JP2002131859A - Infrared sensitive silver halide photographic sensitive material for photographing and infrared sensitive silver halide emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an infrared sensitive silver halide photographic sensitive material having developability common to a color photographic sensitive material and having high sensitivity and excellent in graininess, infrared effect, and long term storage and also provide an infrared sensitive silver halide emulsion used for the same. SOLUTION: The infrared sensitive silver halide photographic sensitive material for photographing has an infrared sensitive layer and a non-sensitive layer on a substrate. At least one of the infrared sensitive layers contains, in 50% or more of the total projected area, a flat platy silver halide grain having an aspect ratio of >=5 and a coefficient of variation of an equivalent circular conversion diameter of <=20% and spectrally sensitized by a sensitizing dye represented by the following general formula (1), and contains a photosensitive silver halide emulsion containing a novolac type resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an infrared-sensitive silver halide photographic material for photography (hereinafter, also simply referred to as a photographic material or a film) and an infrared-sensitive silver halide emulsion used for the same. The present invention relates to an infrared-sensitive silver halide photographic material for photography which can be developed and an infrared-sensitive silver halide emulsion used therefor.

[0002]

2. Description of the Related Art At present, a widely used photographic image forming method includes a color negative image formed by color photography using a silver halide color light-sensitive material for photographing, a so-called color negative film, and color development. Paper) to produce a positive color print. On the other hand, a positive image can be obtained simply by taking an image with a reversal type silver halide color photosensitive material for photography, a so-called color reversal film, and developing it. It can be viewed directly or printed on color photographic paper (color reversal paper). There is also a so-called positive-positive photographic system that obtains a positive color print. On the other hand, a black-and-white negative-positive photographic system with a strong sense of being replaced by a color photographic system is a method in which a photograph is taken with a silver halide black-and-white photosensitive material for photography (black-and-white negative film) and printed on black-and-white photographic paper (black-and-white negative paper). There is also. Since this black-and-white negative film is subjected to development processing in a different manner from color negative film, the number of development sites capable of corresponding development processing is extremely small, so especially when self-development processing is not performed, The time it takes to get the final black-and-white print is less than an hour at the earliest stores in the prevailing color negative-positive system, whereas it takes a few hours for the black-and-white photographic system. At present, it has a significant weakness that requires more days and a higher unit price.

Some measures have been proposed and implemented to solve the drawbacks hindering the spread of black-and-white negative films. One of them is to provide a monotone image-forming silver halide light-sensitive material for photographing which is compatible with the same development processing as color negative films which are currently most widely used, and is disclosed in U.S. Pat. , 348,
No. 474, JP-B-63-59136 and JP-A-61-2.
No. 36550 discloses a monotone image forming silver halide photosensitive material using a black coupler.

A technique for forming a black dye image by mixing a yellow coupler, a magenta coupler and a cyan coupler used in a general silver halide color light-sensitive material is disclosed in US Pat. 1
86,736, 4,368,255, 5,14
No. 1,844, JP-A-57-56838 and JP-A-57-5.
Nos. 8147 and 58-215645, JP-A-3-10
Nos. 7144, 6-214357, 7-19942
No. 1, JP-A-6-505580 and the like.

[0005] However, all of these techniques are:
Although the development processing can be shared, there is a disadvantage that printing on photographic paper is complicated. Then, Japanese Patent Application Laid-Open No. 9-3
With the technology disclosed in Japanese Patent No. 19042 or the like, the above-mentioned drawbacks have been solved, and a sepia tone monotone image forming silver halide photosensitive material suitable for the same development processing as a color negative film that has become a hot topic in the market has been developed. ing.

On the other hand, as a black-and-white image forming silver halide light-sensitive material for expressing a special photographing effect, a silver halide black-and-white light-sensitive material for infrared rays (also referred to as an infrared black-and-white negative film)
It has been known. This infrared black-and-white negative film is characterized in that the photosensitive wavelength region is considerably longer than that of a general black-and-white photosensitive material in order to produce an infrared effect by infrared light. The infrared effect is an effect that produces a unique depiction that cannot be expressed by a general black-and-white negative film, because the absorption, reflection, and transmission of infrared light differ from those of visible light depending on the subject to be photographed. The use of this infrared black-and-white negative film is widely used mainly for business purposes such as scientific photography, appraisal photography, and archeology photography. In addition, the effect on the photo of the difference in the absorption and reflectance of the blue sky, the sea, leaves and grass against infrared light gives a fantastic expression, and is also favored by users who like landscape photography and mountain photography. Is also used in portrait photography to take advantage of the difference in the reflectance of human skin. This infrared black-and-white negative film also performs the same development processing as the above-mentioned general-purpose black-and-white negative film, and has the same weakness as the above-mentioned black-and-white system.

On the other hand, since the infrared black-and-white film has a long wavelength region of photosensitive wavelength, it must be handled with care so that refrigerated storage is a preferable storage method. This is due to the sensitizing dye for forming a spectral sensitivity distribution in a long wavelength region, and causes problems such as easy fogging in photographic performance and fog easily generated by long-term storage. The occurrence of fog has a very large effect on image quality, such as deterioration of image quality, particularly graininess. In addition, these sensitizing dyes remain on the film after the development processing, so that a problem called so-called residual color contamination easily occurs, and there is also a problem that the image storability is deteriorated and the density balance during printing is hindered.

Recently, several countermeasures have been proposed and implemented to overcome these disadvantages of black-and-white negative films. As an example, there is a development of a black-and-white image forming silver halide photosensitive material suitable for the same development processing as a color negative film, which has become a topic in the market, using the technology disclosed in Japanese Patent Application Laid-Open No. 9-319042. An example in which the technology disclosed in Japanese Patent Application Laid-Open No. 9-319042 or the like is applied to an infrared black-and-white negative film is disclosed in Japanese Patent Application Laid-Open No. 10-148.
No. 919 and the like.

Techniques for sensitizing silver halide used for infrared black and white negative films include those relating to chemical sensitization and those relating to spectral sensitization. Chemical sensitization includes chalcogen sensitization such as sulfur sensitization, selenium sensitization, and tellurium sensitization, and noble metal sensitization using a noble metal.In the past, chalcogen sensitization and noble metal sensitization have been applied to infrared-sensitive emulsions. There is no applied example,
JP-A-3-84545, JP-A-4-146431, and JP-A-5-146431
The chemical sensitization method disclosed in -281645 and the like is sulfur and sulfur / gold sensitization and was insufficient to achieve the object of the present invention. Further, in spectral sensitization, as described above, the conventional sensitizing dye for providing a photosensitive wavelength region in the infrared region is very unstable, and there is also a problem of adsorption to silver halide, The problem is that the spectral sensitization efficiency is lower than that of sensitizing dyes introduced in general color negative films. Furthermore, it is better to harden the gradation in design in order to bring out the infrared effect more.For example, means for hardening the gradation such as increasing the amount of silver halide applied or increasing the amount of various couplers are available. However, an increase in fog is a concern, which causes other adverse effects on other photographic performances, such as a decrease in image quality due to deterioration in graininess.

However, the above-mentioned Japanese Patent Application Laid-Open No. 10-14 / 1998
Also in the technology disclosed in No. 8919 and the like, the above-mentioned storability, improvement in photographic performance such as graininess are not mentioned,
Further improvements are desired.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to have the same development suitability as a color photographic light-sensitive material, high sensitivity, granularity, and redness. An object of the present invention is to provide an infrared-sensitive silver halide photographic material for photography excellent in external effects and long-term storage stability, and an infrared-sensitive silver halide emulsion used therefor.

[0012]

The above object of the present invention has been attained by the following constitutions.

1. In an infrared-sensitive silver halide photographic material for photography having an infrared-sensitive layer and a non-light-sensitive layer on a support, at least one of the infrared-sensitive layers is at least 50% of the total projected area. Are tabular silver halide grains having an aspect ratio of 5 or more, and have a coefficient of variation of equivalent circle diameter of 20.
% Or less, which is characterized by containing a photosensitive silver halide emulsion which has been spectrally sensitized by the sensitizing dye represented by the general formula (1) and contains a novolak resin. Infrared-sensitive silver halide photographic material for photography.

