JPH08248554A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide the silver halide photographic sensitive material high in sensitivity even in the case of rapid processing and improved in residual dye stains. CONSTITUTION: The photographic sensitive material has a layer containing a silver halide emulsion spectrally sensitized in the presence of an iodine ion- releasing agent and a ratio of the content of calcium in this emulsion layer to that of the sensitizing dye in this layer is 0.05-1.0:1.0. It is preferred that the silver chloride content in the silver halide grains contained in this emulsion is >=50mol%.

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 having high sensitivity and improved residual color even in rapid processing.

[0002]

2. Description of the Related Art The demand for rapid processing of silver halide photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) is increasing year by year. In particular, in medical X-ray photosensitive materials, there is a great demand for rapid processing from the viewpoint of increasing the number of photographs taken due to an increase in inspection items and speeding up diagnosis in emergency medical care. However, as the processing time is shortened, the sensitivity is lowered and the performance of the developer needs to be improved, but the performance cannot be improved as expected due to the influence of the waste liquid on the environment. Therefore, it is necessary to design the sensitivity of the photosensitive material to be high in advance.

Various techniques are known for increasing the sensitivity of silver halide grains. Above all, on the grain surface during spectral sensitization
Using an iodide solution such as KI solution, silver iodide is localized on the surface of silver halide grains by conversion between iodide ions and silver halide on the surface of grains, thereby increasing the adsorption efficiency of the sensitizing dye. It is known. However, when iodide ions are added to the reaction solution in a free state, a region having a non-uniform iodide ion concentration distribution is generated, and an emulsion having a uniform iodine composition between grains cannot be prepared, and proper spectral sensitization is performed. It cannot be carried out, and it is difficult to always obtain a high-sensitivity emulsion.

Further, there is a technique in which silver iodide fine particles are used in place of the aqueous iodide salt solution to carry out the conversion as described above.
It is disclosed in JP-A-2-68538. By using this, it is possible to prepare an emulsion with a relatively uniform surface iodine composition between grains,
Higher sensitivity can be achieved. However, it has a drawback that the residual color after development is increased.

On the other hand, in light-sensitive materials, gelatin is generally used as a hydrophilic colloid for preventing fusion or aggregation of silver halide grains. It is known that gelatin contains calcium ions (Ca ²⁺ ) in an amount derived from its raw material or manufacturing conditions.

[0006]

In view of the above problems, an object of the present invention is to provide a light-sensitive material having high sensitivity and improved residual color even in rapid processing.

[0007]

The above object of the present invention has a layer containing a silver halide emulsion spectrally sensitized in the presence of an iodide ion-releasing agent, and the calcium ion content in the layer. Is divided by the spectral sensitizing dye content in the layer to give a value of 0.
It is achieved by a silver halide photographic light-sensitive material characterized by being in the range of 05 to 1.0.

The average silver chloride content of the silver halide grains contained in the silver halide emulsion is preferably 50 mol% or more.

The present invention will be described in detail below.

As a result of intensive studies by the present inventors, it was discovered that the amount of calcium ions in the silver halide emulsion spectrally sensitized in the presence of an iodide ion-releasing agent affects the sensitivity. Further, according to the present invention, it was found that the unexpected effect that the residual color after the development processing is improved can be obtained by optimizing the ratio of the amount of calcium ion and the amount of the sensitizing dye.

In the present invention, the content of calcium ion (Ca ²⁺ ) in the silver halide emulsion layer is 0.05 to 1.0, which is the weight of the spectral sensitizing dye in the silver halide emulsion layer. The preferable lower limit is 0.1 and the upper limit is 0.8. The calcium ions contained in gelatin occupy most of the calcium ions in the emulsion layer unless otherwise specified. The calcium ion in gelatin is derived from the raw material, but the calcium ion content can be determined by appropriately combining raw material selection, production condition selection, ion exchange treatment and the like. The gelatin used in the present invention may have a calcium ion content of about 3000 ppm, such as lime gelatin, but a calcium ion content of 2000 ppm or less is preferable.

The calcium ion content in the silver halide emulsion layer in the present invention may be achieved only by the calcium ion in gelatin, but may be adjusted by adding a calcium salt. Specific examples of the calcium salt used in the present invention include water-soluble calcium chloride, calcium iodide, calcium bromide, calcium nitrate and the like, but calcium chloride and calcium bromide are most preferable. The calcium salt may be added at any position from the time of preparing the silver halide grains to the time of preparing the coating solution.

The iodide ion-releasing agent used in the present invention can be synthesized according to the following synthetic method. JA
m.Chem.Soc., 76,3227-8 (1954), J.Org.Chem.16,798 (195
1), Chem.Ber.97,390 (1964), Org.Synth.V, 478 (1973),
J.Chem.Soc.1951,1851, J.Org.Chem.19,1571 (1954), J.
Chem.Soc. 1955, 1383, Chem. Commu. 1971, 1112 and the like can be mentioned.

The iodide ion-releasing agent used in the present invention releases iodide ion by reacting with a base and / or a nucleophilic reagent. As the nucleophilic reagent used at this time, the following chemical species are preferable. Can be mentioned. For example, hydroxide ion, sulfite ion, hydroxylamine, thiosulfate ion, mercaptans, sulfinates, carboxylates, alcohols, ureas, thioureas, phenols, hydrazines, hydrazides, phosphines, Examples include sulfides. In the present invention, the release rate and timing of iodide ions can be controlled by controlling the concentration of the base or nucleophile, the method of addition, and the temperature of the reaction solution. The preferred concentration range of the iodide ion-releasing agent is 1 × 10 ⁻⁵ to 10 mol, more preferably 1 × 10 ^−4.
~ 5 moles.

The preferred temperature range is 30 to 80 #C, more preferably 35 to 60 #C. At high temperatures above 80 # C, iodide ion release rate is generally extremely fast, and
At a low temperature below 30 #C, the iodide ion release rate is extremely slow, which is not preferable.

In the present invention, when a base is used for releasing iodide ions, a change in liquid pH may be used. At this time, the range of pH is preferably 2 to 12, and more preferably 5 to 10 for controlling the iodide ion release rate and timing.

Further, a nucleophile and a base may be used in combination,
At this time as well, the pH may be controlled within the above range to control the iodide ion release rate and timing.

When iodide ions are released from the iodide ion-releasing agent, all iodine atoms may be released or some of them may remain without being decomposed.

In the present invention, the iodide ion release rate can be determined by controlling the temperature, the pH, the concentration of the iodide ion releasing agent, the base, and the nucleophile as described above, and a preferable iodide ion release can be obtained depending on the purpose. You can choose the speed.

