JPH07119959B2 - Ultra-fast processing silver halide photographic material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material. In particular, the present invention relates to a silver halide photographic light-sensitive material for X-ray which enables ultra-rapid processing.

[Prior Art] In recent years, the consumption of silver halide photographic light-sensitive materials has been increasing. Therefore, the number of silver halide photographic light-sensitive materials developed is increased, and it is required to further accelerate the development processing, that is, to increase the processing amount within the same time.

The above tendency is also found in the field of X-ray sensitive materials such as medical X-ray films. That is, the number of times of diagnosis is rapidly increased by enforcing regular health checkups, the number of inspection items is increased in order to make the diagnosis more accurate, and the number of X-ray photographs taken is increasing.

On the other hand, it is also necessary for the examinee to know the diagnosis result as quickly as possible.

That is, there is a strong demand for developing and performing diagnosis more quickly than in the past. Especially for angiography, intraoperative photography, etc., it is essentially necessary to see the photograph in a short time.

In order to meet the demands of the medical community, it is necessary to accelerate the automation of diagnosis (imaging, transportation, etc.) and process X-ray film more rapidly.

However, when ultra-rapid processing is carried out, (a) the density is insufficient (sensitivity, contrast and maximum density decrease), (b) the fixing is not sufficiently carried out, and (c) the film is insufficiently washed with water. And (d) insufficient drying of the film causes problems. Insufficient fixing and insufficient washing with water cause a change in color tone during film storage, which causes deterioration in image quality.

One way to solve these problems is to reduce the amount of gelatin. However, when the amount of gelatin is reduced, troubles such as coating unevenness and coating streaks during coating of the silver halide photosensitive material are likely to occur. In addition, a film with a small amount of gelatin has a problem that when the films are rubbed with each other, or when the film is rubbed with another substance, the density of the film is higher than that of other parts after development, that is, so-called scratch blackening is likely to occur. is there.

Although ultra-rapid processing is desired as described above, the ultra-rapid processing referred to in the present specification means that the developing tank, the crossover portion, the fixing tank, and the crossover portion are inserted after the leading edge of the film is inserted into the automatic developing machine. , The whole time until the film edge comes out of the dry part after passing through the washing tank, crossover part, and dry part [in other words, the total length of the processing line (m) is the line transfer speed (m / se
The quotient (sec.) divided by c.) is 20 to 60 seconds. It is well known in the art that the time for the crossover portion should be included here, but even in the crossover portion, the liquid of the previous process is substantially swollen in the gelatin film, so that it is substantially This is because it can be considered that the treatment process is in progress.

JP-B-51-47045 describes the importance of the amount of gelatin in rapid processing, but the processing time is 60 to 120 seconds in total, including the transitional part. However, this processing time cannot satisfy the recent demand for ultra-rapid processing.

[Object of the Invention]

As described above, the first object of the present invention is that the total processing time is 20
To provide a silver halide photographic light-sensitive material excellent in sensitivity, contrast, maximum density, fixing property, drying property, etc. by solving the above-mentioned problems of the prior art when performing ultra-rapid processing of from 60 seconds to 60 seconds. It is in.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which causes less troubles during coating even when the amount of gelatin is small.

A third object of the present invention is to provide a silver halide photographic light-sensitive material which produces less scratch blackening even when the amount of gelatin is small.

[Structure and Action of Invention]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material for X-rays having at least one photosensitive silver halide emulsion layer and at least one protective layer on at least one side of a support, and the outermost layer on one side of The surface tension of the coating liquid to be formed is simultaneously multi-layered under the condition that the surface tension of the coating liquid forming the layer adjacent to the outermost layer is 6 dyn / cm or more, and the amount of gelatin on one side is 2.20 to 3.10 g / m. the silver halide photographic light-sensitive material for X-rays, which is a ^2, was achieved.

In a preferred embodiment, the average grain size of the silver halide emulsion grains used in the silver halide emulsion layer is 0.30 to 1.50.
μm, more preferably 0.40 to 1.30 μm, most preferably
The aspect which is 0.40-1.10 micrometers can be mentioned.

In another preferred embodiment, in a silver halide photographic emulsion consisting essentially of silver iodobromide and silver halide grains having a multilayer structure, any adjacent homogeneous iodine distributions of the silver halide grains The difference in the average iodine content of the two layers (having a coating layer or between the inner core and the coating layer) is 10 mol% or more, and the average iodine content of the outermost layer is 10 mol% or less, and Chemical sensitization of silver halide grains.

Here, the particles having a multilayer structure have a coating layer of an arbitrary halogen composition provided on the outside of the inner core, and the coating layer may be only one layer, or two or more layers, for example, 3 layers.
It may be laminated with four layers. The number of layers is preferably 5 or less.

As the silver halide of the inner core and the coating layer, silver bromide,
Although silver iodobromide and silver iodide are used, a mixture with a small amount of silver chloride may be used. Specifically, silver chloride may be contained in an amount of about 10 mol% or less, preferably about 5 mol% or less.

Further, the outermost layer is preferably substantially silver bromide or substantially silver iodobromide (iodine content is 10% or less), and is preferably several%.
May contain less than chlorine atoms.

The average iodine content of the entire silver halide grains of the present invention is 10
It is preferably at most mol%, more preferably at most 6 mol%.

For example, in Xray sensitive materials and the like, iodine may cause problems such as development suppression and infectious development, so in practice, it is preferable that the iodine content is not more than a certain level.
In any case, the method of the present invention has an effect of reducing stress fog, but for this reason, the total iodine content is preferably 10 mol% or less, more preferably 7 mol% or less, and further preferably 5 mol% or less. Most preferred.

When the inner core is composed of silver iodobromide, it is preferably a homogeneous solid solution phase.