2. In an infrared-sensitive silver halide photographic material for photography having an infrared-sensitive layer and a non-photosensitive layer on a support, at least one of the infrared-sensitive layers has an average silver iodide content. It comprises 0.5 to 8 mol% of silver iodobromide grains, is spectrally sensitized by the sensitizing dye represented by the general formula (1), contains a novolak-type resin, and has the general formula (2) An infrared-sensitive silver halide photographic light-sensitive material for photography, comprising a light-sensitive silver halide emulsion containing the compound represented by formula (1).

3. In an infrared-sensitive silver halide photographic material for photography having an infrared-sensitive layer and a non-photosensitive layer on a support, at least one of the infrared-sensitive layers has an average silver iodide content. It comprises 0.5 to 8 mol% of silver iodobromide grains, is spectrally sensitized by the sensitizing dye represented by the general formula (1), and contains a photosensitive silver halide emulsion containing a novolak type resin. And number average molecular weight 500 or more and 200
An infrared-sensitive silver halide photographic light-sensitive material for photographing, comprising a vinylpyrrolidone polymer of 00 or less.

4. The light-sensitive silver halide emulsion contained in at least one of the infrared-sensitive layers shifts the maximum spectral sensitivity wavelength of the J-aggregate of the infrared sensitizing dye toward the longer wavelength side by 30 nm or more, and spectrally sensitizes the emulsion. 4. The infrared-sensitive silver halide photographic light-sensitive material for photography according to any one of the items 1 to 3, wherein:

5. Wherein at least one of the infrared-sensitive layers contains a yellow color coupler, a magenta color coupler, and a cyan color coupler.
5. The infrared-sensitive silver halide photographic light-sensitive material for photography according to any one of items 4 to 4.

6. The infrared-sensitive layer comprises a plurality of layers having different sensitivities, and all of the plurality of layers contain a yellow coloring coupler, a magenta coloring coupler, and a cyan coloring coupler. Item 2. An infrared-sensitive silver halide photographic material for photography according to item 1.

[7] At least one of the infrared-sensitive layers contains a yellow color coupler, a magenta color coupler and a cyan color coupler, and a DIR coupler having a content of 0.3% by mass or more and 5.0% by mass or less based on the total amount of the couplers. Item 7. The infrared-sensitive silver halide photographic light-sensitive material for photography according to any one of Items 1 to 6, wherein the material is contained.

8. The infrared-sensitive layer comprises a plurality of layers having different sensitivities, all of the plurality of layers containing a yellow coloring coupler, a magenta coloring coupler and a cyan coloring coupler, and 0.3% by mass based on the total amount of the coupler. 8. The infrared-sensitive silver halide photographic light-sensitive material for photography according to any one of the above items 1 to 7, which contains at least 5.0% by mass or less of a DIR coupler.

9. The infrared-sensitive layer comprises a plurality of layers having different sensitivities, all of the plurality of layers contain a yellow coloring coupler, a magenta coloring coupler, a cyan coloring coupler and a DIR coupler, and a yellow coloring coupler in the plurality of layers. 9. The infrared-sensitive silver halide photographic material for photography according to any one of the above items 1 to 8, wherein the mass ratios of the magenta color-forming coupler and the cyan color-forming coupler are all the same.

10. The infrared-sensitive layer is composed of a plurality of layers having different sensitivities, and all of the plurality of layers contain a yellow coloring coupler, a magenta coloring coupler, a cyan coloring coupler, and a DIR coupler, and DI in the plurality of layers is used.
Item 10. The infrared-sensitive silver halide photographic light-sensitive material for photography according to any one of Items 1 to 9, wherein the mass ratio of the R coupler / the total amount of the color-forming couplers is all the same.

11. Chemical sensitization wherein the photosensitive silver halide emulsion according to any one of the above items 1 to 4 is added in the order of a chemical sensitizer, a novolak resin, and a sensitizing dye represented by the general formula (1). An infrared-sensitive silver halide emulsion prepared by the above steps.

12. 12. The infrared photosensitive material according to the above item 11, wherein the content of the sensitizing dye represented by the general formula (1) is 30% or more and 80% or less of the amount of the saturated adsorption on the silver halide emulsion. Silver halide emulsion.

13. 13. The infrared-sensitive silver halide emulsion according to the above item 11 or 12, comprising a compound represented by the general formula (3).

As described above, conventional sensitizing dyes having a photosensitive wavelength region in the infrared region are very unstable in structure, have a weak adsorptivity, and have a large problem of low spectral sensitization efficiency. was there. The present inventors have conducted intensive studies in view of the above problems, and as a result, as spectral sensitization in the infrared region, the combination of the structure of the silver halide grains and the sensitizing dye has selectivity, and in particular, a specific tabular plate. Silver halide grains have been found to be extremely effective in terms of adsorptivity and spectral sensitization efficiency. Further, the improvement of the adsorption site of the sensitizing dye and the order of adding the chemical sensitizer and the sensitizing dye have an unexpectedly large effect on the adsorptivity, stability and J-aggregate formation of the sensitizing dye. It was possible to reduce the amount of dye, and the possibility of improving residual color contamination was found. As a result, significant improvements in storage stability, spectral sensitization efficiency, etc. were realized. In addition to providing the same processing suitability as silver halide color photographic light-sensitive materials, it realizes the gradation high contrast which is an important factor for exhibiting the infrared effect, and is concerned with the high contrast. As a means for improving the increase in graininess, the composition ratio of each coupler, the usage ratio of a DIR coupler, and the like are set in a specific range to obtain a hard tone and excellent graininess for use in an infrared-sensitive silver halide photographic photosensitive material for photography. Material could be realized.

Hereinafter, the present invention will be described in detail. First, the photosensitive silver halide emulsion according to the present invention will be described below.

The silver halide grains used in the present invention include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular shapes such as spheres and plates, and those having twin planes. Silver halide grains having a crystal defect or a composite silver halide grain thereof may be used. However, in the invention according to claim 1, as a photosensitive silver halide emulsion used in the infrared-sensitive layer, total projection is performed. One feature is that 50% or more of the area is tabular silver halide grains having an aspect ratio of 5 or more (hereinafter also simply referred to as tabular grains), and the aspect ratio is 50% or more of the total projected area. Is 5 to 1
00, more preferably 50% or more of the total projected area has an aspect ratio of 5 to 50, and particularly preferably 50% or more of the total projected area has an aspect ratio of 5 to 20.
It is.

Tabular grains are crystallographically classified as twins. Twins are silver halide crystals that have one or more twin planes in one grain, and the twin morphology is classified by Klein and Moiser.
Correspondents (Photographhish K
orrespondenz), Vol. 99, p100, and Vol. 100, p57.

The tabular grains according to the present invention preferably have two twin planes parallel to the main plane. The twin plane can be observed with a transmission electron microscope. The specific method is as follows. First, contained tabular grains,
A silver halide photographic emulsion is coated on a support such that the main planes are oriented substantially parallel to each other to prepare a sample. This is cut using a diamond cutter to obtain a thin section having a thickness of about 0.1 μm. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

The distance between two twin planes in the tabular grains according to the present invention is determined by observing a section using the above-mentioned transmission electron microscope and showing a cross section cut almost perpendicularly to the main plane. Is arbitrarily selected, and the distance between the two twin planes having the shortest distance among the even twin planes parallel to the main plane is obtained for each particle and averaged.

In the present invention, the distance between twin planes is a factor that affects the supersaturation state during nucleation, such as gelatin concentration, gelatin species, temperature, iodine ion concentration, pBr, pBr.
It can be controlled by appropriately selecting a combination of various factors such as H, ion supply speed, and stirring rotation speed. In general, the more the nucleation is performed in a supersaturated state, the narrower the distance between twin planes can be. The details of the supersaturation factor can be referred to, for example, the descriptions in JP-A-63-92924 and JP-A-1-213637. The average distance between twin planes is 0.01 to 0.05 μm
Is preferably, and more preferably, 0.013 to 0.025 μm.
m.

The thickness of the tabular grains of the present invention can be obtained by observing a section using a transmission electron microscope as described above, similarly calculating the thickness of each grain, and performing averaging. The thickness of tabular grains is 0.05-1.5μ
m is preferable, and more preferably 0.07 to 0.50 μm
It is.