The iodide ion-releasing agent may be added at any time from the formation of silver halide grains to the end of the chemical ripening step, but the preferable addition timing of the iodide ion-releasing agent in the present invention is as follows. It is a chemical ripening step, and it is preferable that it is present at the same time as the chemical sensitizer and the spectral sensitizing dye in the reaction liquid of the aging container. The chemical aging process here is
It refers to the period from the time when the physical ripening and desalting operations of the silver halide emulsion of the present invention are completed to the time when the chemical sensitizer is added and then the operation for stopping the chemical ripening is performed. Sodium thiosulfate is preferably used as the chemical sensitizer which is present in the reaction solution at the same time as the iodide ion releasing agent.

The following method is preferable for controlling the release of iodide ions in the present invention. That is, by changing the pH, the concentration of the nucleophilic substance, the temperature, etc. from the iodide ion-releasing agent added to the reaction solution and already uniformly distributed, usually, by changing from low pH to high pH, In this method, iodide ions are uniformly controlled and released throughout the reaction solution. A base and / or a nucleophilic substance for controlling the reaction rate of iodide ion releasing reaction may be present in the reaction solution before adding the iodide ion releasing agent, but the iodide ion releasing agent is uniformly added. It is preferable to add it in a distributed state.

The preferable range of the amount of iodide ions released from the iodide ion-releasing agent is not particularly limited and depends on the intended characteristics of the silver halide grains formed, but generally speaking, the total amount of silver halide is To 1 × 10 ^-5 to 10 mol%
And more preferably 1 × 10 ^{−4 to} 5 mol%, especially 1 × 10 ^−4.
˜1 × 10 ⁻¹ mol%.

The iodide releasing agent of the present invention has the following general formula (I):
It is preferable that it is a compound shown by (V).

[0024]

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The iodide ion-releasing agents of the general formulas (I) to (V) release iodide ions by reaction with a base and / or a nucleophile, a substitution reaction, an elimination reaction or a hydrolysis reaction. It is a compound.

The divalent organic group represented by L in the general formulas (I) to (V) is an aliphatic group, an aromatic group, a heterocyclic group or a group formed by combining these, and further, these groups. Group, -O- group, -N (R)-group, -CO- group, -CS-
Group, -S- group, -SO- group, -SO ₂ - group, -P (R) group, -PO
It is a group formed by combining (R) -groups (wherein these Rs represent a hydrogen atom or a monovalent group). The aliphatic group contained in L may be either saturated or unsaturated, preferably has 1 to 30 carbon atoms, and is particularly preferably a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms.
The aromatic group contained in L is preferably a monocyclic or bicyclic aryl group, and may be condensed with another heterocycle. The heterocyclic group contained in L may be saturated or unsaturated, and N,
A 5- or 6-membered ring containing one or more of O, P, S and Se is preferable. Particularly preferred is a nitrogen-containing 5-membered or 6-membered heteroaromatic ring, and typical examples are a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, an oxazole ring, a thiazole ring, or a benzo thereof. Examples include condensed rings.

The divalent group represented by L in the general formulas (I) to (V) may be substituted, and typical substituents include, for example, an alkyl group, an aralkyl group, an alkenyl group,
Alkynyl group, alkoxy group, aryl group, substituted amino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, alkyl or arylthio group, alkyl or arylsulfonyl group, alkyl or arylsulfinyl group, hydroxy group, halogen Examples thereof include an atom, a cyano group, a sulfo group, an aryloxycarbonyl group, an acyl group, an alkoxycarbonyl group, an acyloxy group, a carbonamido group, a sulfonamide group, a carboxyl group, a phosphoric acid amide group, a diacylamino group, and an imide group. Preferred substituents are an alkyl group (preferably having 1 to 20 carbon atoms), an aralkyl group (preferably having 7 to 30 carbon atoms), an alkoxy group (preferably having 1 to 20 carbon atoms), a substituted amino group. (Preferably an amino group substituted with an alkyl group having 1 to 20 carbon atoms), an acylamino group (preferably having 2 to 30 carbon atoms), a sulfonamide group (preferably having 1 to 30 carbon atoms) , A ureido group (preferably having 1 to 30 carbon atoms), a phosphoric acid amide group (preferably having 1 to 30 carbon atoms) and the like. These groups may be substituted.

In the general formulas (I) to (V), the iodide ion represented by I is preferably bonded to the carbon atom of the divalent organic group represented by L. Particularly preferably, I is bonded to the part of the aliphatic group contained in L. When I binds to the aromatic group moiety of L, the aromatic group is a benzene ring (including condensed ring), and a cyano group, a nitro group, a sulfonyl group at the ortho position or rose position of I. It is preferable to have an electron-withdrawing substituent such as When I is bonded to the heterocyclic group moiety of L, the heterocycle is a 5-membered or 6-membered nitrogen-containing heteroaromatic ring (including those condensed), and I is nitrogen on the heteroaromatic ring. It is preferably attached to a carbon atom adjacent to the atom or located on a carbon atom which is sandwiched by two atoms from the nitrogen atom.

The cation represented by M ⁺ in the general formula (I) is a hydrogen ion or a monovalent cation. Preferred is a substituted or unsubstituted ammonium ion, an alkali metal ion (eg, Na ⁺ , K ⁺ , Li ⁺ ) or another metal ion (eg, 1 / 2Mg ²⁺ , 1 / 2Ca ^2+, etc.).

In the general formula (II), Q ⁺ represents a group containing a quaternary ammonium salt, a tertiary sulfonium salt or a quaternary phosphonium salt, preferably a group containing a quaternary ammonium salt. The quaternary ammonium salt contained in Q ⁺ is a usual ammonium salt having four substituents on the nitrogen atom,
It may be a quaternized heteroaromatic group (for example, N-substituted pyridinium, N-substituted imidazolium), a substituted immonium salt, a substituted amidinium salt, a substituted uronium salt, a substituted guadinium salt, or the like. Q ⁺ is preferably represented by the following general formula (II-1) or general formula (II-2).