Here, the homogeneity can be explained more specifically as follows.

That is, the X-ray diffraction analysis of the silver halide grain powder is performed.
When I got Cu-K_β Surface index of silver iodobromide using X-ray [200]
Half-width of the peak of Δ2 = 0.30 (deg) or less
Means and. At this time, the day fractometer
The conditions of use are that the scanning speed of the goniometer is ω (deg / mi
n), time constant r (sec), receiving slit width r
(Mm), ωr / r ≦ 10.

As the halogen composition of the inner nucleus, the average content of iodine is preferably 40 mol% or less, more preferably 0 to 20.
Mol%.

The difference in silver iodide content between two adjacent layers (any two coating layers or the coating layer and the inner core) is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably Is 25 mol% or more.

Further, as the silver iodide content of the coating layers other than the outermost coating layer,
It is preferably 10 mol% to 100 mol%.

When the silver halide grains are composed of three or more layers and the coating layer is composed of silver iodobromide, it is not necessary that they are all homogeneous, but all layers are homogeneous silver iodobromide. Is preferred.

Coating layer (or inner core) with high iodine content
In the case of a negative type silver halide emulsion, it is preferably present below the outermost surface. In the case of a positive type silver halide emulsion, it may be inside or on the surface.

The silver iodide content of the outermost coating layer is preferably 10 mol% or less, more preferably 0 to 5 mol%.

Regarding the iodine content of the inner core and the coating layer of the silver halide grain used in the practice of the present invention, for example, JI Goldstein, DB Williams (W
illiams) "X-ray analysis in TEM / ATEM" Scanning Electron Microscopy (1977), Volume 1 (IIT Research Institute), p. 651 (19)
It can also be obtained by the method described in (March 1977).

When the silver halide grains used in the practice of the present invention are composed of, for example, two layers, the inner core preferably has a higher iodine than the outermost layer, and when composed of three layers, a coating other than the outermost layer is provided. It is preferable that the layer or the inner core has higher iodine than the outermost layer.

The present invention is preferably applicable to chemically sensitized silver halide grains. This is because if the particles are not sensitized, the sensitivity itself is very low and scratch blackening and pressure desensitization do not occur in the first place.

The silver halide grains used in the present invention may be either positive type or negative type.

In the case of negative type, the degree of chemical sensitization is 6 which is the optimum sensitization when the sensitivity point of "fog +0.1" is taken in optical density.
It is preferable to carry out chemical sensitization so as to be 0% or more.

In the case of the positive type, the degree of chemical sensitization is such that the chemical sensitization is performed inside the grain so that it becomes 60% or more of the maximum sensitization when the sensitivity point of "maximum density -0.1" is taken in optical density. It is preferable.

The average grain size of the silver halide grains used in the present invention is
The length of the ridge when converted into a cube having an equal volume is defined as the particle size, and is represented by the average value.

In the present invention, the surface tension of the coating liquid forming the outermost layer is higher than the surface tension of the liquid forming the layer adjacent to the outermost layer.
It is applied under a condition of 6 dyn / cm or more, but in order to make the surface tension difference of the liquid used for the outermost layer (usually the uppermost layer) and the adjacent layer (the layer immediately below it) 6 dyn / cm or more. At least one kind of surfactant may be used for the uppermost layer, and a surface active agent may or may not be used for the layer immediately below the uppermost layer. The surfactants used in the uppermost layer and the layer immediately below may be the same or different.

Further, the difference in surface tension between the liquid used in the uppermost layer and the layer immediately below it is preferably 8 dyn / cm or more, more preferably 10 dyn / cm or more, and most preferably 12 dyn / cm or more.

The "outermost layer" in the present invention is usually the outermost layer literally, and is generally formed as the uppermost layer as described above. Although a coating may be applied, the present invention of course includes such a thing.

Examples of the above-mentioned surfactant that can be used in the present invention include saponins (steroidal), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers,
Polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols And nonionic surfactants such as alkyl esters of sugars. Further, alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-
N-alkyl taurines, sulfosuccinates,
Such as sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc., carboxy group, sulfo group, phospho group,
Examples thereof include anionic surfactants containing an acidic group such as a sulfate ester group and a phosphate ester group. Further, amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkylbetaines, and aminoxides can be mentioned. In addition, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles Can be mentioned. Further, a fluorine-containing surfactant, a fluorine-containing surfactant having a polyoxyethylene group, or the like can be used.

As an alkylene oxide-based surfactant, Japanese Patent Publication No.
-9610, DT-2648746, JP-A-53-129623, 54-89624, and
54-98235, 58-203435, 58-208743, 60-80848, 60
60-94126 and the like. As an example of the combined use of an alkylene oxide-based surfactant and another compound, Japanese Patent Application Laid-Open No. 54-8
9626, 55-70837, 57-11341, 57-109947, 59-74
554, 60-76741, 60-76742, 60-76743, 60-8083
9, Same 60-80846, Same 60-80847, Same 50-131293, Same 53-29715
Etc.

Examples of anionic surfactants include JP-A-53-21922 and GB-150.
3218, Japanese Examined Patent Publication No. 56-1617 and higher alcohol sulfates, higher alkyl sulfonates, alkylbenzene sulfonates, dialkyl sulfosuccinates, acylmethyl taurides, N-acyl sarcosinates, fatty acid monoglyceride sulfates, α-sulfones. Acid etc. are mentioned.

