of 0.4 wt% based on the latex solids.

[0113]

[Chemical formula 26]

On the above-mentioned first undercoat layer on both sides, a second undercoat layer having the following composition was applied on each side so that the coating amount was as described below, and 155 was applied on both sides by a wire bar coater system. It was applied and dried at ℃.・ Gelatin 80 mg / m ²・ Dye Dispersion B (as dye solid content) 8 mg / m ²・ Coating aid-VI 1.8 mg / m ²・ Compound-VII 0.27 mg / m ²・ Mat agent Average particle size 2 0.5 μm polymethylmethacrylate 2.5 mg / m ²

[0115]

[Chemical 27]

Preparation of Photographic Material The above emulsion layer and surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . A coated sample was prepared in this manner.

Sensitometry After the coated sample was exposed to green light for 1/20 second, it was processed by the following automatic developing machine. [Automatic processor processing] The automatic processor is "Fuji X Ray Processor CEPROS-M" manufactured by Fuji Photo Film Co., Ltd.
The drive shaft was modified so that the total processing time was 30 seconds. The dry blowing temperature was set to 55 ° C.

Developer Formulation PartA Potassium hydroxide 18.0 g Potassium sulfite 30.0 g Sodium carbonate 30.0 g Diethylene glycol 10.0 g Diethylenetriaminepentaacetic acid 2.0 g 1- (N, N-diethylamino) ethyl-5-mercaptotetrazole 0.1 g L-ascorbic acid 43.2 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.0 g Water was added to 300 ml.

Part B Triethylene glycol 45.0 g 3.3 ′ ′-Dithiobishydrocinnamic acid 0.2 g Glacial acetic acid 5.0 g 5 Nitroindazole 0.3 g 1-Phenyl-3-pyrazolidone 3.5 g Water 60 ml

PartC Glutaraldehyde (50%) 10.0 g Potassium bromide 4.0 g Potassium metabisulfite 10.0 g Water was added to 50 ml PartA 300 ml, PartB 60 ml and PartC5.
Add water to 0 ml to make 1 liter and adjust to pH 10.90. Part A 4.50 liters, Part B0.
90 liters and 0.75 liters of Part C were filled in a CE-DF1 bottle manufactured by FUJIFILM Corporation for use in 1.5 liters of the working solution. Development Starter Solution Acetic acid was added to the development replenisher solution to adjust the pH to 10.20, which was used as a development starter solution.

As the fixing solution, CE-F1 manufactured by Fuji Photo Film Co., Ltd. was used. Development temperature: 35 ° C. Fixing temperature: 35 ° C. Drying temperature: 55 ° C. Replenishment amount (both developing solution and fixing solution) 25 ml / 10 × 12 inches (325 ml / m ² ) Each as shown in Table 2. Sample 10 x 1
Table 2 also shows the results obtained by running 600 sheets of 2-inch size film.

[0122]

[Table 2]

Here, the sensitivity is a relative value of the reciprocal of the exposure amount required to obtain the fog plus blackening density of 1.0 with the developing solution. As the results in Table 2 show, the combination of the photosensitive material of the present invention and the developing solution is good, with no change in sensitivity at the start and in the running solution.

Example 3 During grain formation of the emulsion A of the present invention in Example 1, 10 ⁻⁷ mol of K ₃ IrCl ₆ was added per mol of silver halide, and further 10 ⁻⁵ mol of yellow blood salt was added. Other than that, coated samples were prepared in the same manner as in Examples 1 and 2, and
When the sensitometry was evaluated by the development processing method described in 2, excellent performance was confirmed.