In the present invention, one of the features is that 50% or more of the total projected area of the silver halide grains are tabular grains having an aspect ratio (grain size / grain thickness) of 5 or more. Are tabular grains having an aspect ratio of 7 or more in 60% or more of the total projected area, and more preferably tabular grains having an aspect ratio of 9 or more in 70% or more of the total projected area.

Further, the invention according to claim 1 is characterized in that the variation coefficient of the equivalent circle-equivalent diameter is 20% or less. The particle diameter of the tabular grains according to the present invention is determined by the circle equivalent diameter of the projected area of the silver halide grains (the diameter of a circle having the same projected area as the silver halide grains; (Also called diameter)
5.0 μm is preferred, and more preferably 0.5 to 3.0.
μm. As a method of measuring the equivalent circle diameter, a sample in which latex balls having a known particle diameter serving as an internal standard and silver halide particles are applied so that the main plane is oriented in parallel is prepared on a support, and a carbon is formed from a certain angle. After shadowing is performed by an evaporation method, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area and thickness of each particle are determined using a developing device or the like. In this case, the projected area of the particles can be calculated from the projected area of the internal standard. In the present invention, the average value of the aspect ratio, the particle size, and the grain thickness is arbitrarily measured by using the shadowing method to measure 1,000 or more silver halide grains contained in the silver halide emulsion, and the arithmetic average thereof is used. The average value that can be obtained.

In the present invention, the coefficient of variation of the equivalent circle equivalent diameter (grain size) of the silver halide grains is a value defined by the following equation using the value obtained from the above measurement.

Coefficient of variation of grain size (%) = (standard deviation of grain size / average of grain size) × 100 The feature that the variation coefficient of the silver halide grains of the present invention is 20% or less. However, it is more preferably 16% or less.

The average silver iodide content of the tabular grains according to the present invention is preferably at least 0.1 mol%, more preferably from 0.5 to 10 mol%, and in particular,
In the invention according to 3, the average silver iodide content is 0.5 to 8 m
ol% of silver iodobromide emulsion.
More preferably, the average silver iodide content is 0.5 to 5 mol%.
Silver iodobromide emulsion. The tabular grains according to the present invention are emulsions mainly containing silver iodobromide as described above,
A silver halide having another composition, for example, silver chloride can be contained as long as the effects of the present invention are not impaired.

The distribution state of silver iodide in the silver halide grains can be detected by various physical measurement methods. For example, as described in the Abstracts of the Annual Meeting of the Photographic Society of Japan, 1981, It can be measured by low temperature luminescence measurement, EPMA method, or X-ray diffraction method. In the present invention, the silver iodide content and the average silver iodide content of each silver halide grain are determined by the EPMA method (El
electron Probe Micro Analyz
er method).
According to this method, a sample in which emulsion grains are well dispersed so as not to be in contact with each other is prepared, and element analysis of a very small portion can be performed by X-ray analysis by electron beam excitation for irradiating an electron beam. By determining the characteristic X-ray intensity of silver and iodine emitted from each grain by this method, the halogen composition of each grain can be determined. If the silver iodide content is determined for at least 50 grains by the EPMA method, the average silver iodide content can be determined from the average of these. The average silver iodide content is measured by other well-known methods such as fluorescent X-ray analysis, ICP (induction plasma) emission spectrometry, and ICP mass spectrometry. Can also be determined by measuring

The tabular grains in the present invention preferably have a more uniform silver iodide content between grains in one kind of tabular grains. When the distribution of silver iodide content among grains was measured by the EPMA method, the relative standard deviation was 3
It is preferably 0% or less, more preferably 20% or less.

In a preferred embodiment of the tabular grains of the present invention, tabular grains having a low silver iodide region having an average silver iodide content lower than the average silver iodide content of the grains at the center of the grains are provided. Particles. With respect to the conditions, the measurement can be performed by the EPMA method in which the measurement beam diameter is sufficiently narrowed. The ratio of the low silver iodide region to the total silver content of the grains is preferably 40% or more, and more preferably 50% or less.
More preferably, it is more preferably at least 60%.

The halogen composition on the surface of the tabular grains of the present invention is determined by the XPS method (X-ray Photoelectron).
n Spectroscopy method: X-ray photoelectron spectroscopy)
Can be determined by: The silver iodide content on the surface of the tabular grains is preferably at least 1 mol%, more preferably 2 to 20 mol%, and still more preferably 3 to 20 mol%.
15 mol%.

The tabular grains according to the present invention may have dislocation lines in both the central region and the peripheral region of the main plane. The central region of the main plane of the tabular grains as used herein means a tabular area having a radius of 80% of the radius of a circle having the same area as the main plane of the tabular grains and located in a circular portion when the center is shared. A region having a thickness of a particle. On the other hand, the peripheral region of the tabular grains refers to a region having an area corresponding to the annular region outside the central region, existing around the tabular grains, and having a thickness of the tabular grains.

The number of dislocation lines present in one particle is measured as follows. A series of particle photographs with different inclination angles with respect to the incident electrons are taken for each particle to confirm the existence of dislocation lines. At this time, if the number of dislocation lines can be counted, the number of dislocation lines is counted. For example, when dislocation lines exist densely or dislocation lines cross each other,
When the number of dislocation lines per particle cannot be counted, it is counted that there are many dislocation lines.

The tabular grains according to the present invention have a number ratio of 3
It is preferable that 0% or more have dislocation lines in both the central region and the outer peripheral region of the principal plane, and the number of dislocation lines in the outer peripheral region is 20 or more per particle, and 50% or more (number ratio ) Preferably has dislocation lines in both the central region and the peripheral region of its main plane, and the number of dislocation lines in the peripheral region has at least 30 per particle,
It is further preferred that 70% or more (number ratio) of the tabular grains have dislocation lines in both the central region and the peripheral region of the main plane, and the number of dislocation lines in the peripheral region is 40 or more per particle. preferable.

As a method for introducing dislocation lines into silver halide grains, for example, a method in which an aqueous solution containing iodide ions such as potassium iodide and a water-soluble silver salt solution are added by double jet, or a method including silver iodide. A method of adding a fine grain emulsion,
A method of adding only a solution containing iodide ions;
Known methods such as a method using an iodide ion releasing agent as described in No. 11781 can be used to form dislocations originating dislocation lines at desired positions. Among these methods, a method of adding a fine grain emulsion containing silver iodide and a method of using an iodide ion releasing agent are particularly preferable.
When an iodide ion releasing agent is used, sodium p-iodoacetamidobenzenesulfonate, 2-iodoethanol, 2-iodoacetamide and the like can be preferably used. Dislocation lines of silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci. En
g. 11 (1967) 57 and T.I. Shiozawa,
J. Soc. Photo. Sci. Japan 35 (19
72) It can be observed by a direct method using a transmission electron microscope at low temperature described in 213. The tabular grains of the present invention may be either grains whose latent image is mainly formed on the surface or grains mainly formed inside the grain.

The tabular particles according to the present invention are produced in the presence of a dispersion medium, that is, in an aqueous solution containing the dispersion medium. Here, the aqueous solution containing a dispersion medium refers to an aqueous solution in which a protective colloid is formed in an aqueous solution by gelatin or another substance capable of forming a hydrophilic colloid (a substance capable of serving as a binder), preferably a colloidal protective substance. It is an aqueous solution containing gelatin. When gelatin is used as the protective colloid, even if the gelatin is lime-treated,
Either one treated with an acid may be used. The details of the method for producing gelatin are described in Arthur Guice, The Macromolecular Chemistry of Gelatin (Academic Press, 1964). Examples of hydrophilic colloids other than gelatin that can be used as protective colloids include, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates and the like. Saccharide derivatives such as cellulose derivatives, sodium alginate, starch derivatives, etc .; mono- or polysaccharides such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. There are many types of synthetic hydrophilic polymeric substances, such as copolymers. In the case of gelatin, it is preferable to use one having a jelly strength of 200 g or more in the puggy method.

As the means for forming tabular grains according to the present invention, various methods well known in the art can be used. That is, a single jet method, a controlled double jet method, a controlled triple jet method, or the like can be used in any combination. However, in order to obtain monodisperse grains, silver halide grains are generated. It is important to control pAg in the liquid phase in accordance with the growth rate of silver halide grains. p
As the Ag value, a region of 7.0 to 12 is used, and preferably, a region of 7.5 to 11 can be used. In determining the addition rate, the techniques described in JP-A-54-48521 and JP-A-58-49938 can be referred to.