[0031]

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In these formulas, R ¹ , R ² and R ³ may be different or the same and each represents an aliphatic group, an aromatic group or a heterocyclic group, and Z is a 5- to 7-membered heterocyclic group. Represents the group of atoms necessary to form a ring. More specifically, R
^{1 to} R ³ are alkyl groups having 1 to 30 carbon atoms, alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 or 3 carbon atoms, and 6 carbon atoms.
An aryl group having 30 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, and a heterocyclic group having 4 to 30 carbon atoms are preferable. As R ^{1 to} R ³ , a group having 20 or less carbon atoms is preferable, and a group having 12 or less carbon atoms is particularly preferable.
Further, any two or more of R ^{1 to} R ³ may combine to form a ring, and any one of R ^{1 to} R ³ may bond to a group represented by L in the general formula (II). You may form a ring. The heterocycle formed by Z and a nitrogen atom is preferably a 5- or 6-membered ring. Particularly preferred is a nitrogen-containing heteroaromatic ring, and typical examples include a pyridine ring, a pyridazine ring, a pyrimidine ring,
Examples thereof include a pyrazine ring, a triazine ring, an imidazole ring, an oxazole ring, a thiazole ring or a benzo-condensed ring thereof. Also in this case, Z and the group represented by L in the general formula (II) may combine to form a ring. General formula (II-
The groups represented by R ^{1 to} R ^{3 in 1} ) and Z in the general formula (II-2) may be substituted, and examples of preferred substituents are listed as the substituent of L in the general formula (I). I can give you what I did.

[0033] In the general formula (II) Y ^- anion represented by a counter anion Q ^+. Halide ions Preferred examples except iodide ion, nitrate ion, nitrate ion, sulfite ion, p- toluenesulfinic acid ion, a sulfonate ion, half ester anions nitrate, phosphate ion, carboxylate ion, BF ₄ ^- , ClO ₄ ^-, P
F ₆ ^- and so on. Y ⁻ may combine with the groups represented by L and Q ⁺ in the general formula (II) to form an inner salt.

In the general formula (V), R ⁴ and R ⁵ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms (eg methyl, ethyl, isopropyl, butyl, 2-ethylhexyl, cyclohexyl), Aralkyl group having 7 to 20 carbon atoms (eg benzol, phenethyl), 6 to 6 carbon atoms
The 20 aryl groups (eg phenyl, naphthyl) may be the same or different from each other. R ⁴ and R ⁵ may be substituted, and examples of the substituent include those listed as the substituent of L in the general formula (I). Also, R ⁴ ,
R ^{5 s} may combine with each other to form a ring, preferably a 5- or 6-membered ring (for example, a pyrrolidine ring or a piperidine ring).

Particularly preferred as R ⁴ and R ⁵ are hydrogen atoms.

Specific examples of the compounds represented by formulas (I) to (V) are shown below, but the invention is not limited thereto.

[0037]

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[0038]

[Chemical 4]

[0039]

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[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

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[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

In the silver halide grain of the present invention, silver iodochloride, silver chloroiodobromide, silver chlorobromide, silver bromide, silver iodobromide and the like can be used as the silver halide, but iodide chloride is preferred. Silver,
It is silver chloroiodobromide. When silver iodochloride or silver chloroiodobromide is used, the average silver iodide content in the entire silver halide grains is preferably 1.0 mol% or less, but 0.5 mol%
The following are more preferable. The average silver chloride content is 50 mol%
The above content is preferable, and 70 mol% or more is more preferable.

The average grain size of the silver halide grains of the present invention is 0.
The thickness is preferably 15 to 5.0 μm, more preferably 0.4 to 3.0 μm, and most preferably 0.4 to 2.0 μm.

The silver halide grains of the present invention are preferably tabular silver halide grains. The tabular silver halide grains are grains having two parallel main planes facing each other, and have a mean grain size to grain thickness ratio (hereinafter referred to as an aspect ratio) of more than 1.3. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), which is a circle-equivalent diameter of a projected area of the tabular silver halide grain (of a circle having the same projected area as the silver halide grain). Diameter) and thickness refers to the average distance between two parallel major planes forming the tabular silver halide grains.

When tabular silver halide grains are used in the present invention, the aspect ratio is preferably 2 or more, more preferably 2.0 or more and less than 15.0. It is particularly preferably 3 or more and less than 10.

When tabular silver halide grains are used in the present invention, the average thickness is preferably 0.01 to 1.0 μm,
More preferably 0.02-0.40 μm, even more preferably 0.02-
It is 0.30 μm. Particle size and thickness can be optimized to optimize sensitivity and other photographic properties. sensitivity,
Optimum particle size and thickness depending on other factors that influence the photographic characteristics (thickness of hydrophilic colloid layer, hardness, chemical ripening condition, set sensitivity of photographic material, silver coating amount, etc.) Is different.

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

When tabular silver halide grains are used in the present invention, it is preferable that the thickness distribution is small. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) x 100 = width of thickness distribution (%), it is preferably 25% or less, more preferably 20%. It is as follows, and particularly preferably 15% or less.

The silver halide grains of the present invention may have dislocations. Dislocations are, for example, JF Hamilton, Phot.Sci.En
g, 57 (1967), T.Shiozawa, J.Soc.Phot.Sci.Japan, 3
It can be observed by a direct method using a transmission electron microscope at low temperature described in 5,213 (1972). That is, the silver halide grains taken out carefully so as not to apply pressure enough to cause dislocation to the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beam In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass through. Therefore, it is possible to observe more clearly using a high-voltage electron microscope (200 KV or more for particles having a thickness of 0.25 μm). .

The halogen particles of the present invention include (100)
It is also possible to use tabular silver halide grains having as a main plane. The shape of the main plane of the tabular silver halide grain having (100) as the main plane is a right-angled parallelogram or a right-angled parallelogram with rounded corners. The ratio of adjacent sides of the right-angled parallelogram is less than 10, preferably less than 5, more preferably less than 2. In addition, the length of a side when the corner is rounded is represented by the distance between the intersection of the straight line portion of the side and the line obtained by extending the straight line portion of the adjacent side.

When tabular silver halide grains having (100) as the principal plane are used as the halogen grains of the present invention, they can be prepared by the method described in US Pat. No. 5,320,938. That is, it is preferable to nucleate with low pCl in the presence of iodide ions under the condition that the (100) plane is easily formed.
After nucleation, Ostwald ripening and / or growth is performed,
It is possible to obtain tabular silver halide grains having a desired grain size and distribution.

For example, first, a silver salt solution, a halide solution containing iodide ions, and a protective colloid solution are added to the first container to form nuclei, and after the nucleation, the mixed solution is transferred to the second container, Therefore, the method of growing is preferably used. At that time, the growth may be temporarily stopped on the way and used as seed grains to grow silver halide on the seed grains.

Specifically, an aqueous solution containing a protective colloid and seed particles may be present in the reaction vessel in advance, and silver ions, halogen ions, or silver halide fine particles may be supplied as necessary to grow the seed particles. it can.

As the silver halide grain of the present invention (100)
When a tabular silver halide grain having a main plane is prepared, the pCl of the protective colloid solution is preferably in the range of 0.5 to 3.5, more preferably 1.0 to 3.0, and most preferably 1.5 to 2.5. Nucleation is started from the time when the silver salt solution is added to the protective colloid solution, but iodide ions are preferably added simultaneously with or prior to the silver salt solution, and most preferably silver salt. This is the case when it is added to the solution in advance.

