JPH01158430A - Silver halide photographic sensitive material having excellent sharpness and capable of hyper-rapid processing - Google Patents

Abstract

PURPOSE:To permit the rapid processing of the title material by incorporating a specified dyestuff in at least one layer of photographic constituting layers of the sensitive material, and by specifying the amount of gelatin contd. in the photographic constituting layer positioned in the side of a photosensitive silver halide layer in a range of 2.0-3.5g/m<2>. CONSTITUTION:At least one kind of the dyestuff having a max. absorption wavelength (lambdamax) of 400-850nm in the aqueous solution of the dyestuff, is incorporated in at least one layer among either layers of the photographic constituting layers, and the amount of the gelatin contd. in the photographic constituting layer positioned in the side of the photosensitive silver halide is in the range of 2.0-3.5g/m<2>. The dyestuff is not specified, and as the dyestuff can remove the effect of a wavelength, absorbing a prescribed wavelength according to the sensitive material, the dyestuff can be suitably selected from the dyestuffs capable of improving the sharpness of the sensitive material. Thus, the rapid processing of the sensitive material is made possible.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material that can be processed at high speed. In particular, it relates to a silver halide photographic light-sensitive material that is highly sharp and has little residual color after processing even when subjected to ultra-rapid processing.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a demand for speeding up the development processing of the negative layer, that is, increasing the processing amount within the same amount of time.

The above-mentioned trend is also observed in the field of X-ray sensitive materials, such as medical X-ray films. That is, the number of medical examinations is rapidly increasing due to the enforcement of regular health examinations, and the number of examination items is increasing in order to make the diagnosis more accurate, and the number of X-ray photographs is increasing.

On the other hand, it is also necessary to inform the examinee of the diagnosis result as soon as possible.

That is, there is a strong demand for faster development and diagnosis than before. Particularly in angiography photography, intraoperative photography, etc., it is essentially necessary to view the photographs as quickly as possible.

In order to meet the above-mentioned demands of the medical community, it is necessary to promote automation of diagnosis (imaging, transport, etc.) and to process X-ray films more quickly.

However, when ultra-rapid processing is performed, (a) the density is not sufficient (reduction in sensitivity, contrast, and maximum density), (b) the fixing is not sufficient, and (C) the film is not washed with water enough. (d) Problems such as insufficient drying of the film occur. Insufficient fixing and insufficient water washing cause the color tone to change during film storage, resulting in a decrease in image quality.

As mentioned above, ultra-quick processing is desired, and in this specification, ultra-quick processing means that after inserting the leading edge of the film into an automatic developing machine, , the total time it takes for the leading edge of the film to emerge from the drying section after passing through the washing tank, transition section, and drying section [In other words, the total length of the processing line (m) is expressed as the line conveyance speed (m/s
A process in which the quotient (sec,)) divided by c,) is 20 seconds or more and less than 60 seconds. The reason why the time for the transition part should be included here is that it is well known in the industry that the liquid from the previous process is swollen in the gelatin film even at the transition part, so there is virtually no processing time required. This is because it can be seen that the process is progressing.

Japanese Patent Publication No. 51-47045 describes the importance of the amount of gelatin in rapid processing, and the total processing time including the crossing portion is 60 seconds to 120 seconds. However, this processing time cannot meet the recent demands for ultra-quick processing.

One way to solve the above-mentioned problems (a) to (d) is to reduce the amount of gelatin, but as a result of research by the inventors, it was found that sharpness decreases as the amount of gelatin is reduced. Conventionally, it was thought that reducing the amount of gelatin would reduce the film thickness and improve sharpness, but the results were contrary to this.

If the amount of gelatin is reduced in order to make the image suitable for rapid processing, the sharpness will be significantly lowered, so it is necessary to prevent this in order to obtain high quality images.

On the other hand, in the medical field, in order to improve the photographic effect of X-rays during X-ray photography, photosensitive materials have silver halide emulsion layers on both sides of a support (hereinafter referred to as "double-sided photosensitive materials").
When photographing, fluorescent screens are placed in close contact with each surface of the photosensitive material for X-ray exposure, but in this case, the light generated from the fluorescent screens placed on both sides of the photosensitive material causes halogenation of the photosensitive material. It is refracted, reflected and scattered in a complicated manner by the silver emulsion layer, the interior and surface of the support, or the surface of the fluorescent screen, and in particular reaches the emulsion layer on the opposite side and exposes it, significantly reducing the sharpness of the image. A phenomenon occurs that lowers the Such a phenomenon is generally called a crossover phenomenon or a print-through phenomenon, and it is necessary to prevent this phenomenon in order to obtain a highly sharp X-ray image. This phenomenon is particularly noticeable in light-sensitive materials in which the amount of gelatin is reduced, and together with the reduction in sharpness due to the above reasons, the sharpness is significantly deteriorated.

Furthermore, not limited to double-sided photosensitive materials, there is a so-called halation phenomenon in which light that has passed through an emulsion layer is reflected and scattered on the support surface and then sensitizes the emulsion again, and light reflected by one grain sensitizes adjacent grains. Sharpness deteriorates due to the so-called irradiation phenomenon, and reducing the amount of gelatin causes further deterioration of sharpness.

[Purpose of the invention]

The object of the present invention is to provide a silver halide photograph that reduces the amount of gelatin without causing the deterioration of sharpness as described above, and that enables high-speed processing, for example, ultra-rapid processing in which the total processing time is 20 seconds or more and less than 60 seconds. Our purpose is to provide photosensitive materials.

[Structure and operation of the invention]

The object of the present invention described above is that at least one of the photographic constituent layers contains at least one dye having a maximum absorption wavelength (λ□, ) in the range of 400 to 850 nm in an aqueous solution; This is achieved by using a silver halide photographic light-sensitive material in which the amount of gelatin in the photographic constituent layer on the side having photosensitive silver halide is in the range of 2.0 to 3.5 g/rd.

The photosensitive material of the present invention has at least one layer on one side of the support.
It has a photosensitive silver halide emulsion layer as a layer, and may be a double-sided photosensitive material, or may have an emulsion layer on only one side.

Note that the amount of gelatin mentioned above is the amount per one side.

Any dye having a maximum absorption wavelength (λ□X) in an aqueous solution of 400 nm or more and 850 nm or less can be used in the photosensitive material of the present invention, and depending on the photosensitive material, Dyes that can improve sharpness by absorbing a desired wavelength and eliminating the influence of the wavelength can be appropriately selected and used. Generally, these dyes can be selected to have a complementary color relationship with the emission distribution of the light source used with the photosensitive material, and can be added to the hydrophilic colloid layer singly or in combination.

It is preferable that the dye is decolorized or washed away during the development process of the photosensitive material, so that the coloring is no longer visible when the image is completed.

Dyes that are preferably used in the photosensitive material of the present invention and are decolorized or washed away during development include many compounds known as antihalation dyes or antiirradiation dyes for photosensitive materials, such as the following: It will be done. The structural formula and maximum absorption wavelength of an aqueous solution are shown below. However, those that can be used in the present invention are not limited to those exemplified below.

(Exemplary Compounds) SO, Na 03e SO, Na ■ HN(CJs), I" U 5OJa 48B Among the above dye compounds, compounds having a structure included in the following general formula (1) are particularly preferable. can be given.

General formula (I) However, R1 and R2 in the formula are an alkyl group having 1 to 7 carbon atoms, a carboxyl group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an amino group, an acylamino group, or a trifluoromethyl group, and M is hydrogen atom, alkali metal atom, or ammonium group, n is 0.1 or 2.

The above-mentioned dyes exemplified include, for example, British Patent No. 560.385
No., U.S. Patent No. 1.884.035, Special Publication No. 39-2
It can be easily synthesized by the method described in, for example, No. 2069.