Examples of the fluorinated surfactant include, for example, Japanese Examined Patent Publication No. 47-9303,
48-43130, 52-25087, 57-1230, JP-A-49-4673
3, Same 50-16525, Same 50-34233, Same 51-32322, Same 54-1422
4, the same 54-111330, the same 55-557762, the same 56-19042, 56-4109
3, the same 56-34856, the same 57-11341, the same 57-29691, the same 57-6422
8, Same 57-146248, Same 56-114944, Same 56-114945, Same 58-196
544, 58-200235, 60-109548, 57-136534, US-358
9906, -3775126, -4292402, RD-16630, and the like, and the compounds exemplified in JP-A-60-164738.

Preferred examples of the anionic surfactant containing no polyalkylene oxide are shown below in 1-1 to 1-10.

1-1 C ₄ H ₉ O‐SO ₃ Na Preferred examples of the fluorine-containing surfactant are shown below as 2-1 to 2-80.
Shown in.

2-1 C ₃ F ₇ O (CH ₂ CH ₂ O) ₂₀ C ₁₂ H ₂₅ 2-2 C ₃ F ₇ O (CH ₂ CH ₂ O) ₅ C ₃ F ₇ 2-3 C ₆ F ₁₃ O (CH ₂ CH ₂ O) ₁₀ C ₄ H ₉ 2-4 C ₆ F ₁₃ O (CH ₂ CH ₂ O) ₂₀ C ₆ H ₁₃ 2-5 C ₆ F ₁₃ O (CH ₂ CH ₂ O) ₇ CH ₃ 2- 6 C ₉ F ₁₇ O (CH ₂ CH ₂ O) ₂₀ CH ₃ 2-14 C ₆ F ₁₃ O (CH ₂ CH ₂ O) _40- C ₁₈ H ₃₅ 2-15 C ₉ F ₁₇ O (CH ₂ CH ₂ O) _10- H 2-16 C ₁₂ F ₂₃ O (CH ₂ CH ₂ O) ₅₀ ‐CH ₃ 2-21 C ₈ F ₁₇ (CH ₂ CH ₂ O ₅ CH _{2 4} SO ₃ Na 2-22 HCF _{2 8} CH ₂ OCH ₂ CH _{2 4} CH _{2 3} SO ₃ H 2-23 C ₇ F ₁₅ COOCH ₂ CH ₂ O ₄ CH _{2 4} SO ₃ K 2-25 C ₄ F ₉ CH ₂ CH ₂ O ₃ SO ₃ Na 2-32 C ₆ F ₁₃ SO ₃ Na 2-33 C ₈ F ₁₇ SO ₃ Na 2-34 C ₆ F ₁₃ COOK 2-35 C ₈ F ₁₇ SO ₃ COOK 2-37 F ₃ C- (CF ₂ ) _2- COOH 2-38 H- (CF ₂ ) _6- COOH 2-39 CF _3- (CF ₂ ) _6- COONH ₄ 2-40 H- (CF ₂ ) ₁₀ -COOH 2-41 H- (CF ₂ ) _6- CH ₂ -OSO ₃ Na 2-42 H- (CF ₂ ) _3- CH ₂ -OSO ₃ Na 2-48 H- (CF ₂ ) _6- CONH-CH _2- O-SO ₃ Na _{2-54 H- (CF 2) 6 -CH} 2 -O-CH 2 -CH 2 -CH 2 -SO 3 Na 2-55 F 3 C- (CF 2) 6 -CH 2 -O-CH 2 -CH ₂ -CH ₂ -SO ₃ Na _{2-58 F 3 C- (CF 2)} 2 -COO-CH 2 -CH 2 -CH 2 -SO 3 Na 2-59 H- (CF 2) 10 -COO-CH 2 -CH 2 -CH 2 -SO ₃ Na _{2-61 F 3 C- (CF 2)} 2 -COO (-CH 2 CH 2 O) 7 -CH 3 2-63 F ₃ C- (CF ₂ ) _2- CH ₂ O (-CH ₂ CH ₂ O) ₅ H Examples of commercially available fluorine-containing surfactants include those marketed under the trade name of Unidyne by Daikin Industries, Ltd. and under the trade name of Florard by 3M (Sumitomo 3M).

Next, specific examples of the polyoxyethylene surfactant preferably used in the present invention are shown in 3-1 to 3-44.

3-1 C ₁₁ H ₂₃ COOCH ₂ CH ₂ O ₈ H 3-2 C ₁₇ H ₃₃ COOCH ₂ CH ₂ O ₁₅ H 3-3 C ₈ H ₁₇ OCH ₂ CH ₂ O ₇ H 3-4 C ₂₂ H ₄₅ OCH ₂ CH ₂ O ₂₅ H 3-19 C ₁₂ H ₂₃ SCH ₂ CH ₂ O ₁₆ H 3-37 C ₉ H ₁₉ OCH ₂ CH ₂ O ₄ SO ₃ K 3-39 C ₁₈ H ₃₃ OCH ₂ CH ₂ O ₄ SO ₃ Na 3-41 C ₁₂ H ₂₅ OCH ₂ CH ₂ O ₄ CH ₂ COONa Preferred quaternary ammonium salts include the following compounds 4-1 to 4-20.

Next, the particles used for carrying out the present invention will be described. The particle size distribution of the particles used may be narrow or wide.

The grain size distribution of silver halide grains in the photographic emulsion is arbitrary, but it may be monodisperse. Here, the monodisperse is a dispersion system in which 95% of particles fall within ± 60% of the number average particle size, preferably within 40%. Here, the number average grain size is the number average diameter of the projected area diameters of silver halide grains.

The silver halide grains in photographic emulsions are cubic, octahedral, 14
It may have a regular crystal body such as a tetrahedron or a dodecahedron, or have an irregular (irregular) crystal shape such as a spherical shape or a plate shape, or a composite form of these crystal shapes. It may have a. It may consist of a mixture of particles of various crystal forms.