Example 4 Particles were formed according to the recipe of Example 11B of EP 0534395A1. Add a precipitation agent to the emulsion,
Rinse with sedimentation washing method, add gelatin aqueous solution,
The pH was adjusted to 6.2 and pCl3.0. The grain shape of the TEM image of the replica of the emulsion grains was close to the grain shape shown in Fig. 5 of the same specification. A sensitizing treatment was performed in the same manner as in the emulsions A and C of the present invention of Examples 1 and 2, and a thickening agent and a coating aid were added, and coating was performed with the same coating formulation as that of the coating samples of the present invention of Examples 1 and 2. Samples were prepared and compared. The comparison item is Example 1,
The same method as in item 2 was performed. As a result, it was confirmed that the sample of the present invention showed excellent performance.

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[Procedure amendment]

[Submission date] May 24, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

In the particles having a high AgCl content of the present invention, only one of the four corners may be rounded preferentially. Here, "preferentially" means that the volume of the defective portion is 2 times or more of the other volume, 4 times or more in many cases, and 8 times or more in more cases. (Total projected area of the total projected area / tabular grains tabular grains having a preferential defect) = a _7, is preferably 0.08 or more, more preferably 0.15 to 1.
The aspect which occupies 0, more preferably 0.35 to 1.0 is preferable.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction content]

The AgX emulsion of the present invention can be manufactured as follows. Since the tabular grains grow preferentially in the edge direction, they become tabular grains. The defect that enables the preferential growth is called a screw dislocation defect in the present invention. The defects are formed by forming one or more, preferably 1 to 3 and more preferably 1 to 2 halogen composition gap surfaces during nucleation. More preferably Ag with high solubility
The X ₁ layer on, is formed by laminating a low AgX ₂ layer solubility than AgX ₁ layer. That is, it is effective to form the halogen composition gap surface accompanied by the halogen conversion reaction. Solubility is AgCl>AgBr> AgI,
Therefore, it can be said that the higher the Cl ⁻ content and the lower the Br ⁻ and I ⁻ contents, the higher the solubility. More specifically, the halogen composition structure of the nuclei formed during nucleation is, for example, (A
gX ₁ | AgX ₂ ) or (AgX ₁ | AgX ₄ | A
gX ₃ ). For the structure, for example, a silver salt solution (hereinafter referred to as “Ag ⁺ solution”) and a halogen salt solution (hereinafter referred to as “X ⁻ solution”) are simultaneously mixed and added, and the halogen composition of the X ⁻ solution at the gap surface. Can be formed by discontinuously changing, or X ^- solution is added to the dispersion medium solution and then Ag ⁺ solution is added to form AgX ₁ .
Then another X ^- solution was added, followed by Ag ⁺ solution, (A
A gX ₁ | AgX ₂ ) structure can be produced, or a combination thereof can be used. AgX ₁ and AgX
₂ , AgX ₁ and AgX ₄ , and AgX ₄ and AgX ₃ have a Cl ⁻ content or a Br ⁻ content of 25 to 100 mol%,
Preferably 50-100 mol%, more preferably 75-
They differ by 100 mol%. Further / or I ^- content of 5
They differ by 100 mol%, preferably 10-100 mol%, more preferably 30-100 mol%. Others, Cl
^- content difference or Br ^- in accordance with content: difference the provisions, I ^-
An embodiment in which the content difference is 0 to 5 mol% can be mentioned. The size of the nucleus is preferably 0.15 μm or less, 0.0
1 to 0.1 μm is more preferable.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

Nucleation two-stage addition (AgX₁｜ A
gX₂) In case of AgX₁: AgX ₂Molar ratio of nuclei
Formation of three-stage addition (AgX₁| AgX_Four| AgX
₃) AgX₁: AgX_Four: AgX₃The molar ratio of
The most preferable embodiment of the present invention can be obtained by variously changing the method of drawing.
It is possible to select and use the nuclear molar ratio. (AgX
₁| AgX₂), AgX₂Layer thickness is AgX₁layer
It is preferable to cover the surface of 1 layer or more on average with 3 lattices
Amount of layer covering ~ AgX₁10 layers^FourDouble molar amount is more preferable
Yes. (AgX₁| AgX_Four| AgX₃) The Ag
X_FourThe added molar amount of the layer is the AgX₁Of the added molar amount of the layer
0.02 to 10 times molar amount is preferable, 0.1 to 3 times molar amount
Amounts are more preferred. Normally, the gap difference becomes large
The more frequently the defect is formed, the higher the frequency.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