Specific examples of the above dyes and other usable dyes include West German Patent No. 616,007, British Patent No. 584.609, and West German Patent No. 1
．． No. 177.429, Special Publication No. 26-7777, No. 39
No.-22069, No. 54-38129, JP-A-1973-
No. 85130, No. 49-99620, No. 49-114
No. 420, No. 49-129537, No. 50-2882
No. 7, No. 52-108115, No. 57-185038
No. 1.878.961, U.S. Patent No. 1.884.
No. 035, No. 1,912.797, No. 2, 098.8
No. 91, No. 2,150.695, No. 2,274.78
No. 2, No. 2,298,731, No. 2,409,612
No. 2,461,484, No. 2,527.583, No. 2,533.472, No. 2,865゜752,
2,956.879, 3.094.418, 3゜125.448, 3.148.187, 3
, No. 177.078, No. 3,247.127, No. 3,
No. 260,601, No. 3.282.699, No. 3.4
No. 09.433, No. 3,540.887, No. 3,57
5.704, 3,653.905, 3,718
, No. 472, No. 3.865.817, No. 4,070.
No. 352, No. 4,071,312, PR Report 74
It is described in No. 175, PH0TO, ^BS, Sat 28 ('21), etc.

The constituent layer to be added may be any photographic constituent layer of the light-sensitive material. That is, the photosensitive emulsion layer constituting the photosensitive material,
The emulsion layer may be contained in at least one other hydrophilic colloid layer (for example, a non-photosensitive layer such as an intermediate layer, a protective layer, and a subbing layer) that is troublesome to coat. It is preferably added to the silver halide emulsion layer, a layer closer to the support, or both, and more preferably, it is effective to add it to the coating layer facing the transparent support. It is preferable that the concentration of the dye is higher on the side closer to the support.

The amount of the dye added is preferably 0.2/nl to 20
■/nl, more preferably 0.8mg/rd ~1
5mg/%.

Such dyes that function as filters are
It can be introduced into the hydrophilic colloid layer by conventional methods.

That is, when this dye is made into an aqueous solution of an appropriate concentration and used to color the emulsion layer, it is added to the silver halide emulsion solution before coating.
In addition to an aqueous solution of a hydrophilic colloid, these solutions may be applied onto the support directly or via another hydrophilic colloid layer by various methods.

It may be added at any time during the production of the photosensitive material. From an operational point of view, it is preferable to do this immediately before coating.

As mentioned above, it is preferable that the concentration of the dye is higher on the side closer to the support, but in order to fix the dye on the side closer to the support in this way, it is preferable to use a mordant agent.For example, Non-diffusible mordant agents can be used to bind at least one of the above-mentioned dyes, such as those described in German Patent No. 2.263.031 and British Patent No. 1.221.131.
No. 1,221.195, JP-A-50-47624
No. 50-71332, Special Publication No. 51-1418,
U.S. Patent No. 2.548.564, U.S. Patent No. 2,675.31
No. 6, ° 2,795.519, 2,839,40
No. 1, No. 2,882.156, No. 3,048.487
No. 3,184.309, No. 3,444゜138, No. 3,445.231, No. 3,706,563,
Compounds described in Japanese Patent No. 3,709,690, Japanese Patent No. 3,788,855, etc. can be preferably used.

Preferably, a polymer or copolymer represented by the following general formula (M I ) is particularly effective.

General Formula [M1] In the formula, Q is an atomic group necessary to complete the imidazole ring nucleus together with the N atom, X is an acid group, an acid anion, or a halide anion, and n is 0 to 1.

General formula (MII) In the formula, R11R2 and R3 are C1 to C3 alkyl groups (
This alkyl group may have a substituent or may be an alkylene group or an arylene group, p and q are 0 or 1, and X represents an acid anion or a halide anion.

General formula (Mn[) -CH, -CH- An integer of 1 to 2, m represents an integer of O to 1.

The polymer or copolymer represented by the above general formula (Mn) is more preferably one represented by the following general formula (MIV).

General Formula (MIV) In the formula, RI', RZ' and R3' are an alkyl group of CI=Cs (this alkyl group may have a substituent), and X is an acid anion or a halide anion.

Specifically, the following can be mentioned.

X:)'-25 near 5 x:y=25 near 5 CH31e x: y =66.7: 33.3x: y
=66.7: 33.3X:)F=75:25 X:F=50:50 x: y: z-48:48: 4x:
y: z = 49:49: 210゜ ■ C6HI3 Cl0 X: 3F = 50:50 11゜
No. 418, JP-A-51-73440, JP-A No. 53-129
No. 034, No. 54-74430, No. 54-15583
It can be easily synthesized by the method described in No. 5, No. 55-22766, etc.

These compounds are used after being dissolved in water or a hydrophilic organic solvent (e.g. methanol, acetone), etc. When carrying out the present invention, methods for combining the non-diffusible mordant and the dye are known in the art. Although various methods can be used, a method of binding in a gelatin binder is particularly preferred.

In addition, a method of binding in an applicable binder and dispersing in an aqueous gelatin solution using ultrasonic waves or the like can also be applied.

Although the bonding ratio varies depending on the compound, usually 0.1 to 10 parts of the non-diffusible mordant is bonded to 1 part of the water-soluble dye. The amount added as water-soluble dye is determined by combining with non-diffusible mordant.
The dye can be used in larger amounts than alone.

When cicada is contained in a light-sensitive material, a new constituent layer containing a combination of a dye and a non-diffusible mordant may be provided as a constituent layer, and its position can be selected arbitrarily, but it is preferably placed on a transparent support. The gelatin used in the present invention may be either lime-treated or acid-treated. For details on the method of manufacturing gelatin, see Arthur Vuis, The Macromolecular Chemistry of Gelatin, (Academic Press, 1)
Published in 1964). Hydrophilic colloids other than gelatin that can be used include, for example, gelatin derivatives, graft polymers of gelatin and other polymers,
Proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfate esters; W! such as sodium alginate and starch derivatives; Derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
There are a wide variety of synthetic hydrophilic polymeric materials such as monopolymers or copolymers such as polyvinylpyrazole. In the case of gelatin, it is preferable to use gelatin having a jelly strength of 200 or more in the baggie method for the photosensitive emulsion layer.

The light-sensitive material of the present invention is suitable for high-speed processing, and even when subjected to ultra-high-speed processing as described above, excellent photographs can be obtained without the above-mentioned problems.

In a preferred embodiment of the present invention, the photosensitive material of the present invention is processed in an automatic processor in which the processing time is 20 seconds or more and less than 60 seconds.

Preferred grains as silver halide grains used in the present invention are firstly disclosed in JP-A-58-113.927 and JP-A-58-113.927;
-113.928 and JP-A-59-105.
636, pages 252-253, 60-147.
It is preferable to use the tabular grains disclosed in Japanese Patent No. 727.

Second, as another preferable grain, a silver halide photographic emulsion consisting of silver halide grains having a multilayer structure is used, and any two adjacent layers of the silver halide grains each having a homogeneous iodine distribution ( The purpose is to use photosensitive silver halide grains in which the difference in average iodine content (between coating layers or between an inner core and a coating layer) is 10 mol% or less.

Furthermore, it is preferable that the average iodine content of the outermost layer is 10 mol % or less, and that the silver halide grains are chemically sensitized.

Here, the particles having a multilayer structure are those in which a coating layer made of an arbitrary halogen composition is provided on the outside of the inner core, and this coating layer may be only one layer, or may have two or more layers, for example, three layers.
A layer or four layers may be stacked. Preferably the number of layers is 5 or less.

As the silver halide for the inner core and the coating layer, silver bromide, silver iodobromide, and silver iodide are preferably used, but a mixture with a small amount of silver chloride may be used. Specifically, silver chloride is 10
The content may be about 0 mol% or less, preferably about 5 mol% or less.

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

The average iodine content in the entire silver halide grain is 10 mol%
The following is preferable, and 6 mol% or less is more preferable.