Further, for example, an oxide crystal such as PbO and a silver halide crystal such as silver chloride are combined, a junction type silver halide crystal, an epitaxially grown silver halide crystal (for example, silver chloride on silver bromide, Epitaxial growth of silver iodobromide, silver iodide, etc.), hexagonal crystal, regular octahedral silver iodide, and crystals in which regular hexahedral silver chloride has overlapping orientations may be used.

Further, an emulsion may be used in which ultraflat silver halide grains having a grain diameter of 5 times or more the thickness thereof account for 50% or more of the total projected area. For details, see JP-A-58-127921, 5
It is described in the specification such as 8-113927.

The term "regular grains" as used above means a silver halide emulsion in which at least 80% by weight or number of silver halide grains has a regular shape. Further, a silver halide grain having a regular structure or morphology means a grain that does not include anisotropic growth such as twin planes and grows isotropically. For example, a cube, a tetrahedron, a regular octahedron, It has a shape such as a face piece or a spherical shape. The production method of such regular silver halide grains is
For example, Journal of Photographic Science (J.Phot.Sci.), 5, 332 (1961), Berihite del Bunzengesu-Physik hemi (Ber.Bunsenges.Ph
ys.Chem.), 67, 949 ( 1963), International Congress of photo graphic Science of Tokyo (Intern.Congress Phot.Sci.Tokyo (19
67) etc. Such regular silver halide grains can be obtained by controlling reaction conditions when growing silver halide grains by using a double jet method. In such a simultaneous mixing method, silver halide grains are prepared by adding a silver nitrate solution and a halide solution in substantially equal amounts to an aqueous solution of protective colloid with vigorous stirring.

In the practice of the present invention, for example, in the case of containing regular silver halide grains as described above, it is possible to include irregular silver halide grains. However, when such particles are present, they generally should be no more than about 50% by weight or number of particles. In a preferred embodiment, at least about 60 to 70% by weight consists of regular silver halide grains.

In the production of monodisperse emulsions and / or emulsions having regular silver halide grains, the supply of silver ions and halide ions does not dissolve existing crystal grains with the growth of crystal grains, and conversely, it is necessary to prepare new grains. At the critical growth rate of supplying sufficient and necessary silver halide for the growth of only existing grains, which does not allow generation or growth, or in its allowable range,
It is preferable to increase the growth rate continuously or stepwise. As this increasing method, Japanese Patent Publication No. 48-36890,
No. 52-16364 and JP-A No. 55-142329.

In other words, the supply rate of silver ions and halide ions is such that the growth rate of silver halide grains is 30 to 30 times the critical growth rate.
It is effective to supply 100%.

This critical growth rate varies depending on temperature, pH, pAg, degree of stirring, composition of silver halide grains, solubility, grain size, inter-grain distance, crystal habit, or type and concentration of protective colloid. It can be easily determined experimentally by a method such as microscopic observation of emulsion particles suspended in a liquid phase and measurement of turbidity.

In the practice of the present invention, the silver halide grains used in the silver halide emulsion are, for example, TH James, The Theory of the Photographic Process (Th
e Theory of the Photographic Process), 4th Edition, Ma
Published by cmillan (1977), P. Glfkides, Chemie E.
Chimie et Physigue
Photographigue (Published by Paul Montel, 1967), GFDu
ffin, Photographic Emulsion Chemistry, (The Foc
Al Press, 1966), VLZelikman et al, Making and Coating Photographic Emulsi
on), (published by The Focal Press, 1964), neutral method, acidic method, ammonia method, forward mixing method, back mixing method, double jet method, controlled double jet method, computer It can be manufactured by applying a method such as a version method or a core / shell method.

Also, as another form of the double jet method, a triple jet method in which soluble halogen salts having different compositions are independently added (for example, soluble silver salt, soluble bromine salt and soluble iodine salt)
Can also be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PAg in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
To keep constant, that is, so-called controlled
The double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In order to control the grain growth during the formation of silver halide grains, for example, as a silver halide emulsion, ammonia, rodancali, rodanmon, thioether compounds (e.g., U.S. Pat.Nos. 3,271,157, 3,574,628, 3,704,130, and 3704,130, 4,297,439, 4,276,374,
Etc.), thione compounds (for example, JP-A-53-144,319, JP-A-53-82,408, JP-A-55-77,737, etc.), amine compounds (for example, JP-A-54-100,717, etc.) and the like can be used. . Of these, ammonia is preferred.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

Further, in these silver halide grains or silver halide emulsions, salts of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium and tungsten platinum (soluble salts).
Of these, at least one type is preferably contained. The content thereof is preferably 10 ⁻⁶ to 10 ⁻¹ mol per mol Ag. Particularly preferably, at least one of thallium, palladium and iridium salts is contained. These may be used alone or as a mixture, and the addition position (time) is arbitrary. This is expected to improve flash exposure characteristics, prevent pressure desensitization, prevent latent image fading, sensitize and other effects.

In the practice of the present invention, the pAg of the mother liquor containing the protective colloid is at least 1 during the grain growth before the chemical sensitization as described above.
The aspect which is 0.5 or more can be preferably adopted. Particularly preferably, an atmosphere having a very high bromine ion concentration of 11.5 or more is passed even once. In this way, the effect of the present invention can be further enhanced by increasing the (111) plane and rounding the grains. The ratio of the (111) plane of such particles to the total surface area is preferably 5% or more.

In this case, the rate of increase of the (111) plane (the rate of increase with respect to that before passing through the pAg atmosphere of 10.5 or more) is preferably 10% or more, more preferably 10 to 20%.

Akira Hirata, “Bretin of the Society,” reports on whether the outer surface of the silver halide grain is covered by either the (111) or (100) plane, or how the ratio is measured.・ Scientific Photography of Japan "No.13,5 ~ 15
See page (1963).