Excess X ^- salt concentration during nucleation, or excess A
By lowering the g ⁺ salt concentration, the mixing ratio of twin grains can be reduced. In addition, the mixing ratio increases as the concentration of the dispersion medium decreases and the stirring level deteriorates. Therefore, the conditions may be selected by the try-and-error method so that the finally obtained particles fall within the aspect of the present invention. After the screw dislocation defects are formed by the formation of the halogen composition gap surface at the time of nucleation and the halogen conversion reaction at the interface, the temperature is then raised preferably by 10 ° C. or more, more preferably by 20 to 70 ° C. Mature. Aging is preferably performed in a (100) plane forming atmosphere. Aging conditions are preferably selected from the nucleation condition range. By the ripening, tabular grains are preferentially grown, non-tabular grains are extinguished, and the tabular grain ratio is increased. The ripening rate generally increases with increasing pH in the pH 1-6 region and with increasing Cl ^- concentration in the pCl 1-3 region.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

After increasing the tabular grain ratio, a solute is then added to further grow the tabular grains. As a solute addition method, 1) an ion addition method (a method of adding an Ag ⁺ liquid and an X ⁻ liquid), 2) a method of previously forming AgX fine particles and adding the fine particles, 3) a combination method of both Can be mentioned. In order to preferentially grow the tabular grains in the edge direction, it is necessary to grow the tabular grains at a low supersaturation concentration within a range that does not undergo Ostwald ripening. That is, it is necessary to control the concentration at a low supersaturation level with high accuracy. Method 2) is more preferable because it enables this. It is preferable because each tabular grain can be grown uniformly.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0017

[Correction method] Change

[Correction content]

In the fine grain emulsion addition method, the diameter is 0.15 μm or less, preferably 0.1 μm or less, more preferably 0.1 μm or less.
Add an AgX fine grain emulsion having a diameter of 06 to 0.006 μm,
The tabular grains are grown by Ostwald ripening. The fine grain emulsion can be added continuously or intermittently. The fine grain emulsion can be continuously prepared by supplying the AgNO ₃ solution and the X ^- salt solution in a mixer provided in the vicinity of the reaction vessel, and immediately added to the reaction vessel immediately, or in advance in another vessel. It is also possible to add it continuously or intermittently after it is prepared in a batch manner.
The fine grain emulsion can be added in a liquid form or as a dry powder. It is also possible to mix the dry powder with water immediately before addition to liquefy it and add it.
The added fine particles are preferably added in such a manner that they disappear within 20 minutes, more preferably 10 seconds to 10 minutes. If the disappearance time becomes long, ripening occurs between the fine particles and the particle size becomes large, which is not preferable. Therefore, it is preferable not to add the entire amount at once. It is preferable that the fine particles are substantially free of twinned grains. Here, the multi-twin grain means a grain having two or more twin planes per grain. The term "substantially free" means that the ratio of multiple twin grains is 5%.
It is preferably 1% or less, more preferably 0.1% or less. Further, it is preferable that substantially no single twin crystal grains are contained. Furthermore, it is preferable that the screw dislocation is not substantially contained. Here, the term "substantially free" is in accordance with the above-mentioned rules.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

As the support of the photographic light-sensitive material of the present invention,
It may be preferred to have a thickness of 150-250 μm. This is essential from the viewpoint of handleability when observing on a medical Schaukasten. Further, the material is preferably a polyethylene terephthalate film, and particularly preferably colored blue. The support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment for improving the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex or the like may be provided, and a gelatin layer may be further provided thereon. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrocolloid layer can be further improved.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction content]