For example, in -Xray material, etc., iodine may increase problems such as inhibition of development and infectious development, so it is actually preferable to keep the content of iodine below a certain level. The total iodine content in the entire particle is preferably 10 mol% or less, more preferably 7 mol% or less, and most preferably 5 mol% or less.

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

Here, being homogeneous can be more specifically explained as follows.

That is, when performing X-ray diffraction analysis of silver halide grain powder, the planar index (2
00) peak half-width is Δ2θ=0.30 (deg)
It means that: The conditions for using the diffractometer at this time are ωτ/, where the scanning speed of the goniometer is ω (deg/m1n), the time constant is τ (sec), and the width of the receiving slit is r (crane).
r≦10.

As for the halogen composition of the internal core, the average iodine content is preferably 40 mol% or less, more preferably 0 to 40% by mole.
It is 20 mol%.

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

In addition, the silver iodide content of coating layers other than the outermost coating layer is as follows:
Preferably it is 10 mol% to 100 mol%.

When silver halide grains consist of three or more layers and the coating layer consists of silver iodobromide, it is not necessary that they all be homogeneous, but all layers must be made of homogeneous silver iodobromide. is preferred.

Such a coating layer (or inner core) with high iodine content
In the case of a negative-working silver halide emulsion, it is preferable that it exists below the outermost surface. In the case of a positive-working silver halide emulsion, the silver iodide content of the outermost coating layer on the surface is preferably 10 mol % or less, more preferably 0 to 5 mol %.

Regarding the iodine content of the inner core and coating layer of silver halide grains used in the practice of the present invention, for example, J.
1. Goldstein, D.
B. Williams rT E
"X-ray analysis in M/ATEM" Scanning Electron Microscope (1977), i1m'
.

NIT Research Institute), No. 65
It can also be determined by the method described on page 1 (March 1977).

For example, when the silver 10-genide grain used in the practice of the present invention is composed of two layers, it is preferable that the inner core has a higher code than the outermost layer, and when it is composed of three layers, it is preferable that the inner core has a higher code than the outermost layer. It is preferable that the coating layer or inner core has a higher iodine content than the outermost layer.

The present invention can be preferably applied to chemically sensitized silver halide grains.

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

In the case of a negative type, it is preferable to apply chemical sensitization so that the optical density is 60% or more of the optimum sensitivity when taking the sensitivity point of "Fog + 〇, I J". .

In the case of a positive type, the degree of chemical sensitization is determined by chemically sensitizing the inside of the particle so that it becomes 60% or more of the maximum sensitivity when taking the sensitivity point of "maximum density - ○, 1" in the optical density. It is preferable to apply

The average grain size of the silver halide grains used in the present invention is:
The particle size is defined as the length of the diameter when converted to a sphere of equal volume, and is expressed as the average value.

The particle size can be determined with a centrifugal Stokes diameter meter or measured with an electron microscope.

In the present invention, the average grain size of the silver halide emulsion grains used in the silver halide emulsion layer is preferably 0.20 to 2.
．． 50 μI11. More preferably 0.30”1.30
An embodiment may be mentioned in which the diameter is .mu.m, most preferably 0.30 to 1.10 .mu.m.

The particle size distribution of the particles used may be narrow or 100 mm wide.

Further, the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, and may be monodisperse.

Here, monodisperse means a dispersion system in which 95% of the particles fall within ±60%, preferably within 40%, of the number average particle size. Here, the number average grain size is the number average diameter of the projected area diameter of silver halide grains.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may have a regular crystal shape such as a tetrahedron or a dodecahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or a composite of these crystal shapes. It can be something that has a shape. It may also consist of a mixture of particles of various crystalline forms.

In addition, for example, a junction type silver halide crystal that combines an oxide crystal such as PbO and a silver halide crystal such as silver chloride, and an epitaxially grown silver halide crystal (
For example, silver chloride, silver iodobromide, silver iodide, etc. are grown epitaxially on silver bromide. ), a hexagonal crystal, a crystal in which a regular hexahedral silver chloride is aligned over a regular octahedral silver iodide, etc. may be used.

Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area. For details, see JP-A-58-127.
921, No. 58-113927, etc.

The above-mentioned regular grains refer to a silver halide emulsion in which at least 80% of the silver halide grains by weight or number of grains have a regular shape. Furthermore, the term "silver halide grains with a regular structure or morphology" refers to grains that do not include anisotropic growth such as twin planes, and which grow equidistantly, such as cubic, tetradecahedral, octahedral, and dodecahedral , has a spherical shape, etc. ``The method for producing such regular silver halide grains is described, for example, in Journal of Photographic Science (J, Phot, Sci.), 5.
．． 332 (1961), Ber, Bunse
nges, Phys, CheIII,),
67+949 (1963), International Conference of Photographic Sciences of Tokyo (Intern, Con)
Gress Photo, Sci, Tokyo.

(1967) and others. Such regular silver halide grains can be obtained by adjusting the reaction conditions when growing silver halide grains using a simultaneous mixing method. In such a simultaneous mixing method, silver halide grains are produced by adding approximately equal amounts of a silver nitrate solution and a halide solution to an aqueous solution of a protective colloid while vigorously stirring the solution.

When carrying out the present invention, for example, when containing regular silver halide grains as described above, it is possible to contain irregular silver halide grains. However, if such particles are present, they generally should not account for more than about 50% by weight or number of particles. In preferred embodiments, at least about 60-70% by weight
consists of regularly ordered silver halide grains.

In the production of monodispersed emulsions and/or emulsions with regular silver halide grains, supply of silver ions and halide ions is important so that existing crystal grains are not dissolved away as the crystal grains grow, and conversely, new grains are created. At a critical growth rate that does not allow generation or growth and provides sufficient silver halide to grow only existing grains, or within its allowable range,
Preferably, the growth rate is increased continuously or stepwise. As for this increasing method,
No. 90, No. 52-16364, JP-A-55-1423
It is described in Publication No. 29.

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

This critical growth rate is determined by the temperature, pH, pAg, degree of stirring,
Composition, solubility, particle size, interparticle distance of silver halide grains,
Although it varies depending on the crystal habit or the type and concentration of protective colloid, it can be easily determined experimentally by methods such as microscopic observation of emulsion particles suspended in a liquid phase and turbidity measurement.

It is also possible to use a combination of internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2086.

In the practice of this invention, the silver halide grains used in the silver halide emulsion are, for example, T, )l.

James, The Theory of the Photographic Process
e Photo-graphic Process),
4th edition, published by Macmillan (1977), P
, by Glfkides, Chimie etPhysig Photography (Chimie etPhysig
ue Photography (Paul M.
onte1, 1967), G., F., Duf.
fin, Photographic Emulsion Chemistry,
Chemistry) (The Focal Pr.
ess, 1966), V., L., Zelikm.
Making and Coating Photographic Emulsions by anet al.
and Coating PhotographicE
mulsion), (The Focal Pres.
Neutral method, acidic method, ammonia method, forward mixing method, back mixing method, double jet method, Chondrold double jet method, congersion method, core/shell method, etc. It can be manufactured by applying methods such as method.

Another form of the double jet method is the triple jet method, in which soluble halogen salts of different compositions are added independently (e.g., soluble silver salt, soluble bromine salt, and soluble iodine salt).
can also be used.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used.

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

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (
For example, U.S. Patent No. 3,271157, U.S. Patent No. 3,574
．． No. 628, No. 3.704.130, No. 4.29
7.439, 4.276.374, etc.), 4th compound (for example, JP-A-53-144,319, JP-A-53-82.408, JP-A-55-77.737) etc.), amine compounds (e.g. JP-A-54-100.71
No. 7) etc. can be used. Among them, ammonia is preferred.

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

These silver halide grains or silver halide emulsions contain at least one salt (soluble salt) of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, and tungsten platinum. is preferably contained. Its content is preferably between 10-b and 10-b per mol Ag.
− 'Mole.