During grain growth before chemical sensitization, the mother liquor containing protective colloid
It is possible to easily confirm whether or not the (111) plane is increased by 5% or more by Hirata's measurement method by once passing through an atmosphere having a pAg of at least 10.5 or more.

In this case, it is desirable that the above-mentioned pAg is set after the addition of about 2/3 of the total amount of silver added and before the so-called desalting step which is usually performed before chemical sensitization. this is,
This is because it is easy to obtain a monodisperse emulsion having a narrow grain size distribution.

The aging in an atmosphere having a pAg of 10.5 or more is preferably performed for 2 minutes or more.

By such pAg control, the (111) plane is increased by 5% or more and the shape is rounded, so that a preferable one having the (111) plane of 5% or more with respect to the total surface area of the particle is obtained. You can

In order to remove the soluble salts from the emulsion after the precipitation or after the physical ripening, the Nudel washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (for example, polystyrene) may be used. A precipitation method (flocculation method) using a sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. The process of removing soluble salts may be omitted.

The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, for example, D.
Grundragen del Fotografischen Flotse Mitt Gilberhalogeneden (Die Grun
dlagen der Photographischen Prozesse mit Silberhal
ogeniden), Academische Verlagaesellschaft, 1968, 675
The method described on page 734 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanines); a reducing substance (eg, silver-tin silver, amine) , Hydrazine derivatives,
Reduction sensitization method using formamidinesulfinic acid, silane compound; noble metal compound (eg, gold complex salt, P
A noble metal sensitization method using a complex salt of a metal of Group VIII of the periodic table such as t, Ir, Pd) or the like can be used alone or in combination.

These examples are described in US Pat.
No. 1,574,944, No. 3,410,689, No. 2,278,947, No. 2,728,668, No. 3,656,955, etc., for reduction sensitization method U.S. Patent No. 2,983,609, No. 2,419,974 case 4,054,
No. 458, etc., US Patent No.
No. 2,448,060, British Patent No. 618,061 and the like.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon nucleus is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon nucleus is fused to the nucleus of
That is, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadol nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

A specific example of the spectral sensitizing dye is described in, for example, P. Glafkides's “Chimi Photographique (Chimi
e Photographigue ”(2nd edition, 1957: Paul Montel, Paris) Chapters 35-41 and FM Hamer's“ The Cyanine And
The Cyanine and Reiated
Compounds) "(Interscience (Interacienc
e)), and U.S. Patent Nos. 2,503,776 and 3,459,553.
No. 3,177,210, Research Disclosure, Volume 176, 17643 (issued in December 1978), Item 23, IV, Item J, etc.

Typical examples thereof are U.S. Pat.Nos. 2,688,545 and 2,977,229.
No. 3, No. 3,397,060, No. 3,522,052, No. 3,527,64
No. 1, No. 3,617,293, No. 3,628,964, No. 3,666,4
No. 80, No. 3,672,898, No. 3,679,428, No. 3,703,
No. 377, No. 3,769,301, No. 3,814,609, No. 3,83
7,862, 4,026,707, British Patent 1,344,281,
No. 1,507,803, JP-B-43-4936, JP-A-53-12375, JP-A-52-110618 and JP-A-52-109925.

When the sensitizing dye is used in the present invention, it can be used in the same concentration as that used in a usual negative type silver halide emulsion. In particular, it is advantageous to use a dye concentration that does not substantially reduce the intrinsic sensitivity of the silver halide emulsion. About 1.0 × 10 ⁻⁵ to about 5.0 × 10 ⁻⁴ mol of the sensitizing dye per mol of silver halide, particularly about 4.0 × 10 5 of the sensitizing dye per mol of silver halide.
It is preferably used at a concentration of ^{-5 to} 2.0 x 10 ^-4 molar.

A dye that does not itself have a spectral sensitizing effect or a substance that does not substantially absorb visible light together with a sensitizing dye,
A substance exhibiting supersensitization may be included in the emulsion. For example,
Aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,743,510) , A cadmium salt, and an azaindene compound may be included. U.S. Pat.Nos. 3,615,613, 3,615,641 and 3,617,295
No. 3,635,721 is particularly useful.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadrinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. Many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulfinic acid, benzenesulphonic acid amide and the like can be added.

For more information, see EJBirr, Stabilization of
Stabilization of Photographic Silver Halide
Emulsions), Focal Press, 1974, etc.

Compounds that can be used include, for example, thiazolium salts described in U.S. Pat.Nos. 2,131,038 and 2,694,716; azaindenes described in U.S. Pat.Nos. 2,886,437 and 2,444,605: U.S. Pat.
, Etc .: Lauzols: US Pat. No. 3,23
Sulfocatechols described in 6,632 and the like: Oxides described in British Patent No. 623,448 and the like:
U.S. Pat.Nos. 2,403,927, 3,266,897, 3,397,
Mercaptotetrazoles described in No. 987, etc., Nitrones: Nitroindazoles: US Pat. No. 2,83
Polyvalent metal salts described in No. 9,403 (Polyvalent
metal snlts): thiuronium salts described in US Pat. No. 3,220,839 (thinroninmsalts): palladium, platinum and gold salts described in US Pat. Nos. 2,566,263 and 2,597,715.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as irradiation prevention and halation prevention.
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.

In the light-sensitive material of the present invention, when the hydrophilic colloid layer contains a dye or an ultraviolet absorber, they may be mordanted with a cationic polymer or the like.