As the silver halide grain of the present invention (100)
In the case of preparing tabular silver halide grains having as a main plane, iodine can be introduced up to the solid solution limit of silver iodide and silver chloride, but iodine in the protective colloid solution at the start of nucleation is The ion concentration is preferably 10 mol% or less, more preferably 0.01 mol% or more and 10 mol% or less, and most preferably 0.05 mol% or more and 10 mol% or less.

As the silver halide grain of the present invention (100)
When tabular grains having a main plane of (4) are prepared, the addition time of the silver salt solution during nucleation is preferably 5 seconds or more and less than 1 minute. Further, it is preferable that both the silver salt solution and the halide solution be added at the time of nucleation. It is particularly preferable to add iodine ions. Further, the bromine ion in the protective colloid solution at the time of nucleation may be present as long as the chlorine ion is present in an amount of 50 mol% or more.

When silver halide grains containing silver chloride are prepared in the present invention, the silver chloride content of the nucleus is 50 mol% or more, preferably 70 mol% or more, more preferably 90 mol% or more.
It is at least mol%. The pH during nucleation is preferably 2-8. The temperature is preferably 30 to 90 ° C, more preferably 35 to 70 ° C. The amount of silver added during nucleation is 0.1 of the total silver amount.
It is preferably from mol% to 10 mol%.

In preparation of the silver halide grains of the present invention, a known silver halide solvent such as ammonia, thioether or thiourea can be present.

In the preparation of the silver halide grains of the present invention, a silver salt solution and a halide solution are added during the growth by the double jet method, and the addition rate is adjusted according to the growth of grains such that new nucleation does not occur and Ostwald Particles having a desired particle size and distribution can be obtained by a method in which the size distribution does not spread due to aging, that is, a method of gradually changing the rate within the range of 30 to 100% of the rate at which new nuclei are generated. As another condition for further growth, a method in which silver halide fine particles are added, dissolved, and recrystallized to grow, as described in Section 88 of 1983 Annual Meeting of the Photographic Society of Japan, is also preferably used. In particular, silver iodide fine particles, silver bromide fine particles,
Fine grains of silver iodobromide and fine grains of silver chloride are preferably used.

The silver halide grains of the present invention may be so-called halogen conversion type grains. Halogen conversion is 0.2 to 0.5 mol% based on silver
Is preferable, and the conversion may be carried out during physical ripening or after completion of physical ripening. As a method for halogen conversion, an aqueous halogen solution or silver halide fine particles having a smaller solubility product with silver than the halogen composition on the grain surface before halogen conversion is usually added. The fine particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

In producing the silver halide grains of the present invention, stirring conditions during production are extremely important. As the stirring device, the device disclosed in JP-A-62-160128, in which the additive liquid nozzle is installed in the liquid near the mother liquid inlet of the stirrer, is particularly preferably used. At this time, the stirring rotation speed is 100 to 1
It is preferably 200 rpm.

The silver halide grain of the present invention contains a cadmium salt during the grain forming step and / or the growing step.
Metal ions are added using at least one selected from zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt), and iron salt (including complex salt), and the inside of the particle is added. And / or it is preferable that the surface of the particles contains these metal elements.

In the present invention, it is also preferable to add a silver halide solvent before the desalting step in order to accelerate the developing rate. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is preferably added in an amount of 1 × 10 ^{−3 to} 3 × 10 ⁻² mol per mol of silver.

In the present invention, it is preferable to use gelatin as the dispersion medium for the protective colloid of silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low molecular weight gelatin (molecular weight of 20,000 to 100,000),
Modified gelatin such as phthalated gelatin is used. Other hydrophilic colloids can also be used. Specifically, Research Disclos
ure, hereinafter abbreviated as RD) Volume 176, NO.17643 (December 1978)
Examples include those described in Section IX.

In the preparation of the tabular silver halide grains of the present invention, unnecessary soluble salts may be removed during the growth of the silver halide grains, or they may be contained therein.
In the case of removing the salts, RD Vol. 176, No. 17643 II
It can be performed based on the method described in the section.

In the present invention, the conditions of the chemical ripening step, such as pH, pAg, temperature and time, are not particularly limited, and the conditions generally used in the art can be used. For chemical sensitization, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a selenium sensitization method using a selenium compound, a tellurium sensitization method using a tellurium compound, or a reducing substance is used. The reduction sensitization method to be used, gold and other noble metal sensitization methods using a noble metal can be used alone or in combination, and among them, sulfur sensitization method, selenium sensitization method, tellurium sensitization method, reduction sensitization method, etc. Is preferably used.

In the case of selenium sensitization, the selenium sensitizers used include a wide variety of selenium compounds. For example, in this regard, U.S. Patents 1574944, 1602592, 1623499.
JP-A-60-150046, JP-A-4-25832, JP-A-4-109240
No. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N,
N'-triethylselenourea, 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-selenobutylate, etc.), selenophosphates (eg, tri-p-triselenophosphate, etc.), selenides (triphenylphosphine selenide, Diethyl selenide, diethyl diselenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, selenoketones, and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. U.S. Patent No. 1574944
No. 1602592, 1623499, 3297446, 329
7447, 3320069, 3408196, 3408197, 3
442653, 3420670, 3591385, French patent
No. 2693038, No. 2093209, No. 52-34491, No. 52-344
No. 92, No. 53-295, No. 57-22090, JP-A-59-180536
No. 59-185330, 59-181337, 59-187338,
59-192241, 60-150046, 60-151637, 61-
246738, JP 3-4221 A, 3-24537 A, 3-111838 A
No. 3, No. 3-116132, No. 3-148648, No. 3-237450, No. 4-
No. 16838, No. 4-25832, No. 4-32831, No. 4-96059, No.
4-109240, 4-140738, 4-140739, 4-147250
No. 4, No. 4-149437, No. 4-184331, No. 4-190225, No. 4-
191729, 4-195035, British Patent 255846, 861984
issue. In addition, Journal of Photographic Sci by HESpencer
It is also disclosed in the scientific literature such as ence magazine, 31: 158-169 (1983).

The amount of the selenium sensitizer used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but generally about 10 ^-8 to 10 ^-4 mol per mol of silver halide is used. Further, the addition method may be a method of adding it by dissolving it in water or an organic solvent such as methanol or ethanol alone or in a mixed solvent depending on the properties of the selenium compound to be used, or by adding it in advance with a gelatin solution. Alternatively, the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion of a mixed solution with a polymer soluble in an organic solvent may be used.