Particularly preferably, at least one of thallium, palladium, and iridium salts is contained. These may be used alone or in combination, and the addition position (time) is arbitrary. This improves flash exposure characteristics,
It is expected to have effects such as prevention of pressure desensitization, prevention of latent image progression, and sensitization.

In order to remove soluble salts from the emulsion after precipitation or physical ripening, the Tardel water washing method, which involves gelling gelatin, may be used. For example, a precipitation method (flocculation method) using gelatin derivatives (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, but it is preferably chemically sensitized. For chemical sensitization, for example H.
photography
Prozesse mit Silverhaloge
Niden), Akade-mische Verlag (Akade-mische Verlag)
aesellschaft) 1968, 675-7
The method described on page 34 can be used.

That is, sulfur sensitization using sulfur-containing compounds (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active gelatin silver; reducing substances (e.g., silver-tin salts, amines); hydrazine derivatives,
Reduction sensitization method using formamidine sulfinic acid, silane compounds); noble metal compounds (e.g. gold complex salts, p
t.

A noble metal sensitization method using complex salts of metals in group (I) of the periodic table such as Ir and Pd can be used alone or in combination.

Specific examples of these include, for the sulfur sensitization method, U.S. Pat.
U.S. Patent No. 3.656.955, etc., and U.S. Patent No. 2.983゜609 and U.S. Pat.
No. 4, - No. 4.054.458, etc., and US Pat. No. 2.599.083, US Pat.
48.060, British Patent No. 618.061, etc.

Sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Typical examples are U.S. Pat. No. 2.688,543 and U.S. Pat.
77゜229, 5,397.060, 3.32
No. 2.052, 5°327; No. 601, 3,61
No. 7.293, No. 5,636.960, No. 3,666
．． No. 450, No. 3,272.898, No. 3,679.
No. 428, No. 3,703.377, No. 3,769,3
No. 01, No. 3,814゜609, No. 3,537.56
No. 2, No. 4,026.707, British Patent No. 1,344,
No. 281, No. 1,207.503, Special Publication No. 1977-45
No. 36, No. 53-12373, JP-A No. 53-1106
No. 15, No. 53-109923.

Together with the sensitizing dye, it is a dye that itself does not have a spectral enhancement effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

For example, aminostilbene compounds substituted with a nitrogen-containing heterocyclic group (e.g., U.S. Pat. No. 5,533,590;
．． 638.721), aromatic organic acid formaldehyde condensates (e.g., U.S. Pat. No. 3,743,51)
0), cadmium salts, azaindene compounds, etc.'. U.S. Patent 5,615.615
The combinations described in No. 3,615.641, No. 5,617,295, No. 3,635, and '121 are particularly effective.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxadorinthion; azaindenes, e.g. Triazaindenes, tetraazaindenes (
antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. A number of compounds known as can optionally be added.

For more information, please visit t! , J. Birr, Stabilization of Photographic Silver Halide Emulsions.
fPhotographic 5ilver Ha
ride IimulsionS), FocalP
ress, 1974, etc.

Compounds that can be used include, for example, U.S. Pat.
Thiazolium salts described in U.S. Pat. No. 38 and U.S. Pat. Urazoles described in U.S. Patent No. 3,287.135, etc.: U.S. Patent No. 3,236,6
Sulfocatechols described in U.S. Patent No. 32, etc.: Oximes described in U.K. Patent No. 623.448, etc.: U.S. Patent No. 2.403.927, U.S. Patent No. 3.266
．． Mercaptotetrazoles described in U.S. Pat. No. 897, U.S. Pat.
metal 5 alts): US patent tube 3,220
．． Thiuronium salt (th
iuronium salts): U.S. patent cylinder 2.56
The photographic emulsion layer of the photographic light-sensitive material of the present invention described in Japanese Patent No. 6.263 and No. 2.597.715 contains, for example, polyalkylene oxide or its like for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also include derivatives such as ethers, esters, and amines, 1,000-onythyl compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active vinyl compound (1,3,5-) react°
active halogen compounds (2,4-dichloro-6-hydroxy-3-
triazines, etc.), mucohalogen acids (mucochloric acid,
mucophenoxychloric acid, etc.), etc.) can be used alone or in combination.

From the viewpoint of graininess and drying properties, when the silver halide photographic material of the present invention is immersed in an aqueous solution of 1.5% by weight of sodium hydroxide at 50.0°C without stirring, the silver halide grains separate from the support. It is preferable to harden the film by adding a hardening agent so that the time until detachment is 10 minutes or more, more preferably 15 minutes or more.

When the silver halide photographic material of the present invention is processed, for example, in a roller conveyance type automatic processing machine, it is often processed in a state from development to drying. The water content of the photographic material is 6.0.
It is preferably in the range of ~15.0 g/trr, particularly preferably in the range of 9.0-14.0 g/rrl. In this specification, the water content of a silver halide photographic material is determined by the following measuring method under conditions of 25° C. and 75% relative humidity. That is, 20C1lX2
A sample exposed to the amount of light necessary to obtain the maximum density of 0 CIl was processed using an automatic processor KX-5 manufactured by Konishiroku Photo Industry ■.
00 (processing speed selector switch at 90 seconds) (the outline of its configuration is shown in Figure 1), and the developer was Konishiroku Photo Industry ■.
A predetermined amount of Starter XD-9O3 (manufactured by the same company) was added to the manufactured Kura XD-90, and this was used at 35°C, and Sakura New XF (manufactured by the same company) was used as the fixer at 32°C, and the washing water was Automatic development was carried out by supplying tap water at 18° C. at a rate of 31°C per minute. The drying rack of the automatic developing machine (indicated by reference numeral 92 in Figure 1) was removed, and 101 sheets of the same sample as the moisture content measurement sample were processed in succession at an interval of 1 sheet/12 seconds, including the 101st sample. A water amount measurement sample is taken out of the squeeze rack (indicated by reference numeral 91 in FIG. 1) at the point where it exits, and the weight is measured after 15 seconds. (At this time, make adjustments in advance so that the power to the drying system does not turn on.) The weight at this time is Ww (g).

Next, after thoroughly drying the sample, heat the sample at 25℃ for 1 hour or more.
It is left to stand under conditions of 5% RH, and its weight is measured. Let this be Wa (g). The water content is calculated from the following formula.

Water content (g/rrr) = Ww −wa x (1000
0a&/20cm x 20ca+) The location for weight measurement must be a location where the wind speed is 0.5 m/sec or less.

The photographic material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the 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 (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid. , methacrylic acid, α,β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and the like can be used. Note that the term (meth)acrylate mentioned above is an abbreviation for both acrylate and methacrylate.

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

A matting agent and/or a smoothing agent may preferably be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention.

As the matting agent, known matting agents can be used, but polymer matting agents or silica matting agents are more preferable.
The average particle size is preferably 0.3 μm to 12 μm, especially 3 μm.
Preferably, the diameter is in the range of μm to 9 μm.

Specific examples of polymer matting agents used in the practice of the present invention include water-dispersible vinyl polymers such as polymethyl methacrylate, cellulose acetate propionate, and starch. Particularly preferred are matting agents made of water-dispersible vinyl polymers such as homopolymers of acrylic esters such as methyl methacrylate, glycidyl acrylate, and glycidyl methacrylate, or copolymers of these acrylic esters with each other or with other vinyl monomers. . Among these, spherical matting agents of polymethyl methacrylate having an average particle diameter of 3 μm to 9 μm are particularly preferred.

The matting agent is added to the protective layer above the emulsion layer or, for example, to the protective layer on the back side, but it is more preferable to add the above-mentioned polymer matting agent to the protective layer on the emulsion layer side. For example, when processing a photographic light-sensitive material containing a polymer matting agent with a roller conveyor type automatic developer, the light-sensitive material will not slip.