As such a dye, those described in Research Disclosure, Volume 176, P23-26, Absorbing and filter soybeans are used.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt. A compound, a urethane derivative, a urea derivative, an imidazole derivative, 3-pyrazolidones and the like may be included.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

When gelatin is used in the practice of the present invention, the gelatin may be either lime-treated or acid-treated. See Arthur Weuice, The Macromolecular Chemistry of Gelatin, for more details on how to make gelatin. (Academic Press, 1964
Issued annually).

Examples of the hydrophilic colloid that can be used include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose,
Cellulose derivatives such as cellulose sulfates,
Sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers. There are various types of synthetic hydrophilic polymeric substances such as

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chrome 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-2-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichlor-6-hydroxy-3-). Triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycyclo acid etc.), etc. can be used alone or in combination.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.
For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

A protective layer is preferably provided on the silver halide photographic light-sensitive material of the present invention, and this protective layer is a layer made of a hydrophilic colloid, and the hydrophilic colloid used is the one described above. The protective layer may be a single layer or a multilayer.

A matting agent and / or a leveling agent may be added to the emulsion layer or protective layer of the silver halide photographic light-sensitive material of the present invention, preferably in the protective layer. Examples of the matting agent are water-dispersible materials such as polymethylmethacrylate having an appropriate particle size (particle size of 0.3 to 5 μm, or 2 times or more, especially 4 times or more the thickness of the protective layer is preferable). Organic compounds such as vinyl polymers or inorganic compounds such as silver halide and strontium barium sulfate are preferably used. The smoothing agent is useful for preventing adhesion failure similar to the matting agent, and is particularly effective for improving the frictional characteristics related to the camera compatibility during projection or projection of movie films. Specific examples are liquid paraffin, Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or silicones such as their alkylene oxide addition derivatives. Is preferably used.

Various additives may be added to the photographic light-sensitive material of the present invention, if necessary. Examples thereof include dyes, development accelerators, brightening agents, color fog inhibitors, and ultraviolet absorbers. Specifically, Research Disclosure No. 176, pages 22-31 (RD-17643,1
978) can be used.

The silver halide photographic light-sensitive material of the present invention may be optionally provided with an antihalation layer, an intermediate layer, a filter layer and the like.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers can be embodied by coating on one side or both sides of a flexible support usually used for photographic light-sensitive materials. What is useful as a flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthaleal, polycarbonate, a baryter layer or α-. Examples include paper coated or laminated with an olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer).
The support may be colored with a dye or pigment. The surface of these supports is generally subjected to a subbing treatment in order to improve adhesion with a photographic emulsion layer or the like. The surface of the support may be subjected to corona irradiation, ultraviolet irradiation, flame treatment or the like before or after the undercoat treatment. For details, those described in “Supports” of Research Disclosure, Vol. 176, p. 25 are used.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method or the like can be used. For details, the method described in "Costlng procedures" in Research Diroclosure, Vol. 176, pp. 27-28 can be used.

Specific examples of the silver halide photographic light-sensitive material of the present invention include Xray light-sensitive material, lith light-sensitive material, black-and-white photographic light-sensitive material, color negative light-sensitive material, color reversal light-sensitive material, color photographic paper, colloid transfer process, silver salt. It can be used for a diffusion transfer process, a die transfer process, a silver dye bleaching method, a print-out sensitive material, a heat-developable photosensitive material and the like.

The exposure for obtaining a photographic image may be performed using a usual method. That is, natural light (sunlight), tungsten lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, cathode ray tube flying spot, light emitting diode, laser light (for example, gas laser, YAG laser, dye laser, semiconductor) Any of various light sources including ultraviolet light such as a laser) can be used. It may also be exposed by light emitted from a fluorescent substance excited by electron beams, X-rays, γ-rays, α-rays, etc. The exposure time is usually 1/1000 second to 1 second used in a camera. Exposure time of course, exposure shorter than 1/1000 seconds,
For example, 1/10 ⁴ to 1/10 ⁶ using a xenon flashlight or cathode ray tube
Second exposures can be used, and exposures longer than 1 second can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed.

For the photographic processing of the light-sensitive material of the present invention, for example, Research Disciosure No. 176, No. 25-3
Any of various methods and various processing solutions as described on page 0 (RD-17, 643) can be applied.
This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

In addition, depending on the case, various other developing methods (for example, thermal development) can be used.

For example, the developing solution used for black and white photographic processing can contain a known developing agent. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3).
-Pyrazolidone), aminophenols (eg N-
Methyl-p-aminophenol) and the like, alone or in combination. The developer generally contains various other preservatives, alkali agents, pH buffers, antifoggants, etc., and further contains a solubilizing agent, a toning agent, a development accelerator, a surfactant, and a defoaming agent. , A water softener, a hardening agent, a viscosity imparting agent, etc. may be included.

As a special form of development processing, the developing agent in the photosensitive material,
For example, a method may be used in which the photosensitive material is contained in the emulsion layer and is processed in an alkaline aqueous solution for development. Hydrophobic developing agents can be incorporated into the emulsion layer by various methods described in Research Disclosure 169 (RD-16928) U.S. Patent No. 2,739,890, British Patent No. 813,253 or West German Patent No. 1,547,763. Can be included. Such a development treatment may be combined with a silver salt stabilization treatment with thiocyanate.

As the fixer, a fixer having a generally used composition can be used. As the fixing agent, in addition to thione sulfate and thiocyanate, organic sulfur compounds known to be effective as a fixing agent can be used. The fixer may contain a water-soluble aluminum salt as a hardening agent.

In the photographic emulsion layer of the photographic light-sensitive material of the present invention, a color-forming coupler, that is, an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) is developed in a color development process by oxidation coupling. Possible compounds may be included. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetyltamalone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides). , Etc., and cyan couplers include naphthol couplers and phenol couplers.
It is desirable that these couplers are non-diffusible ones having a water group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, it may be a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler).