The temperature of the chemical ripening using the selenium sensitizer is
The range of 40 to 90 ° C is preferable. More preferably 45 ° C or higher
It is below 80 ℃. The pH is preferably in the range of 4 to 9 and the pAg is preferably in the range of 6 to 9.5.

Regarding the tellurium sensitizer and the sensitizing method, US Pat. Nos. 1623499, 3320069, 3772031 and 35312 are applicable.
No. 89, No. 3655394, British Patent No. 235211, No. 1121496
No. 1295462, No. 1396696, Canadian Patent No. 800958
And Japanese Patent Laid-Open No. 4-204640 and 4-333043. Examples of useful tellurium sensitizers include telluroureas (eg, N, N-dimethyl tellurourea, tetramethyl tellurourea, N-carboxyethyl-N, N'-dimethyl tellurourea, N, N'-dimethyl. -N'phenyl tellurourea), phosphine tellurides (for example, tributylphosphine telluride, tricyclohexylphosphine telluride, triisopropylphosphine telluride, butyl-diisopropylphosphine telluride, dibutylphenylphosphine telluride), telluroamides (for example, , Telluroacetamide, N, N-dimethyl tellurobenzamide), telluroketones, telluroesters, isotellocyanates, and the like. The technique for using the tellurium sensitizer is in accordance with the technique for using the selenium sensitizer.

It is also preferable to carry out so-called reduction sensitization on the grain surface by placing it in an appropriate reducing atmosphere. Preferred examples of the reducing agent include thiourea dioxide and ascorbic acid and their derivatives. Other preferred reducing agents include hydrazine, polyamines such as diethylenetriamine, dimethylamineboranes, sulfites and the like.

The amount of the reducing agent added depends on the type of reduction sensitizer, the grain size of the silver halide grains, the composition and crystal habit, the temperature of the reaction system,
Although it is preferable to change the pH depending on the environmental conditions such as pH and pAg, for example, in the case of thiourea dioxide, as a rough guide, use of about 0.01 to 2 mg per mol of silver halide gives favorable results. In the case of ascorbic acid, a range of about 50 mg to 2 g is preferable per mol of silver halide.

As the conditions for reduction sensitization, the temperature is about 40 to 70.
C, time about 10-200 minutes, pH about 5-11, pAg about 1-1
A range of 0 is preferred (where the pAg value is the reciprocal of the Ag ⁺ ion concentration).

The water-soluble silver salt is preferably silver nitrate.
By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. The pAg during silver ripening is suitably 1-6, preferably 2-4. The conditions such as temperature, pH and time are preferably within the above-mentioned reduction sensitization condition range. As a stabilizer of a silver halide photographic emulsion containing reduction-sensitized silver halide grains, a general stabilizer described below can be used, but it is disclosed in JP-A-57-82831. Antioxidants and / or Papers by VS Gahler [Zei
tshrift fur wissenschaftliche Photographie Bd.63,
133 (1969)] and thiosulfonic acids described in JP-A No. 54-1019 are often used together with good results. The addition of these compounds may be carried out at any stage of the emulsion production process from crystal growth to the preparation process immediately before coating.

The spectral sensitizing dye used in the present invention means, when photoexcited in the state of being adsorbed on silver halide,
It means one that causes electron transfer to silver halide and contributes to photosensitization of silver halide grains, and does not include an organic dye as a filter for light.

As the spectral sensitizing dye used in the present invention, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye, etc. may be used. You can

Useful spectral sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052, 3,619,197, and US Pat.
3,713,828, 3,615,643, 3,615,632, 3,61
No. 7,293, No. 3,628,964, No. 3,703,377, No. 3,666,480
Issue, Issue 3,667,960, Issue 3,679,428, Issue 3,672,897,
No. 3,769,026, No. 3,556,800, No. 3,615,613, No. 3,6
No. 15,638, No. 3,615,635, No. 3,705,809, No. 3,632,34
No. 9, No. 3,677,765, No. 3,770,449, No. 3,770,440,
Same 3,769,025, same 3,745,014, same 3,713,828, same 3,5
67,458, 3,625,698, 2,526,632, 2,503,77
6, JP-A-48-76525, JP-A-5-88293, and Belgian Patent 691,807.

The addition amount of the spectral sensitizing dye is not uniform depending on the kind of the dye, the purpose of the spectral sensitization or the emulsion composition, but is 1 × 10 ⁻⁴ mol to 1 × 10 ⁻³ mol per mol of silver halide. It may be in the range, preferably 2 × 10 ⁻⁴ mol to 8 × 10 ⁻⁴ mol. The sensitizing dye may be added at any time after the grain growth step and before the chemical sensitization (ripening).

The sensitizing dye is a hydrophilic solvent such as methanol,
It may be added after being dissolved in ethanol or the like or dispersed in an aqueous solvent in a solid state.

The solubility of each of the above spectral sensitizing dyes in water is in the range of 2 × 10 ^-4 to 4 × 10 ^-2 mol / liter.

In the present invention, when the spectral sensitizing dye is mechanically ground and dispersed in an aqueous solvent, various dispersers are effectively used. Specifically, a high speed stirrer, a ball mill, a sand mill, a colloid mill, an attritor, an ultrasonic disperser or the like is used.

In the present invention, when the spectral sensitizing dye is dispersed and used in an aqueous solvent, the solid fine particles of the spectral sensitizing dye preferably have a particle size of 5 μm or less, more preferably 0.01 μm.
It is 1 μm or less.

[0088] The hydrophilic binder of the silver halide emulsion layer in the present invention, if the emulsion layer is on both sides of the support preferably supports per side 3.0 g / m ² is 2.0 g / m ² or less. When it is on one side of the support, it is preferably 6.0 g / m ² or less, more preferably 4.0 g / m ² or less.

The light-sensitive material of the present invention includes a black-and-white light-sensitive material (for example, medical light-sensitive material, printing light-sensitive material, general photographic negative light-sensitive material, etc.), color light-sensitive material (for example, color negative light-sensitive material, color reversal light-sensitive material, Photosensitive materials for color printing, etc.), photosensitive materials for diffusion transfer, photothermographic materials, etc., but black and white photosensitive materials are preferred, and medical photosensitive materials are particularly preferred.

The silver halide emulsion of the present invention may contain a developing agent such as aminophenol, ascorbic acid, pyrocatechol, hydroquinone, phenylenediamine or 3-pyrazolidone in the emulsion layer or a layer having other layers.