The step of preparing tabular grains according to the present invention is broadly divided into a nucleation step, a ripening step (nucleus ripening step) and a subsequent growing step. It is also possible to separately grow a previously prepared nuclear emulsion (or seed emulsion). The growth process may include several stages, such as a first growth process and a second growth process. The growth process of tabular grains according to the present invention means all the growth processes from the nucleus (or seed) formation to the end of grain growth, and the start of growth refers to the start of the growth process. In the production of the tabular grains according to the present invention, a known silver halide solvent such as ammonia, thioether, thiourea or the like may be present, or a silver halide solvent may not be used.

In the tabular grains according to the present invention, in order to selectively form dislocation lines in the central region of the main plane, the pH is increased in the ripening step after nucleation so that the thickness of the tabular grains is increased. Aging is important, but if the pH is too high, the aspect ratio will be too low, making it difficult to control the aspect ratio in subsequent growth steps. It also causes unexpected fog deterioration. Therefore, the pH / temperature of the aging step is from 7.0 to 11.0 / 40.
~ 80 ° C, preferably 8.5-10.0 / 50-70 ° C
Is more preferred.

In the tabular grains according to the present invention, in order to form dislocation lines selectively in the outer peripheral region, an iodine ion source (for example, silver iodide) for introducing dislocation lines into the outer peripheral region in the growth step. It is important to increase the pAg in the grain growth after adding the fine particles and the iodine ion releasing agent to the base grains. However, if the pAg is too high, so-called Ostwald ripening proceeds simultaneously with the grain growth, and the tabular grains are reduced. The monodispersity deteriorates. Therefore, pAg when forming the outer peripheral region of the tabular grains in the growth step
Is preferably from 8 to 12, and more preferably from 9.5 to 11. When an iodine ion releasing agent is used as an iodine ion source, dislocation lines can be effectively formed in the outer peripheral region by increasing the amount of iodine ion releasing agent. The amount of the iodide ion releasing agent to be added is preferably 0.5 mol or more per mol of silver halide, more preferably 2 to 5 mol.

The tabular grains according to the present invention may be those obtained by removing unnecessary soluble salts after the growth of the silver halide grains, or may be those containing the same. Also, desalting can be performed at any point during silver halide growth, as in the method described in JP-A-60-138538. When removing the salts, research and
It can be carried out based on the method described in Disclosure No. 17643, Section II. More specifically, in order to remove the soluble salt from the emulsion after the formation of the precipitate or after the physical ripening, it is possible to use a Noudel washing method performed by gelling gelatin, and inorganic salts, anionic surfactants, A precipitation method (flocculation) using an anionic polymer (eg, polystyrene sulfonic acid) or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin, etc.) may be used. As a specific example, a method described in JP-A-5-72658 can be preferably used.

The silver halide emulsion according to the present invention preferably contains a polyvalent metal atom and at least one selected from the group consisting of ions and complexes thereof.

More specifically, the inside or surface of silver halide grains contained in the silver halide emulsion according to the present invention is
The face-centered cubic crystal lattice structure of the silver halide constituting the silver halide grains preferably contains a polyvalent metal (dopant) other than the contained silver or halide ions.

As the polyvalent metal (dopant), F
e, Co, Ni, Ru, Rh, Pd, Re, Os, I
r, Pt, Mg, Al, Ca, Sc, Ti, V, Cr,
Mn, Cu, Zn, Ga, Ge, As, Se, Sr,
Y, Mo, Zr, Nb, Cd, In, Sn, Sb, B
a, La, W, Au, Hg, Tl, Pb, Bi, Ce, and metals, ions, and the like from the third to seventh periods (most commonly, the fourth to sixth periods) of the periodic table. At least one selected from salts containing these (including complex salts) and other compounds containing these can be used, but it is preferable to select from single salts or metal complexes.

When selected from metal complexes, a six-coordinate complex,
Five-coordinate complexes, four-coordinate complexes, and two-coordinate complexes are preferable, and octahedral six-coordinate complexes and planar four-coordinate complexes are more preferable.

[0057] As a ligand which forms a complex, CN ^-,
CO, NO ₂ ^-, 1,10-phenanthroline, 2,2 '
-Bipyridine, SO ₃ ⁻ , ethylenediamine, NH ₃ , pyridine, H ₂ O, NCS ⁻ , NCO ⁻ , O ₃ ⁻ , SO ₄ ⁻ , O
_{^{H -, N 3 -, S}} 2 -, F -, Cl -, Br -, I - or the like can be used.

In order to incorporate a polyvalent metal into the silver halide emulsion according to the present invention, the following known techniques can be applied.

B. H. Carroll; "Iridiu
m Sensitization: A Literat
ure Review ”, Photographic
Science and Engineering, Vol. 24, No. 6, November / December 1980, 265-265
267, U.S. Patent Nos. 1,951,933 and 2,6
28,167, 3,687,676, 3,76
Nos. 1,267, 3,890,154, 3,90
Nos. 1,711, 3,901,713 and 4,173
No. 483, No. 4,269,927, No. 4,413,0
No. 55, No. 4,477,561, No. 4,581, 32
No. 7, 4,643,965, 4,806,462
No. 4,828,962, No. 4,835,093
Nos. 4,902,611 and 4,981,780
No. 4,997,751 and 5,057,402
No. 5,134,060 and 5,153,110
No. 5,164,292, 5,166,044
No. 5,204,234, 5,166,045
No. 5,229,263 and 5,252,451
No. 5,252,530, EPO No. 0244184
Nos. 0488737, 0488601, 03
No. 68304, No. 0405938, No. 0509674
No. 0563946 and Japanese Patent Application No. 2-249588
No. WO93 / 02390.

Examples of the preferred polyvalent metal compound in the present invention include K ₂ IrCl ₆ , K ₃ IrCl ₆ , 2IrBr ₆ , In
Cl ₃ , K ₄ Ru (CN) ₆ , Pb (NO ₃ ) _{2 and the} like.

In the present invention, at least one selected from the group consisting of polyvalent metal atoms and their ions and complexes thereof is Ru, Os, Rh, Co, In, Ir, G
a, Ge, Pd, Pt atoms, and at least one selected from the group consisting of ions and complexes thereof, or Fe atoms other than hexacoordination complexes having cyanide ligands, and the group consisting of the ions and complexes thereof More preferably, it is at least one selected.

In the silver halide photographic emulsion according to the present invention, a polyvalent metal atom other than Ir and at least one selected from the group consisting of Ir atoms, ions and complexes thereof, and ions and complexes thereof. And at least one selected from the group consisting of:

In the present invention, in order to incorporate a polyvalent metal into a silver halide photographic emulsion, doping may be carried out during physical ripening of the silver halide grains, or the silver halide grains may be formed in the course of formation (generally, water-soluble). During the addition of the water-soluble silver salt and the water-soluble alkali halide),
Further, the doping may be performed while the formation of silver halide grains is temporarily stopped, and thereafter the formation of grains may be further continued. In addition, doping is performed after silver halide grain formation is completed,
A dopant may be introduced on the surface of the silver halide grains.
The dopant can be introduced by performing nucleation, physical ripening, and grain formation in the presence of the dopant. In general, the concentration of the dopant is suitably in the range of 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol. And a range of 2 × 10 ^-6 to 1 × 10 ^-4 mol is particularly preferred.

The sensitizing dye to be added to the above-mentioned silver halide emulsion so as to have photosensitivity in the visible light region includes:
For example, Research Disclosure (hereinafter sometimes abbreviated as RD) No. 308119 996, IV
A, A-J, RD No. 17643 23-24, R
D No. 18716 648-9, polymethine dyes including cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, merostyril and streptocyanin. be able to.

As the infrared-sensitive sensitizing dye, any one capable of imparting infrared sensitivity to a silver halide emulsion may be used.
Although not particularly limited, the invention according to claim 1 is characterized in that the infrared-sensitive silver halide emulsion is spectrally sensitized with the sensitizing dye represented by the general formula (1). is there. By using the sensitizing dye represented by the general formula (1), the effect of the present invention can be further exhibited and high sensitivity can be obtained. Although the reason is not clear, it is speculated that these sensitizing dyes are excellent in the adsorptivity to the tabular grains according to the present invention.