Smoothing agents help prevent adhesion failure similar to matting agents, and
It is particularly effective for improving frictional properties related to the projection of motion picture film or camera compatibility during projection, and specific examples include waxes such as liquid paraffin, esters of higher fatty acids, polyfluorinated carbonized Hydrogens or derivatives thereof, silicones such as polyalkylpolysiloxane, polyarylpolysiloxane, polyalkylarylpolysiloxane, or alkylene oxide addition derivatives thereof are preferably used.

It is preferable to use a plasticizer in the light-sensitive material of the present invention in order to prevent fog during coating and drying, and to prevent fog and desensitization caused by bending under low humidity conditions. Examples of plasticizers include JP-A No. 48-63715 and JP-A No. 43-4
No. 939, No. 47-8745, U.S. Patent No. 306, 47
No. 0, No. 2,960.404, No. 3.412.159
issue.

3,791.857 etc. can be used, but preferably at least 2
At least one polyhydric alcohol compound having three or more hydroxyl groups is contained. Such compounds include alcohols that have 2 to 12 hydroxyl groups and 2 to 20 carbon atoms, and in which the hydroxyl groups are not conjugated with a conjugated chain, that is, an oxidized form cannot be written. is preferred. Furthermore, the melting point is preferably 50°C or higher and 300°C or lower. Examples of compounds include JP-A-62-14744
There is one described in No. 9.

In carrying out the present invention, surfactants can be used in the photosensitive material for various purposes, such as saponin (steroid type), alkylene oxide derivatives (such as polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl Ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters,
polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone),
Examples include nonionic surfactants such as glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. In addition, alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfonate Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as alkyl polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphate esters, etc. can be used. Further examples include amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides.

Also, alkylamine salts, aliphatic or aromatic quaternary
Examples include cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings. Furthermore, a fluorine-containing surfactant, a fluorine-containing surfactant having a polyoxyethylene group, etc. can be used.

As an alkylene oxide type surfactant,
1-9610, DT-2648746, Japanese Unexamined Patent Publication No. 1973
-129623, 54-89624, 54-982
35, 58-203435, 5B-208743,
Examples include 60-80848 and 60-94126. Examples of using alkylene oxide surfactants in combination with other compounds include JP-A-54-89626 and JP-A-54-89626;
-70837, 57-11341, 57-1099
47, 59-74554, 60-76741, 6
0-76742, 60-76743, 60-808
39, 60-80846, 60-80847, 5
0-131293, 53-29715, and the like.

As an anionic surfactant, JP-A-53-21922
, CB-1503218, Japanese Patent Publication No. 56-1617 and higher alcohol sulfate ester salts, higher alkyl sulfonates, alkylbenzene sulfonates, dialkyl sulfosuccinates, acylmethyl taurides, N-acyl sarcosinates, fatty acid monoglyceride sulfates,
Examples include α-sulfonic acid.

Examples of fluorine-containing surfactants include Japanese Patent Publication No. 47-93
03, 48-43130, 52-25087, 5
7-1230, JP-A No. 49-46733, JP-A No. 50-16
525, 50-34233, 51-32322, 54-14224, 54-111330, 55-5
57762, 56-19042, 56-41093
, 56-34856, 57-11341, 57-
29691, 57-64228, 57-14624
8, 56-114944, 56-114945, 5B-196544, 58-200235, 60-
109548, 57-136534, US-3589
906, same 3775126, same 4292402, R
D-16630 and the like, and compounds exemplified in JP-A No. 60-164738.

Various other additives may be used in the photographic material of the present invention, if necessary. For example, dyes, development accelerators, fluorescent whitening agents, color anti-capri agents, ultraviolet absorbers, etc. Specifically, research disclosure (
RESEARCH DISCLOSURE) No. 176 No. 2
Those described on pages 2 to 31 (RD-17643, 1978) can be used.

The silver halide photographic material of the present invention may also be provided with an antihalation layer, an intermediate layer, a filter layer, etc., if necessary.

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers can be embodied by being coated on one or both sides of a flexible support commonly used in photographic light-sensitive materials.

Useful as flexible supports are films of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or alpha-olefin polymers. (For example, paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like.

As the undercoating treatment, it is preferable to use the technique described in Japanese Patent Application No. 60-25704. The surface of the support may be subjected to corona irradiation, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment. For details, those described in "5upports JO" of Research Disclosure, Vol. 176, P, 25 are used.

In the photographic 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, etc. can be used. For more information, see Research Disclosure, Volume 176, P, 27-28.
The method described in procedures J can be used.

Specific examples of the silver halide photographic material of the present invention include Xray photosensitive material, Lith photosensitive material, black and white photosensitive material, color negative photosensitive material, color reversal photosensitive material, color photographic paper, colloid transfer process, and silver salt photosensitive material. It can be used in diffusion transfer processes, die transfer processes, silver dye bleaching methods, printout sensitive materials, heat developable sensitive materials, etc.

Exposure to obtain a photographic image may be performed using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, light emitting diodes, laser lights (e.g. gas lasers, YA
Any of various light sources including ultraviolet light, such as G laser, dye laser, semiconductor laser, etc., can be used. Alternatively, exposure may be performed using light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like.

Exposure times range from 1/1000 seconds to 1 second, which is normally used with cameras, as well as exposure times shorter than 1/1000 seconds, such as 1/1 seconds using xenon flash lamps and cathode tubes.
Exposures of 0' to 1/10 h seconds can also be used;
Exposures longer than 1 second can also be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter.

For photographic processing of the light-sensitive material of the present invention, for example, Research Disc-1
osure) No. 176, pages 25-30 (RD-17
Any of the various methods and various processing liquids can be applied, such as those described in , 643). Depending on the purpose, this photo processing can be used to form a silver image (
black-and-white photographic processing) or a photographic process that forms a dye image (
color photographic processing). The processing temperature is usually selected between 18°C and 50°C, but temperatures below 18°C or above 50°C may also be used.

Further, various other developing methods (for example, thermal development, etc.) may be used depending on the case.

For example, developers used in black-and-white photographic processing can include known developing agents.

As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), etc. may be used alone or in combination. Can be used. The developing solution generally contains various other preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. It may also contain water softeners, hardeners, viscosity-imparting agents, and the like.

As a special form of development processing, a developing agent is added to the light-sensitive material.
For example, a method may be used in which the photosensitive material is contained in an emulsion layer and developed by processing the photosensitive material in an aqueous alkaline solution. Among the developing agents, hydrophobic ones are described in Research Disclosure No. 169 (RD-16928), US Patent No. 2,739.
890, British Patent No. 813.253 or West German Patent No. 1,547,763. Such development treatment may be combined with silver salt stabilization treatment with thiocyanate.

As the fixer, one having the composition used for -S can be used. As the fixing agent, in addition to thione sulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains a color-forming coupler, which can form a color by oxidative coupling with an aromatic primary amine developer (e.g., phenylenediamine derivative, aminophenol derivative, etc.) during color development processing. It may also contain compounds. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetyl tamarone couplers, open-chain acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetanilides, pivaloylacetanilides). , etc., and cyan couplers include naphthol couplers, phenol couplers, etc. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, there are also colorless DIR couplers in which the product of the coupling reaction is colorless and releases a development inhibitor.
It may also contain a coupling compound.

The silver halide photographic material of the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

The silver halide photographic material of the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (such as those described in U.S. Pat. No. 3,533.794), 4-thiazolidone compounds (such as those described in U.S. Pat. No. 3,314.794,
3,352.651), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamate ester compounds (e.g., U.S. Pat. No. 3,70-2784)
5.805, those described in 3.707.375)
, butadiene compounds (e.g. U.S. Pat. No. 4,045.22)
9), or benzoxidol compounds (eg, those described in US Pat. No. 3,700,455) can be used. Additionally, U.S. Patent No. 3,499
．． 762 and JP-A-54-48535 can also be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted in specific layers.