The silver halide emulsion layer and the non-photosensitive hydrophilic colloid layer of the light-sensitive material of the present invention preferably contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine), bis (vinylsulfonyl) methyl ether, N, N′-
Methylenebis (β- (vinylsulfonyl) propionamide), etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogenates (mucochloric acid, mucophenoxycyclolate, etc.), isoxazoles , 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.
Among them, JP-A-53-41221, the same 53-57257, 59-162456,
No. 60-80846 and the active vinyl compounds described in US Pat.
Active halogen compounds described in 3,325,287 are preferred.

As the hardener of the present invention, a polymeric hardener can be effectively used. For example, dialdehyde starch, polyacrolein, a polymer having an aldehyde group such as acrolein copolymer described in U.S. Patent No. 3,396,029, a polymer having an epoxy group described in U.S. Patent No. 3,623,878,
Polymers having a dichlorotriazine group described in U.S. Pat. No. 3,362,827 and Research Disclosure Magazine 17333 (1978), polymers having an active ester group described in JP-A-56-66841, JP-A-56 -1
42524, U.S. Pat. No. 4,161,407, JP-A-54-65033, Research Disclosure Magazine 16725 (1978), and the like, and polymers having an active vinyl group or a group serving as a precursor thereof are preferable. Particularly preferred are polymers in which the active vinyl group, or its precursor group, is attached to the polymer backbone by a long spacer as described in 56-142524.

In order to make the photographic light-sensitive material of the present invention suitable for rapid processing, an appropriate amount of a hardener is added in advance in the coating step of the light-sensitive material so that the rate of water swelling in the developing-fixing-washing step can be improved. It is preferable to reduce the water content in the light-sensitive material before the start of drying by adjusting.

The light-sensitive material of the present invention preferably has a swelling ratio of 150 to 250% during development processing and a film thickness after expansion of 70 μm or less. If the water swelling rate exceeds 250%, poor drying occurs, and, for example, poor handling occurs in automatic processor processing, especially rapid processing. Further, if the water swelling ratio is less than 150%, uneven development and residual color tend to be deteriorated during development. Here, the water swelling rate means the difference between the film thickness after swelling in each processing solution and the film thickness before the development processing, which is divided by the film thickness before processing and multiplied by 100. .

Dyes can be used in the present invention, and specific examples of the dyes used are JP-A Nos. 52-92716 and 55-12003.
No. 0, 55-155350, 55-155351, 56-12639,
63-197943, JP-A 2-1838, 2-1839, World Patent 88/04794, U.S. Patents 4,861,700, 4,950,586.
, European Patent No. 489,973, etc., and the synthetic methods can also be carried out according to the methods described in these patents.

When a solid fine particle dispersion of a dye is used in the present invention, the production method is described in JP-A-52-92716,
55-155350, 55-155351, 63-197943, 3-1
The methods described in 82743, World Patent WO88 / 04794 and the like can be used. Specifically, it can be prepared using a surfactant using a fine disperser such as a ball mill, a vibration mill, a planetary mill, a sand mill, a roller mill, a jet mill and a disc impeller mill. Also,
After the dye is dissolved in a weak alkaline aqueous solution, the pH is lowered to make it weakly acidic to precipitate fine particle solids, or a weak alkaline solution of the dye and an acidic aqueous solution are mixed at the same time while adjusting the pH. Dispersions of dyes can be obtained by the method of making a solid. The dyes may be used alone or in combination of two or more. When two or more kinds are mixed and used, they may be dispersed individually and then mixed, or may be simultaneously dispersed.

Examples of the support that can be used in the light-sensitive material of the present invention include the above-mentioned RD-17643, page 28 and RD-308.
119, page 1009. A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer.

In the light-sensitive material of the present invention, various additives can be added to the silver halide emulsion according to the purpose. Examples of additives and the like used include Research Disclosure (RD) No. 17643 (December 1978)
No. 18716 (November 1979) and No. 308119 (198)
December, 9) listed in. The places where they are written are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 IV Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic Agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Next, preferable development processing of the light-sensitive material of the present invention will be described.

The processing method of the light-sensitive material of the present invention is preferably a processing method of processing the light-sensitive material of the present invention in a total processing time of 15 seconds to 90 seconds.

Preferred developing solutions for developing the light-sensitive material of the present invention include, as developing agents, JP-A-4-15641 and JP-A-4.
-16841 and the like dihydroxybenzene, such as hydroquinone, para-aminophenols, such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diamiphenol, 3-pyrazolidones, for example, 1 -Phenyl-3-pyrazolidones, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone and the like are preferably used in combination.

The amount of the para-aminophenols and 3-aminopyrazolidones used is preferably 0.004 mol / liter, more preferably 0.04-0.12 mol / liter.

Further, the total number of moles of dihydroxybenzenes, paraaminophenols and 3-pyrazolidones contained in these components of all developing solutions is preferably 0.1 mol / liter or less.

Preservatives may include sulfites such as potassium sulfite, sodium sulfite, reductones such as piperidinohexose reductone,
These are preferably used in an amount of 0.2 to 1 mol / liter, more preferably 0.3 to 0.6 mol / liter. Further, addition of a large amount of ascorbic acid also leads to processing stability.

As the alkaline agent, sodium hydroxide,
Includes pH regulators such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate, potassium triphosphate. Further, the borate described in JP-A-61-28708, JP-A-60-9
Saccharose, acetoxime, 5-described in 3439 specification
A buffering agent such as sulfosalicylic acid, phosphate or carbonate may be used. The content of these agents is such that the pH of the developer is 9.0 to
13, preferably pH 10 to 12.5.

As the solubilizing agent, polyethylene glycols and their esters can be contained, and as the sensitizing agent, for example, a quaternary ammonium salt, a development accelerator, a surfactant and the like can be contained.

As a silver sludge inhibitor, JP-A-56-106 is available.
Silver antifouling agents described in No. 244, sulfides and disulfide compounds described in JP-A-3-51844, and cysteine derivatives or triazine compounds described in Japanese Patent Application No. 4-92947 are preferably used.

As the organic inhibitor, an azole type organic antifoggant, for example, an indazole type, an imidazole type, a benzimidazole type, a triazole type, a benztriazole type, a tetrazole type or a thiadiazole type compound is used.

Examples of the inorganic inhibitor include sodium bromide, potassium bromide, potassium iodide and the like. Besides this, L.
FA Menson, "Photographic Processing Chemistry," 22, published by Focal Press, Inc. (1966)
Those described in pages 6 to 229, US Pat. Nos. 2,193,015 and 2,592,364, and JP-A-48-64933 may be used. As a chelating agent for masking calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant of 8 or more with iron described in JP-A 1-193853 is preferably used as an organic chelating agent. To be Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate, and polyphosphate.