The light-sensitive silver halide emulsion used in the infrared-sensitive layer in the present invention is an infrared-sensitive silver halide emulsion, as long as it has photosensitivity in the infrared light range, The region may have photosensitivity. Specifically, 400
10 from visible light range longer than nm (blue light to green light to red light)
It may have photosensitivity in the near infrared light region shorter than 00 nm. In order to obtain the above sensitivity, an infrared-sensitive silver halide emulsion may be used alone, or a blue-sensitive silver halide emulsion, a green-sensitive silver halide emulsion, and a red-sensitive silver halide emulsion may be used in a certain ratio. May be used as a mixture. Further, a single silver halide emulsion may be provided with photosensitivity by using a blue-sensitive sensitizing dye, a green-sensitive sensitizing dye, and a red-sensitive sensitizing dye in addition to the infrared-sensitive sensitizing dye.

Hereinafter, the sensitizing dye represented by the general formula (1) will be described. In the general formula (1), examples of the alkyl group, aryl group and heterocyclic group represented by R include a methyl group, an ethyl group, a carboxymethyl group,
Examples include a phenyl group, a tolyl group, a pyridyl group, a furyl group, and a thienyl group.

Examples of the aliphatic groups represented by R ₅₁ and R ₅₂ include, for example, methyl, ethyl, propyl, pentyl, sulfopropyl, hydroxyethyl, phenethyl, sulfobutyl, diethylaminosulfopropyl Groups, methoxyethyl groups, naphthoxyethyl groups, carboxymethyl groups, alkyl groups such as carboxyethyl groups, and alkenyl groups such as propenyl groups. R ₅₃ and R ₅₄
Examples of the alkyl, aryl, and heterocyclic groups among the hydrogen atom, alkyl, aryl, and heterocyclic groups represented by are, for example, methyl, ethyl, propyl, butyl, benzyl, and the like. And an aryl group such as a phenyl group and a tolyl group, and a heterocyclic group such as a thienyl group and a furyl group.

Among the hydrogen atom, alkyl group, aryl group, heterocyclic group, halogen atom, alkoxy group, alkylthio group, arylthio group, heteroarylthio group and amino group (including substituted amino group) represented by R ₅₅ Examples of the alkyl group include methyl, ethyl, propyl, butyl, and benzyl groups, and examples of the aryl group include:
Examples of a phenyl group, a group such as a tolyl group, and a heterocyclic group include:
Examples of heterocyclic groups such as thienyl group and furyl group and alkoxy groups include groups such as methoxy group and alkoxy group such as ethoxy group; examples of alkylthio group, arylthio group and heteroarylthio group include methylthio group and phenylthio group. Examples of a group, a group such as a thienylthio group, and an amino group (including a substituted amino group) include groups such as an amino group, a diethylamino group, an anilino group, a piperidino group, and a furylamino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Among the hydrogen atoms or the substitutable groups represented by A _{51 to} A ₅₈ , the substitutable groups include halogen atoms such as chlorine, bromine and iodine, methyl, ethyl and the like.
Examples include an alkyl group such as a butyl group, a trifluoromethyl group and an isopropyl group, an alkoxy group such as a methoxy group, an aryl group such as a phenyl group and a tolyl group, and a carboxyl group.

Examples of the ring formed by bonding between A _{51 to} A ₅₄ and A _{55 to} A ₅₈ include benzene, 2H-1,3-dioxole and the like.

Examples of the ion represented by M ₅₁ include:
In addition to F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , BF ₄ ⁻ , ClO ₄ ⁻ , and PF ₆ ⁻ , trifluoromethanesulfonic acid ion, p-toluenesulfonic acid ion and the like can be mentioned.

The typical sensitizing dyes represented by the above formula (1) are shown below, but the present invention is not limited to these compounds.

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The above-mentioned infrared-sensitive sensitizing dyes are described, for example, by FM Hammer, The Chemistry, Inc.
f Heterocyclic Compounds No. 1
8, The Cyanine Dyes and R
elite Compounds (A. Weish
erger ed. Published by Interscience, N
ew York 1964).

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization.
Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization and substances exhibiting supersensitization are described in Research Disclosure 176, 17
643 (issued in December 1978), page 23, IV, J, or JP-B-49-25500, JP-B-43-4933,
JP-A-59-19032, JP-A-59-192242,
It is described in JP-A-3-15049 and JP-A-62-123454.

The sensitizing dyes used in the present invention are each 1 × 10 ^{−6 to} 5 × 10 ⁻³ per mol of silver halide.
Mol, preferably 1 × 10 ^{−5 to} 2.5 × 10 ⁻³ mol, more preferably 4 × 10 ⁻⁵ to 1 × 10 ⁻³ mol, in the silver halide emulsion.

The sensitizing dye used in the present invention can be directly dispersed in an emulsion. Also, these are firstly used in a suitable solvent such as methyl alcohol, ethyl alcohol, n-
It can be dissolved in propanol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof and added to the emulsion in the form of a solution. Ultrasound can also be used for lysis. As a method for adding the sensitizing dye, as described in US Pat. No. 3,469,987, the dye is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid. As described in JP-B-46-24185, etc .; a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it, and adding this dispersion to the emulsion; US Pat. No. 3,822,135, a method of dissolving a dye in a surfactant and adding the solution to an emulsion; a compound for shifting to a longer wavelength side as described in JP-A-51-74624. And dissolving the dye in an acid containing substantially no water as described in JP-A-50-80826, and adding the solution to the emulsion. A method or the like is used. In addition, US Pat. Nos. 2,912,343 and 3,34
No. 2,605, No. 2,996,287, No. 3,42
9, 835 and the like are used. The above-mentioned sensitizing dye may be uniformly added to the silver halide emulsion before being coated on a suitable support, but may be added at any stage of the preparation of the silver halide emulsion.

Further, in the invention according to claim 4, the maximum spectral sensitivity wavelength (λ _max ) of the J-aggregate of the infrared sensitizing dye is:
One feature is that spectral sensitization is performed by shifting to a longer wavelength side by 30 nm or more.

The maximum spectral sensitivity wavelength λ _{max of the} infrared sensitizing dye due to the J-aggregate in the present invention is a wavelength that appears at 700 nm or more and is determined by the following method. 650-
After giving a predetermined exposure amount at 5 nm intervals up to 900 nm and performing a normal color image processing (for example, CNK-4 manufactured by Konica), the reciprocal of the exposure amount giving a density of minimum density +0.3 is defined as sensitivity, axis - sensitivity, horizontal axis - to produce a spectral sensitivity curve of the infrared-sensitive layer comprising a wavelength, the wavelength giving the maximum sensitivity of the resulting spectral sensitivity curve is defined as lambda _max.

The present invention is characterized in that it is spectrally sensitized by a sensitizing dye represented by the general formula (1).
It is advantageous to have _max . In the present invention, λ _max
There is no particular limitation on the method of shifting the wavelength to the longer wavelength side by 30 nm or more, but it is most effective and preferable to achieve the method by the method according to claim 11 of the present invention. It is preferable that the shift width of λ _{max to} the longer wavelength side is in the range of 30 to 50 nm.

In the twelfth aspect of the present invention, the content of the sensitizing dye represented by the general formula (1) is at least 30% and at most 80% of the adsorption saturated coating amount with respect to the silver halide emulsion. It is characterized by.

The coverage of the sensitizing dye in the present invention, that is, the ratio of the amount of the sensitizing dye added to the amount of the saturated adsorption coverage can be easily obtained from the saturated adsorption amount obtained from a normal adsorption isotherm and the actual adsorption amount. be able to. The saturated adsorption amount of the sensitizing dye can be determined by a conventionally known method.For example, a silver halide emulsion in which the amount of the sensitizing dye is changed in order is prepared, and each emulsion is centrifuged. The spectral absorption spectrum of the supernatant obtained by the treatment is measured. Then, a phenomenon in which the spectral absorption spectrum of the sensitizing dye sharply increases from a certain addition amount or more is observed. The addition amount at that time is defined as the adsorption saturated coating amount.

The coverage of the sensitizing dye used in the silver halide emulsion according to the present invention varies depending on the type of the sensitizing dye.