In carrying out the present invention, various antifading agents can be used in combination, and any color image stabilizer can be used alone or in combination of two or more. Examples of antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. Color developing agents include various primary aromatic amine developers, such as phenylene diamines (e.g. 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
-βmethanesulfamide ethylaniline, 4-amino-
3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition, there is a book by P. A. Mason, “Photographic
graphicProcessing Chemist
ry)-, Published by Focal Press, 1966, pages 226-229, U.S. Pat. No. 2,193.015, U.S. Pat. .

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or anticapri agents such as bromides, iodides, and organic anticapri agents. can include. If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, development accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, competitive couplers, It may also contain a fogging agent such as sodium boron hydride, an auxiliary developer such as 1-phenyl-3-pyrazolidone, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant, and the like.

After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (■), cobalt (■), chromium (Vl), and copper (n), peracids, quinones, and nitroso compounds.

For example, ferricyanide, dichromate, iron (I[
[) or Kobal) (I Complex salts of organic acids, persulfates, permanganates, nitrosophenols, etc. can be used. Among these, potassium ferricyanide, iron ethylenediaminetetraacetate (I[[)
Sodium and iron(I[) ammonium ethylenediaminetetraacetate are particularly useful. Ethylenediaminetetraacetic acid iron (I[[) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Furthermore, the embodiments of the present invention can be applied in exactly the same way to silver halide photographic materials using high contrast agents.

As a high contrast agent, JP-A No. 52-18317,
No. 53-17719, No. 53-17720, No. 61
Tetrazolium compounds disclosed in US Pat. No. 4,166,742 and US Pat.
No. 977, No. 4221857, No. 4224401,
No. 4243739, No. 4272606, No. 4311
There are certain acylhydrazine compounds such as those found in No. 781. These high contrast agents may be added to the light-sensitive silver halide emulsion layer or may be added to another hydrophilic colloid layer on the same side of the support as the silver halide emulsion layer. good. Silver halide photographic materials using a tetrazolium compound or an acylhydrazine compound as a high contrast agent are produced using a PQ type or MQ type developer (p
Particular preference is given to treatment with H10,0-12.9).

In particular, when a high contrast agent is used, a dye having a λmax of 400 to 850 m as shown in this specification may be added to a wood-loving mass containing a high contrast agent to the support, or It may be coated on both the backing layer side and the side containing the high contrast agent with respect to the support.

, l-- Hereinafter, Kurauchi and Zogo [Examples] Examples of the present invention will be described in detail below. It should be noted that, as a matter of course, the present invention is not limited to the examples described below.

Example-1 Emulsion E-1 was obtained by the method shown below. First, 60℃, p
While controlling A g = 8.0 and pH = 2.0, the average particle size was 0.28 μm using the double jet method.
A monodispersed cubic emulsion of silver iodobromide emulsion containing 2.0 mol % of iodide was obtained. This emulsion can be seen from its electron micrograph.
The incidence of twin grains was 1% or less in number. This emulsion is added as a seed crystal to a solution containing protected gelatin kept at 40°C and ammonia added as necessary, and dispersed.
Furthermore, the pH was adjusted with glacial acetic acid.

Using this solution as a mother liquid, a 3.2N ammoniacal silver ion aqueous solution and a halide aqueous solution were added by a double jet method while controlling the flow rate to sequentially form layers with various silver iodide contents. In this case, when forming a layer with a silver iodide content of 30 mol %, the pA and g were controlled to 7.3 and the pH to 9.7. Further, a layer having a silver iodide content of 0 mol % was prepared by controlling pAg to 9.0 or 9.0 or more. That is, 7% of the amount of silver used in the preparation as shown in Figure 2.
up to 20 mol% or more of silver iodide, and then silver iodide 2
A layer with less than 0 mole % was prepared according to the pattern shown in FIG. The emulsion thus obtained was a monodisperse silver iodobromide emulsion with an average grain size of 1.degree. 25 .mu.m and a total ratio of silver iodide to total silver halide of 2 mol %.

Next, in the same manner as E-1, emulsion E-2 with an average grain size of 0.90 .mu.m and emulsion E-3 with an average grain size of 0.65 .mu.m were obtained.

Both E-2 and E-3 were monodisperse emulsions containing 2 mol % of silver iodide.

Excess salts were removed from these three types of emulsions obtained by a conventional aggregation method. That is, the temperature was maintained at 40° C., and an aqueous solution of a formalin condensate of sodium naphthalene sulfonate and magnesium sulfate was added to cause coagulation. After removing the supernatant, pure water at 40° C. was further added, an aqueous magnesium sulfate solution was added again to cause coagulation, and the supernatant was removed. Then, add 2.0% ammonium thiocyanate to each. OXl0-″mol 1 molAgX
Then, appropriate amounts of chloroauric acid and Hypo were added to perform chemical ripening. Then add lime-treated gelatin,
The amount of gelatin applied was adjusted as shown in Table 1. Thereafter, each emulsion was mixed with E1: 25 wt% and E-2: 40% and 1 t%.

E-'3: They were mixed at a ratio of 35 wt%, the additives shown below were added, and further, the exemplary compounds of the dyes mentioned above were added as shown in Table 1 to prepare an emulsion coating solution. Next, prepare a protective film coating solution with the composition shown below, and add 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt so that the melting time becomes the value shown in Table 1. A 2% aqueous solution of a hardening agent was adjusted as appropriate for finishing.

The melting time is expressed as the time required for silver halide grains to separate from the support when immersed in an aqueous solution of 1.5 weight percent sodium hydroxide at 50.0° C. without stirring.

The additives used in the emulsion solution (silver halide coating solution) are as follows. The amount added is expressed per mole of silver halide.

The additives used in the protective layer solution are as follows. The amount added is expressed per 11 coating liquids.

The obtained emulsion coating solution and protective film coating solution were coated in two slide hopper type coaters to coat a copolymer consisting of three monomers: 50-t% glycidyl methacrylate, 10 wt% methyl acrylate, and 40 wt% butyl methacrylate. 17 A copolymer aqueous dispersion obtained by diluting the polymer to a concentration of 10-t% was applied as an undercoat liquid.
On a 5 μm polyethylene terephthalate film base, multilayer coating was carried out on both sides at the same time at a coating speed of 75 m/win so that the amount of gelatin was as shown in Table 1. After drying, sample N
11l~1lh20 was obtained.

The emulsion was coated so that the amount of silver coated was 5.5 g/m.

Sensitivity measurements were performed on the obtained samples as follows. That is, the sample is sandwiched between two optical wedges whose concentration gradients are mirror-symmetrically aligned, and exposed to an equal amount of light for 1/12.5 seconds from both sides at the same time using a light source with a color temperature of 5,400°K.

Then, in accordance with the next step, the film was processed for a total processing time of 45 seconds using a roller conveyance type automatic developing machine that can arbitrarily change the total processing time between 20 seconds and 90 seconds.

Processing temperature Processing time insertion 1.2 seconds development +
Crossing 35℃ 14.6 seconds Fixation + Crossing
33℃ 8.2 seconds washing + crossing 25℃
7.2 seconds squeeze 40℃ to 5.7 seconds Total 45.0 seconds mouth
□The following developing solution and fixing solution were used. The processing temperature was 34° C. for development and 33° C. for fixing.

<Developer> A 1x aqueous solution was prepared, and potassium hydroxide was added to adjust the pH to 10.40.

<Fixer> Glacial acetic acid 5.2 g A 1N aqueous solution was prepared, and glacial acetic acid was added to make a solution with a pH of 4.0.

From the obtained characteristic curve showing the relationship between logE (logarithm of exposure amount) and D (optical density), base density 10 capri density +
The reciprocal of the exposure amount at 1.0 was determined, and the relative sensitivity was determined.