As the development hardening agent, a dialdehyde compound may be used. In this case, glutaraldehyde is preferably used. However, for rapid processing, it is preferable that the hardener is allowed to act in the coating step of the photosensitive material in advance as described above, rather than the hardener is allowed to act in the development processing step.

The processing temperature of the developer of the present invention is preferably
The temperature is 25 to 50 ° C, more preferably 30 to 40 ° C. The development time is 3 to 90 seconds, more preferably 5 to 60 seconds. The processing time of the present invention is 15 to 90 seconds in Dry to Dry, preferably 15 to 50 seconds.

The replenishment in the present invention replenishes the treatment agent fatigue and oxidative fatigue. As a replenishment method, JP-A-55-126
Replenishment according to width and feed rate described in Japanese Patent No. 243, JP-A-60-1049
Area replenishment described in No. 46 or area replenishment controlled by the number of continuously processed sheets described in JP-A-1-149156 may be used, and a preferable replenishment rate is 500 to 150 ml / m ² .

Preferred fixing solutions can include fixing materials commonly used in the art. The pH is 3.8 or more, preferably 4.2 to 5.5. The fixing agent is a thiosulfate such as ammonium thiosulfate or sodium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The concentration of ammonium thiosulfate is 0.1-5 mol /
It is preferably in the range of liter, more preferably 0.8 to 3 mol
/ Liter range.

The fixing solution of the present invention may be one which performs acidic hardening. In this case, aluminum ions are preferably used as the hardener. For example, it is preferably added in the form of aluminum sulfate, aluminum chloride, potassium alum, or the like.

Others In the fixing solution of the present invention, if desired, preservatives such as sulfite and bisulfite, pH buffering agents such as acetic acid and boric acid, mineral acids (sulfuric acid and nitric acid) and organic acids (citric acid and oxalic acid). , Malic acid, etc.), various acids such as hydrochloric acid, pH adjusting agents such as metal hydroxides (potassium hydroxide, sodium hydroxide) and chelating agents having a water softening ability.

As the fixing accelerator, for example, JP-B-45-357.
No. 54, No. 58-122535, No. 58-122536, and the thioethers described in US Pat. No. 4,126,459.

[0117]

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

(Preparation of Em-1) A tabular silver iodochloride emulsion Em-1 was prepared using the following three kinds of solutions.

A low methionine gelatin 214.37 g sodium chloride 1.995 g potassium iodide 149.6 mg finished with water 6090 ml B sodium chloride 10.48 g potassium iodide 149.4 mg finished with water 90 ml C silver nitrate 30.58 g finished with water 90 ml D sodium chloride 165.0g Finish with water to 5640ml E Silver nitrate 479.0g Finish with water to 5640ml While stirring solution A in the reaction vessel at 40 ° C,
The total amount of solution B and solution C was added thereto by the simultaneous mixing method at a flow rate of 180 ml / min over 30 seconds.

Next, after the mixed solution was kept at 40 ° C. for 10 minutes, the solution D and the solution E were added by the simultaneous mixing method at a flow rate of 24 ml per minute over 40 minutes, and subsequently, the solution D and the solution were further added. The remaining total amount of E was added by the simultaneous addition method over 130 minutes while linearly increasing the flow rate so that the initial flow rate was 24 ml and the final flow rate was 48 ml. During this time, pCl was kept at 2.35 throughout. Then, the mixture was adjusted to 1.30 with sodium chloride, desalted using an ultrafiltration membrane, an aqueous gelatin solution containing ossein gelatin was added, and the mixture was redispersed with stirring.

The obtained silver halide emulsion contained 0.06 mol% of iodide, and when observed by an electron microscope, the average grain size (circle diameter conversion) was 1.45 μm, the average thickness was 0.13 μm, the average aspect ratio was 11, grain It was a right-angled parallel four-plate tabular silver halide grain having a size distribution of 18.3%.

(Chemical sensitization using KI solution) Em
After the temperature of -1 was adjusted to 60 ° C, the sensitizing dye D1 (5,5'-dichloro
-1,1 ', 3,3'-Tetraethylbenzimidazolocarbocyanine) was added as a fine dispersion of solid particles in an amount of 425 mg per mol of silver, and then a mixed aqueous solution of ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triethyl The dispersion liquid of phenylphosphine selenide was added, and after 30 minutes, 4.0 × 10 ⁻³ mol of an aqueous potassium iodide solution was added per mol of silver,
Aged for a total of 2 hours. As a stabilizer at the end of aging
Em-1A was obtained by adding an appropriate amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI). Additives other than spectral sensitizing dyes and their addition amounts (per mol of AgX)
Is shown below.

Potassium thiocyanate 95
mg Chloroauric acid
2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.2 mg Stabilizer (TAI) 280 mg Solid fine particle dispersion of spectral sensitizing dye is disclosed in JP-A-5-297.
It was prepared by a method similar to the method described in No. 496.
That is, a predetermined amount of the spectral sensitizing dye is added to water whose temperature has been adjusted to 27 ° C in advance, and a high-speed stirrer (dissolver) is used for 30 to 120 at 3.500 rpm.
Obtained by stirring for minutes.

The above dispersion liquid 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. and stirred to completely dissolve it. 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% sodium dodecylbenzenesulfonate aqueous solution was added thereto.
Then, these two liquids were mixed and dispersed at 50 ° C. for 30 minutes at a peripheral speed of the dispersing blade of 40 m / sec by a high-speed stirring type disperser having a dissolver having a diameter of 10 cm. Then, the ethyl acetate was rapidly removed under reduced pressure with stirring until the residual concentration of ethyl acetate was 0.3 wt% or less. Then, this dispersion was diluted with pure water to obtain 80 kg. A part of the thus obtained dispersion was collected and used in the above experiment.

(Preparation of silver iodide fine grain emulsion) To 6.64 liters of a 5.0% by weight aqueous gelatin solution containing 0.06 mol of potassium iodide, 2 liters of an aqueous solution each containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide were added. Added over 10 minutes. The pH during the formation of fine particles is 2.0 using nitric acid, and the temperature is
The temperature was controlled at 40 ° C. After particle formation, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution.

(Chemical sensitization using silver iodide fine grain emulsion) In the above (chemical sensitization using KI solution), an equimolar silver iodide fine grain emulsion was added instead of the potassium iodide solution ( Chemical sensitization using KI solution) and Em-1
B was prepared.

(Chemical sensitization using iodide ion-releasing agent)
In the above (chemical sensitization using KI solution), instead of the potassium iodide solution, an equimolar iodide ion-releasing agent as shown in Table 1 was added 10 minutes before the addition of the sensitizing dye D1 to adjust the pH.
Em-1 in the same manner as (chemical sensitization using KI solution) except that the pH was lowered to 5.8 after adding the stabilizer TAI to 9.0.
CG was prepared.