When the sensitizing dye is used alone, the saturation coverage can be calculated from the normal adsorption isotherm and the actual coverage can be calculated. In general, the amount of saturated adsorption decreases, so that for each combination of sensitizing dyes used, the coverage must be determined from the substantial amount of saturated adsorption.

The present invention is characterized in that the photosensitive silver halide emulsion contains a novolak resin.

The novolak type resin according to the present invention is a novolak type resin obtained by condensing phenols with aldehydes or ketones, and a gel permeation chromatograph (monodisperse polystyrene of the novolak type resin as a standard). The weight average molecular weight in terms of polystyrene determined by the GPC method is 6,000 to 30,000, 2,000 to 5,
The area ratio of the GPC pattern in the range of 000 and 100 to 1000 is 30 to 90% with respect to the entire area, respectively.
Novolak type resins of 0 to 40% and 20 to 90%.

Specific examples of the phenols used in the production of the novolak resin preferably include phenol and m- or p-alkylphenol.
Examples of the phenol include monovalent, divalent, and trivalent phenols such as catechol, resorcin, hydroquinone, and pyrogallol, but monovalent phenol is preferable. m-
M-cresol, 3,5-
Xylenol, carvacrol, thymol and the like, and as p-alkylphenol, p-cresol,
2,4-xylenol and the like. These phenols can be used alone or in combination.

Examples of the aldehyde include formaldehyde, acetaldehyde, benzaldehyde, acrolein, methacrolein, crotonaldehyde, acrolein dimethyl acetal, and furfural. Of these, preferred is formaldehyde or benzaldehyde. As formaldehyde, an aqueous formaldehyde solution (formalin) and paraformaldehyde which is an oligomer of formaldehyde can be used.
In particular, 37% formalin is industrially produced in large quantities, which is advantageous. Examples of ketones include acetone and methyl ethyl ketone.

The above novolak resin is described in, for example,
Phenol as described in US Pat.
Cresol / formaldehyde copolycondensate resins, and copolycondensate resins of p-substituted phenol and phenol or cresol and formaldehyde, as described in JP-A-55-127553.

In particular, a method for producing a high-ortho novolak resin can be produced by appropriately applying the method. For example, a phenol containing m- / p-mixed cresol is used under the condition of pH 4 to 7 using an organic acid salt of a specific divalent metal as shown in JP-B-4-2181 as a catalyst. A method of addition condensation with an aldehyde, or a method of partially adding and condensing a phenol and an aldehyde with an organic acid salt of a divalent metal as a catalyst and further using an acid as a catalyst can be applied. Also, J.I. Appl.
Chem 1957, pp. 676-688, a method of addition-condensing a phenol with an aldehyde using a hydroxide or oxide of a divalent metal as a catalyst, or a hydroxide or oxidation of a divalent metal. A method can be applied in which a phenol and an aldehyde are partially addition-condensed using a product as a catalyst and then addition-condensation is performed using an acid as a catalyst.

Also, a method of adding an aqueous formalin solution to phenols prepared by mixing m- / p-cresol at a predetermined ratio and condensing the mixture with triethylamine (JP-A-3-253589, JP-A-3-253860) Publications), a method of dissolving phenols and paraformaldehyde in a non-polar solvent such as toluene, and heating to a high temperature under a pressurized condition can be applied.

Further, the invention according to claim 2 is characterized in that the photosensitive silver halide emulsion contains the compound represented by the general formula (2).

As the compound represented by the general formula (2), a compound having an acid dissociation constant of 1 × 10 ⁻⁸ or less and a solubility product with silver ions of 1 × 10 ⁻¹⁰ or less has physical properties. Preferably, Z in the formula is a group of atoms necessary to form a heterocycle, and the heterocycle can be any heterocycle. Particularly preferred are a benzimidazole ring, a benzotriazole ring, and a purine. Ring, 8-azapurine ring and pyrazolopyrimidine ring. The hetero ring may have a substituent or a substituent atom, for example, a halogen atom (for example, each atom of chlorine, bromine, iodine, etc.), a nitro group, an amino group, each of which may be substituted C ₁ -C ₂₀ alkyl groups, C ₁ -C ₁₆ alkylthio groups,
And an alkylamino group.

The acid dissociation constant of the compound represented by formula (2) is preferably in the range of 1 × 10 ⁻⁸ to 1 × 10 ⁻¹⁸ .

The specific examples of the compound represented by formula (2) used in the present invention are shown below, but the present invention is not limited to these.

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The amount of the compound represented by formula (2) to be added to the silver halide emulsion is preferably 2 × 10 ^-7 to 1 × 10 ^-2 mol per mol of silver halide. And more preferably 2 × 10 ^{−7 to} 5 × 10 ⁻³ mol. The method of adding the compound represented by the general formula (2) to a silver halide emulsion is a method of dissolving the compound in a suitable solvent which does not have a harmful effect on the emulsion, for example, water or an aqueous alkaline solution, and adding the compound as a solution. Can be mentioned.
Further, it can be added in the form of solid fine particles. The timing of adding the compound represented by the general formula (2) to the silver halide emulsion is not particularly limited, and may be before, during, or after the chemical sensitization step.

In the invention according to claim 3, the infrared-sensitive silver halide photographic material has a number average molecular weight of 500 to 20.
One of the features is that it contains a vinylpyrrolidone polymer of 000 or less.

The polyvinylpyrrolidone polymer or copolymer used in the present invention refers to a polymer or copolymer having a pyrrolidone nucleus in its molecular structure.

Preferred specific examples of the vinylpyrrolidone polymer or copolymer include, but are not limited to, the following.

P-1: poly (N-vinylpyrrolidone) P-2: N-vinylpyrrolidone-vinyl alcohol copolymer (80:20) P-3: N-vinylpyrrolidone-vinyl alcohol copolymer (70: 30) P-4: N-vinylpyrrolidone-vinyl acetate copolymer (70:30) P-5: N-vinylpyrrolidone-acrylic acid copolymer (90:10) P-6: N-vinylpyrrolidone-2 -Hydroxyethyl acrylate copolymer (70:30) P-7: N-vinylpyrrolidone-acrylamide copolymer (80:20) P-8: N-vinylpyrrolidone-acrylamide copolymer (60:40) P- 9: N-vinylpyrrolidone-dimethylacrylamide copolymer (70:30) P-10: N-vinylpyrrolidone-vinylacetamide copolymer (70:30) P-11: N- vinylpyrrolidone - vinyl acetate -
Vinyl alcohol copolymer (60:30:10) P-12: N-vinylpyrrolidone-2-hydroxyethyl acrylate-vinyl acetate copolymer (70: 2
0:10) P-13: Poly (N-vinyloxazoline) P-14: Poly (N-vinylpiperidone) P-15: Poly (N-vinylsuccinimide) P-16: Poly (N-vinylglutarimide) P -17: N-vinylpyrrolidone-2-methoxyethyl acrylate copolymer (70:30) P-18: N-vinylpyrrolidone-methylvinylether copolymer (80:20) P-19: N-vinylpyrrolidone-N -Vinylpiperidone-2-hydroxyethyl acrylate copolymer (5
0:30:20) P-20: N-vinyl-ε-caprolactam-acrylamide copolymer (60:40) In the present invention, the vinylpyrrolidone polymer or copolymer has a number average molecular weight of 500 to 20,000. Can be used, but it is preferably 1,000 to 9,000. The preferable addition amount of the vinylpyrrolidone polymer or copolymer is 0.1 g or more, more preferably 0.3 g or more, and still more preferably 0.5 g or more, per 1 mol of silver halide. In addition, use of more than 10g
It may not be preferable because sensitivity and physical properties of the film are impaired.

Further, the invention according to claim 13 is characterized in that the infrared-sensitive silver halide emulsion contains the compound represented by the general formula (3).