A precipitating agent was added and the temperature was lowered to 30 ° C.
After washing with precipitation, an aqueous gelatin solution was added, and the pH was adjusted to 6.
2, adjusted to pCl 3.0. Collect a part of the emulsion
Then, a transmission electron micrograph image of a replica of the particle (hereinafter
The "TEM image" is observed. Shape characteristic value of the particle
Was as follows: ((100) flat with aspect ratio 2 or more
Total projected area of plate-like particles / sum of projected areas of all AgX particles) =
a₁= 0.91, aspect ratio 2 or more (100) tabular grains
Average aspect ratio of child (average diameter / average thickness) = a ₂=
8.7, average of (100) tabular grains with aspect ratio of 2 or more
Diameter = a₃= 1.3 μm, (total projected area of twin grains /
(Total projected area of (100) tabular grains with a spectral ratio of 2 or more) =
a_Four= 0, (with an aspect ratio of 2 or more, an edge ratio of 1 to 1.4
Of (100) tabular grain total projected area / total AgX grain projection
Sum of shadow areas) = a_Five= 0.86, (aspect ratio 2 or more
70% of the total projected area from the largest of (100) tabular grains
Coefficient of variation of the diameter distribution of the particles when taken out)
= A₆= 0.059, average thickness = a₇= 0.15 μm

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0084

[Correction method] Change

[Correction content]

Fixer composition Ammonium thiosulfate 140 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid disodium dihydrate 25 mg Sodium hydroxide 6 g upto 1000 ml pH 5.10 (match with acetic acid)

[Submission date] May 24, 1994

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0089

[Correction method] Change

[Correction content]

Example 2 Inventive Emulsion C To a reaction vessel was placed 1200 ml of an aqueous gelatin solution (containing 20 g of deionized alkali-treated gelatin, pH 4.3),
While maintaining the temperature at 41 ° C., the Ag-1 liquid of Example 1 and X
Solution-1 was co-mixed with 12 ml at 50 ml / min. Two
After stirring for a minute, the Ag-2 solution and the X-2 solution were simultaneously mixed and added in an amount of 22 ml at 62 ml / min. After stirring for 2 minutes, Ag
Solution-1 and Solution X-1 were simultaneously mixed and added at 38 ml at 50 ml / min. 23 ml of NaCl-1 solution was added to adjust the pH to 5.0 and the temperature was raised to 75 ° C. After aging for 20 minutes, the temperature was lowered to 65 ° C., AgCl fine grain emulsion (average particle diameter 0.08 μm) was added at a rate of 4 × 10 ⁻³ mol / min AgCl addition, and after 10 minutes addition, AgCl 10 ^{−. It} added for 70 minutes by the accelerated addition method of ⁴ mol / min. After the addition, the mixture was aged for 8 minutes, a precipitating agent was added, the temperature was lowered to 30 ° C., and the precipitate was washed with water. An aqueous gelatin solution was added, and the pH was adjusted to 6.
2, adjusted to pCl 3.0. When a part of the emulsion was sampled and a transmission electron micrograph image of a replica of AgX grains was observed, the shape characteristic values of the grains were as follows. a ₁ = 0.92, a ₂ = 5.5, a ₃ = 1.2 μm, a
_{4 = 0, a 5 = 0.82} , a 6 = 0.077, a 7 =
0.22 μm, silver chloride content 98.26 mol%

Claims (3)

[Claims] 1. At least one of the emulsion layers has 50% or more of the total projected area of all silver halide grains having a Cl ⁻ content of 10 mol% or more, a main plane of {100} plane and a thickness of 0.35 μm or less. And a developing method comprising developing a silver halide photographic light-sensitive material consisting of tabular grains having an aspect ratio of 2 or more with a developing solution containing ascorbic acid and / or a derivative thereof. 2. The developing method according to claim 1, wherein the developing solution containing ascorbic acid and / or its derivative contains 0.3 mol / liter or more of carbonate. 3. The developing method according to claim 1, wherein the amount of the developing replenisher is 300 ml / m ² or less.