(Preparation of Coating Solution and Coating) Additives described below were added to each of the obtained emulsions to prepare an emulsion layer coating solution. At the same time, a filter coating liquid and a protective layer coating liquid described below were also prepared. Using these coating liquids, the coating amount is one side and the silver amount is 1.6.
g / m ² , the amount of gelatin attached was 2.5 g / m ² , two slide hopper type coaters were used to simultaneously coat both surfaces on the support at a speed of 120 m / min, and dried in 2 minutes and 20 seconds. Samples No. 1 to No. 38 were obtained. As a filter layer, glycidyl methacrylate 50 wt%, methyl acrylate 10 wt
%, Butyl methacrylate 40% by weight, the following filter dyes and gelatin were dispersed in an aqueous copolymer dispersion obtained by diluting the copolymer consisting of three kinds of monomers to a concentration of 10% by weight. It was coated in the following layer constitution on a polyethylene terephthalate film base colored in blue with a density of 0.20 at 175 μm.

[0129]

[Chemical 12]

Layer position Layer type Gelatin amount per side (g / m ² ) Upper layer Protective layer 0.8 Intermediate layer Emulsion layer 1.5 Lower layer Filter layer 0.2 In addition, for sample Nos. 27 to 33, the emulsion layer coating solution was prepared. The calcium ion content was adjusted by adding an aqueous calcium chloride solution in an amount corresponding to 663 mg per mol of silver halide. The amount of calcium ions contained in gelatin used for each sample was as shown below as a result of measurement by an atomic absorption method.

No. The amount of Ca ²⁺ (ppm) relative to the weight of dry gelatin 1 150 2 300 3 1000 4 2500 5 5000 Additives used in the emulsion are as follows. The amount of addition is shown in an amount per mole of silver halide.

1,1-dimethylol-1-bromo-1-nitromethane 70 mg t-butyl-catechol 400 mg 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 0.15 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0g Styrene-maleic anhydride copolymer 2.5g Nitrophenyl-triphenylphosphonium chloride 50mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 2g

[0133]

[Chemical 13]

C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g 1-phenyl-5-mercaptotetrazole 15 mg Protective Layer Solution Next, the following was prepared as a protective layer coating solution. The additive is shown in the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide particles (area average particle size 1.2 μm matting agent) 0.5 g (CH ₂ = CHSO ₂ CH ₂ ) ₂₀ (hardener) 500 mg C ₄ F ₉ SO ₃ K 2mg C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g

[0136]

Embedded image

(Evaluation of Samples) (1) Sensitometry (Evaluation of Photographic Performance) Photographic properties were evaluated using the obtained samples No. 1 to No. 38. First, the sample was sandwiched between two intensifying screens (KO-250) and irradiated with X-rays through an aluminum wedge at a tube voltage of 80 kvp, a tube current of 100 mA and 0.05 seconds for exposure. Next is the automatic processor (SRX-50
3) was used and processed with a developer and a fixer having the following formulations.

Developer Formulation Part-A (for 12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g Boric acid 40 g 5-Methylbenzotriazole 1.4 g 5-Nitro Benzimidazole 0.4 g 1-Phenyl-5-mercaptotetrazole 0.25 g 4-Hydroxymethyl-4-methyl-1-phenylpyrazolidone 120 g Hydroquinone 400 g Add water to make 6000 ml.

Part-B (for 12 l finishing) Glacial acetic acid 70 g 5-Nitroindazole 0.6 g N-acetyl-DL-penicillamine 1.2 g Starter glacial acetic acid 120 g Potassium bromide 225 g H0 (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH 1.0 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ HSC ₂ H ₅ ) ₂ 1.0 g 5-methylbenzotriazole 1.5 g Water is added to the final volume of 1.0 l.

Fixer formulation Part-A (for 18.3l finish) Ammonium thiosulfate (70wt / vol%) 4500g Sodium sulfite 450g Sodium acetate trihydrate 450g Boric acid 110g Tartaric acid 60g Sodium citrate 10g Gluconic acid 70g 1- (N , N-Dimethylamino) -ethyl-5-mercaptotetrazole 18g Glacial acetic acid 330g Aluminum sulfate 62g Add water to make 7200ml.

The developer is prepared by adding Part A and Part B to about 5 liters of water.
Was added at the same time, water was added while dissolving with stirring, the pH was adjusted to 12.53 with 12 g of glacial acetic acid. This is used as a development replenisher.

20 ml / l of the above-mentioned starter was added to 1 liter of this development replenisher to adjust the pH to 10.30 to prepare a working solution.

To prepare the fixing solution, Part A was simultaneously added to about 5 liters of water, water was added while stirring and dissolving to make 18.3 liters, and the pH was adjusted to 4.6 using sulfuric acid and NaOH. This is the fixing replenisher.

The processing temperatures are 35 ° C. for development and fixing, respectively.
33 ℃, 20 ℃ wash, 50 ℃ dry, processing time is dry to dry 25
Seconds. The replenishing amount was 65 ml for 1 m ² of film for both development and fixing.

After the treatment, the sensitivity was measured. Sensitivity is expressed as the reciprocal of the exposure amount that gives a density of fog +1.0. Sample No. 1
The relative sensitivity is shown when the sensitivity of is set to 100. The results obtained are shown in Table 1.

(2) Evaluation of residual color The unexposed samples of the respective samples were treated in the same manner as in (1) for residual color evaluation, and residual color contamination was visually evaluated in the following four stages.

A: No residual color B: Slight residual color C: Some amount of residual color but limit of practical range D: Many amount of residual color is not practical Practical results are shown in Table 1.

[0148]

[Table 1]

From the results shown in Table 1, it can be seen that the samples of the present invention are good with high sensitivity and little residual color. That is, the uneven distribution of iodide ions can be alleviated by using an iodide ion-releasing agent. Further, it has been found that by adjusting the amount of calcium ions in the presence of an iodide ion-releasing agent, the loss of dye is improved.

[0150]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having high sensitivity and improved residual color even in rapid processing.

Claims (2)

[Claims] 1. A layer having a silver halide emulsion spectrally sensitized in the presence of an iodide ion-releasing agent, wherein the calcium ion content in the layer is the same as the spectral sensitizing dye in the layer. A silver halide photographic light-sensitive material characterized in that the value divided by the amount is 0.05 or more and 1.0 or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the average silver chloride content of the silver halide grains contained in the silver halide emulsion is 50 mol% or more.