In the general formula (3), R ₁ , R ₂ ,
Examples of the alkyl group represented by R ₃ and R ₄ include groups such as methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and dodecyl. These alkyl groups further include a halogen atom (eg, chlorine,
Bromine, fluorine, etc.), an alkoxy group (for example, methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy, etc.), an aryloxy group (for example, phenoxy, naphthyloxy, etc.), an aryl group ( For example, each group such as phenyl and naphthyl), an alkoxycarbonyl group (for example, each group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, and 2-ethylhexylcarbonyl), and an aryloxycarbonyl group (for example, each group such as phenoxycarbonyl and naphthyloxycarbonyl) ), Alkenyl groups (for example, vinyl, allyl and the like), heterocyclic groups (for example, 2-pyridyl, 3-pyridyl,
4-pyridyl, morpholyl, piperidyl, piperazil,
Groups such as pyrimidyl, pyrazolyl and furyl), alkynyl groups (such as propargyl group), amino groups (such as amino, N, N-dimethylamino and anilino),
It may be substituted by a cyano group, a sulfonamide group (for example, each group of methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octylsulfonylamino, phenylsulfonylamino, etc.) and the like.

Examples of the alkenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a vinyl group and an allyl group.

Examples of the alkynyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include a propargyl group.

The aryl group represented by R ₁ , R ₂ , R ₃ and R ₄ includes, for example, a phenyl group and a naphthyl group.

Examples of the heterocyclic group represented by R ₁ , R ₂ , R ₃ and R ₄ include a pyridyl group (eg, 2-pyridyl, 3-pyridyl)
Each group such as pyridyl and 4-pyridyl), thiazolyl group, oxazolyl group, imidazolyl group, furyl group, thiecole group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, pyrazolyl group, And a tetrazolyl group.

The alkenyl group, alkynyl group, aryl group and heterocyclic group are all the same as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ , and the groups shown as the substituents of the alkyl groups. Can be substituted by a group.

Examples of the substituent represented by R ₅ , R ₆ , R ₇ , and R ₈ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, and an alkoxy group. Carbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, hydrogen atom, mercapto group, alkylthio group, arylthio group , An alkenylthio group, a heterocyclic thio group and the like. These groups can be substituted by the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups shown as the substituents of the alkyl groups.

The ring formed by R ₁ and R ₂ includes, for example, benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole,
And rings such as pyrazine and indole.

It is more preferable that R ₃ and R ₄ form a ring. Examples of the ring that can be formed by R ₃ and R ₄ include rings such as piperidine, pyrrolidine, morpholine, pyrrole, pyrazole and piperazine.

The ring which can be formed by R ₅ and R ₆ , and R ₇ and R ₈ includes, for example, rings such as benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole, pyrazine, indole and the like.

The above-mentioned rings can be substituted by the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the same groups as the rings exemplified as the substituents of the alkyl groups.

The methine group represented by L ₁ or L ₂ may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group,
Examples include an alkoxycarbonyl group and an aryloxycarbonyl group. These groups further include R ₁ , R ₂ ,
It can be substituted by the same substituents as the alkyl groups represented by R ₃ and R ₄ and the groups exemplified as the substituents of the alkyl group.

Specific examples of the compound represented by formula (3) (hereinafter, also referred to as the compound of the present invention) used in the present invention are shown below, but it should not be construed that the invention is limited thereto.

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The compound represented by formula (3) of the present invention can be easily synthesized by a method known to those skilled in the art.

The addition amount of the compound represented by the general formula (3) of the present invention is 2 × 10 ^-7 to 1 × 1 per mol of silver halide.
It is preferable to use 0 ^-2 mol, and more preferably, 2 x 10 ^-7 to
5 × 10 ⁻³ mol is preferred.

As a method for adding the compound represented by formula (3) of the present invention to a silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or pyridine,
Dissolved in a water-soluble solvent such as methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide or a mixture thereof, or diluted with water,
Alternatively, it can be dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can be used during the dissolution process.

Further, the compound represented by the general formula (3) of the present invention is dissolved in a volatile organic solvent as described in US Pat. No. 3,469,987 and the like, and this solution is added to a hydrophilic colloid. A method of adding a dispersed dispersion to an emulsion, JP-B-46
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving and adding this dispersion to an emulsion as described in JP-A-24185 or the like is also used.

Further, the compound represented by the general formula (3) of the present invention can be added to an emulsion in the form of a dispersion by an acid dispersing method.

The compound represented by the general formula (3) of the present invention may be added at any time during the period from the formation of the silver halide grains to the coating step. It is preferred to add.

In the invention according to claim 11, in the chemical sensitization step, the infrared-sensitive silver halide emulsion is prepared in the order of a chemical sensitizer, a novolak resin, and a compound represented by the general formula (1). Characterized by being prepared by adding By adding the compound according to the present invention in the above order, a silver halide emulsion having high sensitivity and excellent infrared effect can be obtained.

The chemical sensitizer that can be used in the infrared-sensitive silver halide emulsion of the present invention is not particularly limited, and examples thereof include chalcogen sensitizers such as sulfur sensitization and selenium sensitization, and gold sensitizers. A noble metal sensitizer such as palladium sensitizer or the like can be appropriately selected and used in the chemical sensitization step of a silver halide emulsion. It is also preferable to combine two or more sensitization methods. The infrared-sensitive silver halide emulsion of the present invention,
The location of the chemical sensitization nucleus can be selected according to the purpose. It is generally preferred to form at least one kind of chemical sensitizing nucleus near the surface.

One of the chemical sensitization methods preferably applicable to the infrared-sensitive silver halide emulsion of the present invention is a single or combination of sensitization using a chalcogen compound and sensitization using a noble metal. , James (TH James)
Author, The Photographic Process, 4th Edition, Macmillan, 1977, (TH James, Th.
e Theory of the Photograph
hic Process, 4th ed, Macmil
lan, 1977), pages 67-76, and can be carried out using RD12.
0, April 1974, 12008; RD 34, 19
June 75, 13452, U.S. Pat. No. 2,642,36
No. 1, No. 3,297,446, No. 3,773,0
No. 3l, No. 3,857,711, No. 3,901,
Nos. 714, 4,226,018, and 3,
No. 904,415 and British Patent 1,315,75.
As described in No. 5, sulfur, selenium, tellurium at pAg 5-10, pH 5-8 and temperature 30-80 ° C.
It can be gold, platinum, palladium or a combination of several of these sensitizers.

In the noble metal sensitization, for example, noble metal salts of gold, platinum and palladium can be used, and among them, gold sensitization, palladium sensitization or a combination of both is preferable. One of the chalcogen sensitization methods that can be preferably performed on the silver halide emulsion of the present invention is sulfur sensitization. Examples of the sulfur sensitizer include hypo, thiourea compounds, rhodanine compounds and U.S. Pat. Nos. 3,857,711, 4,226,018 and 4,054,457. Sulfur-containing compounds can be used. Selenium sensitization is one of the chalcogen sensitization methods that can be preferably performed on the silver halide emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, for example, colloidal metal selenium, selenoureas (for example, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), Selenium compounds such as selenoketones and selenamides can be used. Selenium sensitization is preferably used in combination with sulfur sensitization or noble metal sensitization or both.

The invention according to claim 5 is characterized in that at least one of the infrared-sensitive layers contains a yellow coupler, a magenta coupler and a cyan coupler in the same layer. As for the coupler, particularly preferably, similarly to general silver halide color photographic light-sensitive materials, yellow,
It consists of three types of two-equivalent couplers of magenta and cyan, each of which is contained in the same oil droplet.

The 2-equivalent coupler preferably used in the present invention is represented by the following general formula [K].

[0149]

Embedded image

In the formula, Cp represents a coupler residue, * represents the coupling position of the coupler, and X represents the coupling off with an oxidized form of an aromatic primary amine color developing agent to form a dye when the dye is formed. Represents an atom or group.

Among the coupler residues represented by Cp, representative yellow coupler residues are described in US Pat. Nos. 2,298,443, 2,407,210, 2,875,057, No. 3,048,194, No. 3,265,506, No. 3,447,928 and "Falbukplaaine Litterat-Ulversicht Agfa Mittling (Band II)" @ Far
bkupleleineliteratorturber
siecht Agfa Mitteilung (Ba
ndII) @ 112-126 (1961). Of these, acylacetanilides, for example, benzoylacetanilide and pivaloylacetanilide are preferred.

Representative magenta coupler residues are described in US Pat. Nos. 2,369,489 and 2,343.
703, 2,311,082, 2,600,7
No. 88, 2,908,573, 3,062,65
No. 3, No. 3, 152, 896, No. 3, 519, 429
No. 3,725,067, 4,540,654
No. JP-A-59-162548 and the aforementioned Agfa
Mitteilung (Band II), pages 126 to 156 (1961). Of these,
Pyrazolones or pyrazoloazoles (eg, pyrazoloimidazole, pyrazolotriazole, etc.) are preferred.