Next, the image sharpness was visually evaluated and rated from 1 (poor) to 5 (
Excellent). Incidentally, a value of 3 to 5 poses no problem, but a value of 1 to 2 is not practical.

In addition, the water content was measured using the procedure described above.

In addition, drying properties were evaluated as follows. That is, 45 above
Automatic development is performed in seconds, and the sample that has passed through the drying area is comprehensively evaluated for its texture, degree of stickiness with other samples, etc., and is displayed on a five-point scale from 1 (poor) to 5 (excellent). did.

Note that 3 to 5 poses no problem, but 1 to 2 is not practical.

The above results are summarized in Table 1.

As is clear from Table 1, the samples according to the present invention maintain high sensitivity, have excellent sharpness, and have good drying properties and are suitable for ultra-rapid processing.

Example 2 Using the same method as Example 1, an average grain size of 0.58μ (emulsion E-
4) and a monodispersed silver iodobromide emulsion having an average grain size of 0.4 μm (emulsion E-5) was prepared. Emulsion E used in Example-1
-1, E-4, and E-5 at a mixing ratio of E -1: E-
4: E-5=30wt%: 30wt%: 40wt
%, and after adding 600 μm of the aggravating dye shown below per mole of silver halide, the amount of gelatin was adjusted to the amount shown in Table 2, and the above-mentioned exemplified compound was added to They were added in the types and amounts shown in the table. Thereafter, other additives were added in the same manner as in Example 1, except that 15 g of trimethylolpropane was used) to prepare an emulsion coating solution. Moreover, the protective film coating liquid was prepared in the same manner as in Example-1. However, in this example, polymethyl methacrylate particles with an average particle size of 5.5 μm were used, and the hardening agent was 2-4 μm.
In place of the aqueous solution of -dichloro-6-hydroxy-1,3°5-triazine sodium salt, 35% formalin and 40% glyoxal aqueous solution were used, and the melting times were adjusted to the values shown in Table 2.

The coating solution obtained with the sensitizing dye was coated and dried under the same conditions as in Example-1 to give Sample Groups 21 to -41.

Further, as a non-photosensitive layer coating solution, dyes of the type and amount shown in Table 2 were added, gelatin was added so that the amount of gelatin was as shown in Table 2, and then the compound exemplified as a mordant agent was added. A solution to which 5 and a coating aid were added, an emulsion coating solution (no dye added) prepared in the same manner as above, and a protective film coating were added to the support in the order of the non-photosensitive layer, the emulsion layer, and the protective film layer. Multi-layer coating was applied on both sides at the same time. Thereafter, it was dried, and a sample size 42 was prepared.

Regarding the obtained sample, the sensitivity was determined, the sharpness and dryness were evaluated, and the water content was measured in the same manner as in Example-1.

As is clear from Table 2, according to one of the preferred embodiments of the present invention, the effect can be seen even in dye-sensitized systems. Furthermore, it can be seen that similar effects can be obtained even when one of the other preferred embodiments of the present invention is followed.

In addition, although the composition was the same as that of the sample in this example, the melting time was increased to 13 minutes (20% increase in water content).
Similar evaluations were performed on samples prepared by adjusting the amount of hardener for 30 minutes and 30 minutes (7% reduction in water content), and the same effects as those shown in Table 2 were obtained. Ta.

Example-3 Emulsions E-4 and E-5 used in Example-2 were mixed so that the mixing ratio was E-4: E-5 = 75 wt%: 25 wt%, and then Example-2 Add the sensitizing dye used in 700 hours per mole of silver halide, adjust the amount of gelatin and the type and amount of the above-mentioned exemplified compound as a dye as shown in Table 3, and add other additives in the same way. However, 5 g of trimethylolpropane was used) to prepare an emulsion coating solution. Also,
The protective layer was prepared in the same manner as in Example-1, but polymethyl methacrylate with an average particle size of 7.5μ was used as the matting agent, and the same compound as in Example-1 was used as the hardening agent. A protective film coating solution was prepared so that the time became the value shown in Table 3. Two layers of the obtained two coating solutions were simultaneously coated on one side of the support. After drying, sample N [L43~
Magnet 61 was obtained. The amount of coated silver in the obtained sample was 3.7 g/
It was m.

Next, the sensitivity of the obtained sample was determined in the same manner as in Example 1, the sharpness and dryness were evaluated, and the water content was determined.

The above results are summarized in Table 3.

Iv1 As is clear from Table 3, according to the present invention, the effect is great even in a light-sensitive material in which a light-sensitive silver halide emulsion layer is provided only on one side of the support.

In addition, the same effect as Example 3 was obtained for a sample in which the exemplified compound as a dye was not added to the emulsion layer, but the exemplified compound was added to the non-photosensitive photographic constituent layer provided on the back side.Example 4 Silver halide photographic sensitivity The materials were prepared as follows.

(Preparation of emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol % was prepared as follows.

An aqueous solution containing 23.9 μ of pentabromorodium potassium salt, sodium chloride, and potassium bromide per 160 g of nitric acid t1i and an aqueous silver nitrate solution were simultaneously mixed in an aqueous gelatin solution at 40° C. for 25 minutes while stirring to obtain an average grain size. A silver chlorobromide emulsion with a diameter of 0.17 μm was prepared.

This emulsion was added with 6-methyl-4-hydroxy- as a stabilizer.
After adding 200 μl of 1,3,3a,7-chitrazaindene, the mixture was washed with water and desalted.

Add to this 20 μ of 6-methyl-4-hydroxy-1°3.
After adding 3a,7-chitrazaindene, sulfur sensitization was performed. After sulfur sensitization, 6-methyl-4-
Add hydroxy-1,3,3a,7-chitrazaindene and then add water to 260 mj! An emulsion was prepared.

(Preparation of latex (α) for emulsion addition) Add 0.25 kg of KMDS (dextran sulfate ester sodium salt) manufactured by Founori Sangyo and 0.0 kg of ammonium persulfate to 40 g of water.
A mixed solution of 4.51 kg of n-butyl acrylate, 5.49 kg of styrene, and 0.1 kg of acrylic acid was added over 1 hour to the solution containing 5 kg of n-butyl acrylate, 5.49 kg of styrene, and 0.1 kg of acrylic acid under a nitrogen atmosphere while stirring at a temperature of 81°C. Ammonium sulfate 0.
After stirring for 1.5 hours, the mixture was cooled, and the pH was adjusted to 6 with aqueous ammonia.

The obtained latex liquid was filtered using a Whatman GF/D filter and finished with water to a total weight of 50.5 kg, thereby creating a monodisperse latex liquid (α) for adding an emulsion liquid with an average particle size of 0.25 μm. did.

A silver halide emulsion coating solution was prepared by adding the following additives to the emulsion.

(Preparation of emulsion coating solution) 9 quarts of compound (a) as a bactericidal agent was added to the emulsion. After that, the pH was adjusted to 6 using 0.5N sodium hydroxide solution.
．． 5, and then the following compound (1-1) was added as a high contrast agent at 4×10'-2 mol per mol of silver. Furthermore, per mole of silver halide, 5-mg of a 20% aqueous solution of saponin, 180 mg of sodium dodecylbenzenesulfonate, and 80 mg of 5-methylbenztriazole were added.
, 43d of the latex liquid (α) for adding the emulsion liquid, 60mg of the following compound (b), and styrene as a thickener.
280 mg of an aqueous maleic acid copolymer was successively added thereto and finished to 475-1 with water to prepare an emulsion coating solution E1.

Tetrazolium compounds (
Instead of 1-1), acylhydrazine compound (1-2
) was added thereto to prepare emulsion coating solution E2 in the same manner.

Next, an emulsion protective film coating solution was prepared as follows.