In addition to the DIR coupler, it may also contain a colorless DIR coupling compound whose coupling reaction product is colorless and currently releases an inhibitor.

The silver halide photographic light-sensitive material of the present invention may contain, as an antifoggant, a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative and the like.

The silver halide photographic light-sensitive material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with an aryl group (for example, those described in U.S. Pat. No. 3,533,794), 4-thiazolidone compounds (for example, those described in U.S. Pat. Nos. 3,314,794 and 3,352,651), benzophenone compounds (e.g. 42-2
No. 784), a cinnamic acid ester compound (for example, those described in US Pat. Nos. 3,705,805 and 3,707,375), a butadiene compound (for example, those described in US Pat. No. 4,045,229), or a benzooxide compound (for example, US Those described in Japanese Patent No. 3,700,455) can be used. In addition, U.S. Pat.
Those described in 4-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol-based cyan dye forming coupler), an ultraviolet absorbing polymer, or the like may be used. These UV absorptions may be mordanted to a particular layer.

In carrying out the present invention, the following various anti-fading agents may be used in combination, and the color image stabilizer used in the present invention may be used alone or in combination of two or more kinds. Anti-fading agents include hydroquinone-derived, gallic acid derivatives, p
-Alkoxyphenols, p-oxyphenol derivatives and bisphenols.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are various primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
Methanesulfoamidoethylaniline, 4-amino-3-
Methyl-N-ethyl-N-β-methoxyethylaniline and the like) can be used.

LFA Mason, Photographic Processing Chemis
try), Focal Press, 1966, P226-229, US patent
Those described in 2,193,015, 2,592,364 and JP-A-48-64933 may be used.

Color developers also include pH buffers such as alkali metal sulfites, carbonates, borates, and phosphates, bromides,
A development inhibitor such as iodide and an organic antifoggant or an antifoggant can be contained. If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competing couplers, fogging agents such as sodium boron hydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, polycarboxylic acid chelating agents, antioxidants It may also contain agents.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones, nitroso compounds and the like are used.

For example, Phelician compounds, dichromates, iron (III)
Or an organic complex salt of cobalt (III) such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2
-Aminopolycarboxylic acids such as propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid, persulfates; permanganates; nitrosphenol and the like can be used. Of these, potassium ferrocyanide, sodium iron (III) ethylenediaminetetraacetate and ammonium iron (III) ethylenediaminetetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

〔Example〕

The present invention will be described below with reference to examples. Of course, the invention is not limited to the examples.

Example-1 First, silver iodobromide emulsion E-1 containing 2.0 mol% of silver iodide
Was prepared by normal ammonia method forward mixing. The average grain size of this emulsion was 1.10 μm. This silver iodobromide emulsion E-1 was optimally sensitized with gold and sulfur by adding chloroauric acid, sodium thiosulfate and ammonium thiocyanate.
Stabilized with -hydroxy-6-methyl, 1,3,3a, 7-tetrazaindene.

The stabilized emulsion described above and a protective layer to which a hardener is added,
A silver halide emulsion layer and a protective layer were coated on both sides of an undercoated polyester film support in this order by the slide hopper method at a coating speed of 100 m / min to form two layers at the same time.
The samples No. 1 to No. 28 in the table were obtained. The coated silver amount was 55 mg / dm ² .

Each of the above samples was adjusted so that the amount of hardener was about 9 minutes for the melting time. The above melting time is defined as the time when a sample (silver halide photographic light-sensitive material) cut into 1 cm x 2 cm is dipped in a 1.5% sodium hydroxide solution kept at 50 ° C until the emulsion layer begins to elute. It's time.

Next, the number of coating failures (for example, coating stripes, coating unevenness, etc.) of the sample obtained as described above was measured, and 1 (poor) to 5
It was represented by a five-level display of (excellent). It should be noted that 3 to 5 causes no problem, but 1 to 2 cannot withstand practical use.

Moreover, the sensitivity measurement was performed as follows. That is, the sample is sandwiched between two optical wedges whose density gradients are mirror-symmetrically aligned, and simultaneously exposed from both sides by a light source having a color temperature of 5,400 ° K for 1 / 12.5 seconds.

The processing was performed using a roller-conveying type automatic processor according to the following steps. The total processing time is 45 seconds.

Processing temperature Processing time Insertion-1.2 seconds Development + migration 35 ℃ 14.6 seconds Fixing + migration 33 ℃ 8.2 seconds Wash + migration 25 ℃ 7.2 seconds Squeeze 40 ℃ 5.7 seconds Dry 45 ℃ 8.1 seconds Total-45.0 seconds Developer is XD -90, XF (both trade names of Konishi Rokusha Kogyo Co., Ltd.) was used as the fixer.

From the characteristic curve showing the relationship between the obtained log E (logarithm of exposure dose) and D (optical density), base density + fog density + 1.
The exposure amount at 0 was obtained, and the relative sensitivity was obtained.

The dryness was evaluated as follows. That is, the above-mentioned automatic development processing for 45 seconds was performed, and the sample that had passed through the dry portion was touched and evaluated comprehensively for the degree of scratching with other samples. It is expressed in 5 steps. It should be noted that 3 to 5 causes no problem, but 1 to 2 cannot withstand practical use.
The above results are summarized in Table 1.

For some of the samples, the line speed of the 45-second automatic processor was reduced to 1/2 and the conventional 90-second processing sensitivity was determined. The results are shown in Table 2.

As is clear from Tables 1 and 2, the sample (silver halide photographic light-sensitive material) of the present invention has good coatability, excellent sensitivity and dryness, and is suitable for ultra-rapid processing. I understand. Also, in comparison with the conventional 90 seconds processing,
It can be seen that the processing time can be cut in half and the processing capacity is doubled while maintaining the sensitivity of the conventional system (90 seconds processing of sample No. 3).

Example-2 Emulsion E-2 containing silver halide grains having a multilayer structure
The preparation of E-6 will be described. First, a 3.0N ammoniacal silver nitrate solution and a solution containing 2.0 mol% of potassium bromide and potassium iodide were added to the gelatin solution by the double jet method while maintaining 45 ° C., pAg = 11.0 and pH = 9.0. The addition rate was gradually increased as the particles grew.

The obtained emulsion was an octahedral monodisperse emulsion having an average grain size of 1.05 μm. Further, an ammoniacal silver nitrate solution and a potassium bromide solution were added at a pAg = 11.0 and a pH = 9.0 by a double jet method to form a pure silver bromide shell. The obtained emulsion was an octahedral monodisperse emulsion having an average grain size of 1.10 μm. This emulsion was designated as E-2.

Next, the production method is similar to that of E-2, but the ratio of potassium iodide to potassium bromide is changed, and the core grain size is changed so that the average silver iodide content after shelling is made uniform, and the same. The addition rate at the initial stage of mixing was adjusted so as to obtain a size, and an octahedral silver iodobromide emulsion containing 5 mol%, 10 mol%, 20 mol% and 30 mol% of silver iodide was prepared. The subsequent steps were exactly the same as for E-2 to prepare octahedral monodisperse emulsions having an average grain size of 1.10 μm and designated E-3, E-4, E-5 and E-6, respectively. E
Chemical sensitization and coating were performed on -1 to E-6 in the same manner as in Example 1 to obtain sample Nos. 29 to 38 in Table 3.

These samples were treated for 45 seconds as in Example-1,
I asked for sensitivity. Further, the blackening of the scratches was measured as follows. That is, the sample was conditioned at 23 ° C. and 55% RH for 4 hours, and then the load was continuously changed with a sapphire needle having a radius of 0.3 mil to perform scratching and development.
That is, the smaller the value, the weaker the scratch blackening.

The above results are summarized in Table 3. As is clear from Table 3, the difference in the iodine content between the core and the shell is 10 mol%.
It can be seen that the above-mentioned particles are less likely to cause scratch blackening and have higher sensitivity as the amount of gelatin is smaller than that of particles of less than 10 mol%.

Example-3 An emulsion containing core grains was prepared in the same manner as E-3 to E-6, whereby an octahedron containing 5 mol%, 10 mol%, 20 mol% and 30 mol% of silver iodide was prepared. A silver iodobromide emulsion was prepared. Octahedral monodisperse core / shell emulsions having an average grain size of 1.10 μm were prepared in the same manner as in E-2 except that 2.0 mol% of shell iodide was added to these emulsions.
It was set to 8, E-9, E-10.

These monodisperse emulsions were chemically sensitized and coated in the same manner as in Example-1 to obtain samples No. 39 to No. 46 in Table 4.
For these samples, the blackening of scratches and the sensitivity were obtained in the same manner as in Example-2, and the results are shown in Table 4.

As is clear from Table 4, particles having a difference in iodide content of 10 mol% or more between the core and the shell are less likely to cause scratch blackening as the amount of gelatin is smaller than that of particles having an iodine content of less than 10 mol%. It turns out that the sensitivity is also excellent.

Example 4 A silver iodobromide monodispersed cubic emulsion containing 2.5 mol% of silver iodide having an average grain size of 0.28 μm was obtained by a double jet method while controlling at 60 ° C., pAg = 8.0 and pH = 2.0. A part of this emulsion was used as a core and grown as follows. That is, to the solution containing this core particle and gelatin, an ammoniacal silver nitrate solution at 40 ° C., pAg 8.0 and pH 9.5 and a solution containing potassium iodide and potassium bromide were added by a double jet method to obtain silver iodide. 5
A first coating layer containing mol%, 10 mol%, 20 mol% and 30 mol% was formed.

Then, in each emulsion, except that pAg was 9.0, E-
A second coating of pure silver bromide was formed in exactly the same manner as in 2, and cubic core monodispersed silver iodobromide core / shell emulsions having an average grain size of 1.0 μm were prepared. It was designated as E-13 and E-14. The average silver iodide content of these emulsions was all 3.0 mol%.

These emulsions were subjected to chemical sensitization and coating in the same manner as in Example-1 to obtain samples No.47 to No.54 in Table 5. For these samples, the blackening of scratches and the sensitivity were determined in the same manner as in Example-2, and the results are shown in Table 5.

As is clear from Table 5, in E-12 to E-14 having a layer having a difference in iodide content of 10 mol% or more between the core and the shell, the blackening of scratches occurs as the amount of gelatin decreases. It can be seen that it is difficult and the sensitivity is excellent.

〔The invention's effect〕

As described above, according to the present invention, the total processing time is 20 seconds to
When ultra-rapid processing of 60 seconds is performed, a silver halide photographic light-sensitive material excellent in sensitivity, contrast, maximum density, fixability and dryness can be obtained.

Further, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material which causes less troubles during coating even when the amount of gelatin is small.

Further, according to the present invention, it is possible to obtain a silver halide photographic light-sensitive material with less scratch blackening even with a small amount of gelatin.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material for X-rays having at least one light-sensitive silver halide emulsion layer and at least one protective layer on at least one side of a support, and coating for forming the outermost layer on the one side. The surface tension of the liquid is 6 dyn / c higher than the surface tension of the coating liquid that forms a layer adjacent to the outermost layer.
A silver halide photographic light-sensitive material for X-rays, which is simultaneously multi-layered under a condition of smaller than m and the amount of gelatin on one side is 2.20 to 3.10 g / m ² .