(Preparation of emulsion protective film coating solution P-1) Add 10 Il of pure water to 1 kg of gelatin, and after swelling
℃, and then add a 1% aqueous solution of the following compound (c) as a coating aid to 2.91℃ and the maximum absorption wavelength λl according to the present invention.
65 g of Exemplified Compound (C) as a dye with 1 lax of 400 to 850 nm, 20 g of amorphous silica with an average particle size of 8 μm as a matting agent, and 10 g of amorphous silica with an average particle size of 3 μm as a matting agent.
, and the following compound (d) were sequentially added thereto, the pH was adjusted to 5.4 with citric acid solution, and the pH was adjusted to 171 with water to prepare emulsion protective film coating solution P-1.

Emulsion protective film coating solution P-2 was prepared in exactly the same manner using Exemplified Compound (U) instead of Exemplified Compound (C) as the dye.

Compound (a) IJ Compound (d) n Compound (1-1) Compound (1-2) (Preparation of backing coating liquid B-1) Swell 36 kg of gelatin in water, heat it to dissolve it, and use it as a dye. 1.6 kg of the following compound (Ho 1), 310 g of the compound (Ho 2), 1.9-1 of the compound (Ho 3), and 2.9 kg of the exemplary compound (C) according to the present invention.

Add as an aqueous solution and then add a 20% aqueous solution of saponin to 11
2. Add 5 kg of the following compound (Ho 4) as a physical property modifier, and further add the following compound (Ho 5) as a methanol solution.
and 270 g of the following compound (holo) were added. To this liquid, 800 g of a water-soluble styrene-maleic acid copolymer was added as a thickener to adjust the viscosity, and the pH was further adjusted to 5.4 using an aqueous citric acid solution.Finally, 144 g of glyoxal was added, and water 9601 to prepare backing coating liquid B-1.

Compound (Ho 1) HtSLl, tl Compound (Ho 2) Compound (Ho 3) Compound (Ho 4) Copolymer latex of C However, m:n=1:1 Compound (Ho 5) Compound (Ho Holo) ■ Next, the backing layer For coating the protective film layer, protective film coating liquid P-3 was prepared as follows.

(Preparation of protective film coating solution P-3) Swell 50 kg of gelatin in water, heat and dissolve, add 340 g of 2-sulfonate succinic acid bis(2-ethylhexyl) ester sodium salt, and add polymethyl methacrylate as a matting agent. (average particle size approximately 0.4tt) to 1
．． 7kg, add 3.4kg of sodium chloride, further add 1.1kg of glyoxal and 540g of mucochloric acid, finish to 100x with water, and prepare protective film coating liquid P-3.
was prepared.

(Preparation of evaluation samples) Each of the above-mentioned coating liquids was prepared using Example-1 of JP-A-59-09941.
It was applied to both sides of a polyethylene terephthalate film (thickness 100μ) coated with an undercoat layer, and Table 4
The evaluation sample shown in was prepared. At that time, coat the backing lower layer with coating solution B-1 on one side of the support coated with the undercoat layer.
The dry weight of gelatin is 2g/m2, and at the same time, a backing protective film layer is applied on top of the gelatin using protective film solution P.
-3, the gelatin was coated and dried so that the dry weight of gelatin was Ig/rrf. Next, an emulsion layer was coated on the other side of the support so that the gelatin dry weight was as shown in Table 4, and an emulsion protective film layer was applied on top of the emulsion layer using protective film solution P-1 so that the gelatin dry weight was as shown in Table 4. Evaluation samples 62 to 79 were prepared by coating and drying the emulsion layer at the same time while adding formalin as a hardening agent in the amounts shown in Table 4.

Table 4 shows the combinations of emulsion coating solution and emulsion protective film coating solution.
Corresponds to the combination of high contrast agent and dye shown in .

(Evaluation of Photographic Performance) The automatic processor and processing conditions were the same as in Example-1, and the processing time was only 45 seconds. However, as shown in Table 4, two types of developer solutions (Developers ① and ②) were prepared as shown below and used for high-contrast silver development. The fixer used had the following composition.

For exposure, only the emulsion side was irradiated through an optical wedge using an electrodeless discharge tube manufactured by Fusion, USA. The sensitivity is expressed as a relative value of density 2.5 and the reciprocal of the exposure amount given, with sample 62 being set as 100. Sharpness was evaluated visually. The ranking method is based on Example-1. The dryness was evaluated by touch, and the ranking method was the same as in Example-1.

Developer solution ■ (Composition ■) Pure water (ion-exchanged water) 1 sod Ethylenediaminetetraacetic acid disodium salt 2 g Diethylene glycol 50 g Potassium sulfite (
55%-/V aqueous solution > 100 d potassium carbonate
50 g hydroquinone
15 g 5-Methylbenzotriazole 200 ■ 1-Phenyl-5-mercaptotetrazole 30 ■ Potassium hydroxide Amount to adjust the pH of the solution to 10.4 Potassium bromide 4.5 g (composition ■) Pure water (ion-exchanged water) 3 ■ Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 ■Acetic acid (
90% aqueous solution) 0.3 relative 5-nitroindazole 110 mgl-
When using 500 mg of phenyl-3-pyrazolidone as a developer, dissolve it in 500 mg of water in the order of composition ① and composition ②, and use II! , and used it.

Developer ◎ Hydroquinone 45.0gN-
Methyl-p-aminophenol% sulfate 0.8g Sodium hydroxide 18.0g Potassium hydroxide 55.0g 5-sulfosalicylic acid 45.0g Boric acid
25.0g potassium sulfite 1
10.0 g ethylenediaminetetraacetic acid dinatrilam salt 1.0 g potassium bromide 6.0 g 5-methylbenzotriazole 0.6 gn-butyl-jetanolamine 15.0 g Add water
11 (pH = 11.6) Fixer prescription (composition ■) Ammonium thiosulfate (72.5% 117 water solution) 2
30 ml Sodium sulfite 9.5g, Sodium acetate trihydrate 15.9g Boric acid
6.7g sodium citrate dihydrate 2g acetic acid (90% -/- aqueous solution)
8.1mm! (Composition ■) Pure water (ion-exchanged water) 17 d Sulfuric acid (50% -/- aqueous solution) 5.8 g aluminum sulfate (An!z (aqueous solution with h conversion content of 8.1% -/-) 2
6.5 g When using a fixer, the above compositions (1) and (2) were dissolved in 500% water in that order, and the fixing solution was finished to 12.

The pH of this fixer was about 4.3.

As is clear from Margin Table 4 below, it can be seen that even in silver halide photographic materials using high contrast agents, good sharpness and drying properties can be obtained in rapid processing according to the present invention.

〔Effect of the invention〕

As mentioned above, according to the present invention, it is possible to reduce the amount of gelatin while maintaining high sharpness, and the total processing time is 20 seconds to 6.
It is possible to provide a photosensitive material that can be suitably applied to ultra-quick processing of 0 seconds.

[Brief explanation of the drawing]

FIG. 1 is a block diagram showing an example of an automatic developing machine that can be used in an embodiment of the present invention. FIG. 2 is a graph showing the amount of silver used in preparing emulsions in Examples. DESCRIPTION OF SYMBOLS 1... Film insertion stand, 2... Film basket, 3... Operation panel, 31... Remote control receiver, 4
... roller, 5 ... conveyance path, 6 ... developer tank,
7... Fixing tank, 8... Washing tank, 9... Drying section, 9
1... Squeeze rack, 92... Drying rack. Figure 1

Claims (1)

[Claims] 1. In a silver halide photosensitive material having at least one photosensitive silver halide emulsion layer on at least one side of the support, at least one of the photographic constituent layers is coated with an aqueous solution. The maximum absorption wavelength (λ_m_a_x) of is 400
It is characterized by containing at least one kind of dye in the range of ~850 nm, and the amount of gelatin in the photographic constituent layer on the side having photosensitive silver halide is in the range of 2.0 to 3.5 g/m^2 A silver halide photographic light-sensitive material. 2. The silver halide photographic material according to claim 1, which is processed in an automatic processor for a total processing time of 20 seconds or more and less than 60 seconds.