Representative cyan coupler residues are described in US Pat. Nos. 2,367,531 and 2,423,733.
No. 0, 2,474,293, 2,772,162
No. 2,895,826, 3,002,836
No. 3,034,892, No. 3,041,236 and the aforementioned Agfa Mittelung (Band)
II) pages 156 to 175 (1961). Of these, phenols and naphthols are preferred.

The leaving atom or group represented by X includes, for example, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group,

[0155]

Embedded image

(X ₁ represents an atomic group necessary for forming a 5- or 6-membered ring together with at least one atom selected from the group consisting of nitrogen, carbon, oxygen, nitrogen and sulfur in the formula) A monovalent group such as an acylamino group or a sulfonamide group and a divalent group such as an alkylene group;
In the case of a valent group, X forms a dimer.

For details of the skeleton, leaving group (atom) and exemplary compounds of the yellow coupler residue, magenta coupler residue and cyan coupler residue, see JP-A-10-14.
No. 8919.

In the invention according to claim 7, at least one of the infrared-sensitive layers contains a yellow coloring coupler, a magenta coloring coupler, and a cyan coloring coupler, and has a mass of 0.3% by mass based on the total amount of the couplers. % Of DIR coupler of 5.0% by mass or less.

The structure of the DIR coupler (inhibitor releasing type coupler) which can be used in the present invention is not particularly limited. Specific examples of the DIR coupler are described in, for example, JP-A-4-114153. D-1 to D-34
In the present invention, these compounds can be preferably used. Further, specific examples of other DIR couplers include, for example, U.S. Pat. Nos. 4,234,678, 3,227,554, and 3,643.
No. 7,291, No. 3,958,993, No. 4,419,886, No. 3,93
3,500, JP-A-57-56837,
No. 51-13239, U.S. Pat. No. 2,072,3
No. 63, No. 2,070,266, RD
Examples described in 40145, section XIV, and the like can be given.

According to the ninth aspect of the present invention, the mass ratio of the yellow color coupler, the magenta color coupler, and the cyan color coupler contained in the infrared-sensitive layer is the same. The invention according to Item 10 is characterized in that the mass ratio of the DIR coupler to the total amount of the color coupler is the same. The same mass ratio in the present invention means that each ratio is 0.95 to 1.
05.

The constitution of the infrared-sensitive silver halide photographic light-sensitive material for photography of the present invention is not particularly limited as long as it has an infrared-sensitive layer and a non-photosensitive material. 10
The invention according to the first aspect is characterized in that the infrared-sensitive layer is composed of a plurality of layers having different sensitivities. For example,
Examples thereof include a two-layer structure including a high-speed emulsion layer and a low-speed emulsion layer, and a three-layer structure including a high-speed emulsion layer, an intermediate emulsion layer, and a low-speed emulsion layer. A high-sensitivity emulsion layer may be provided from a far side of the support, or a high-speed emulsion layer may be provided from a side near the support. As the non-photosensitive layer, an antihalation layer,
An intermediate layer, a protective layer and the like may be optionally provided as needed.

In the infrared-sensitive silver halide photographic light-sensitive material for photography according to the present invention, a visible light absorber can be used in order to exhibit an excellent infrared effect. The visible light absorber may be anything that efficiently absorbs light in the visible region and transmits near-infrared light. A substance that efficiently absorbs light having a wavelength shorter than 500 nm is preferable, and a substance that efficiently absorbs light having a wavelength shorter than 580 nm is more preferable.
A substance that efficiently absorbs light having a wavelength shorter than m is more preferable.

As the visible light absorber used in the present invention, water-soluble dyes, oil-soluble dyes, alkali-soluble dyes,
In addition to various dyes such as a dye added by a method of dispersing solid fine particles, fine particle colloidal silver such as yellow colloidal silver and magenta colloidal silver can also be used. Further, a sensitizing dye or silver halide grains having the sensitizing dye adsorbed thereon may be used as the visible light absorber. Alternatively, some of the above means can be used in combination.

In the present invention, the visible light absorber may be contained at any position where visible light can be efficiently cut off. However, the visible light absorber may be contained at a position farthest from the infrared-sensitive layer farthest from the support. It is preferable to add an oil-soluble dye or a dye to be added by a method of dispersing solid fine particles, or a fine particle colloidal silver to the photosensitive layer.

The infrared-sensitive silver halide photographic light-sensitive material for photography according to the present invention is developed by a processing apparatus for a color negative-positive system in a laboratory in the same manner as a normal color negative film, and printed on a color paper to produce a monochrome image. Can be obtained. At this time, it is effective to add a colored coupler to adjust the density balance of the negative so that printing can be performed under printing conditions close to those of a general color negative film.

Colored couplers are well known in the field of color negative-positive photography, have a hue in an unreacted state, and react with an oxidized color developing agent to produce yellow,
A dye image such as magenta or cyan may be formed, or the image may be colorless. Generally, it refers to an unreacted hue that differs from a hue after a reaction. The colored coupler is a yellow colored magenta coupler, a magenta colored cyan coupler, or a yellow colored cyan coupler. These may be used according to the purpose, and two or more colored couplers may be used in combination. Examples of the skeleton of the colored coupler, conditions for use, and exemplary compounds include those described in JP-A-10-148919.

For the items other than the constituent factors of the infrared-sensitive silver halide photographic light-sensitive material for photography of the present invention described above, the following items can be used.

The silver halide emulsion according to the present invention can be used alone in the same infrared-sensitive layer, or corresponds to the silver halide emulsion according to the present invention within the range not to impair the effects of the present invention. Silver halide emulsions may be included. For those silver halide emulsions,
The one described in RD308119 can be used.

In constructing a color light-sensitive material using the silver halide emulsion of the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization in addition to the above-mentioned ones is used. can do. Additives used in such a process are described in RD38957, Sections IV and V, RD4
0145, and the like.

Known photographic additives that can be used in the present invention include RD38957, Sections II to X and RD4014.
Those described in I to XIII of item 5 can be used.

The additive used in the present invention is RD4014
It can be added by the dispersion method described in section VIII of 5, etc.

In the present invention, the RD38957
Known supports described in Section XV and the like can be used.

The light-sensitive material of the present invention includes the aforementioned RD3895
Auxiliary layers such as a filter layer and an intermediate layer described in the section 7 XI can be provided.

The light-sensitive material can have various layer structures such as a normal layer, a reverse layer, and a unit structure described in RD38957, section XI.

The light-sensitive material of the present invention includes, for example, the type / serial number, manufacturer name, emulsion No. Various information on photographic materials such as, for example, shooting date and time,
Aperture, exposure time, lighting conditions, filters used, weather,
Various information when shooting the camera, such as the size of the shooting frame, the model of the camera, the use of anamorphic lenses, etc., such as the number of prints, selection of filters, customer's color preference, the size of the trimming frame, etc. Magnetic recording for inputting various information required at the time, for example, various information obtained at the time of printing, such as the number of prints, selection of a filter, preference of a customer's color, size of a trimming frame, and other customer information. A layer may be provided.

In the present invention, the magnetic recording layer is preferably applied to the support on the side opposite to the photographic component layer. The undercoat layer, the antistatic layer (conductive layer), It is preferable that a magnetic recording layer and a slip layer are formed.

To develop the light-sensitive material of the present invention, for example, T.I. H. James, Theory of the Photographic Process 4th Edition (The Theor
yof The Photographic Process
ss Forth Edition) pages 291 to 3
34 pages and Journal of the American Chemical Society (Journal of the Am
known chemicals described in Vol. 73, p. 3, 100 (1951), and the above-mentioned RD38957, XVII to XX and RD401.
The development can be carried out by a usual method described in Section XXIII of No. 45.

In the present invention, a monochrome image can be obtained by printing on the black and white photographic paper or color photographic paper from the monochrome image negative film of the present invention which has been subjected to the color development processing. It is preferable to obtain a monochrome or sepia monochrome image print.

It is preferable to use the unexposed infrared-sensitive silver halide photographic light-sensitive material for photography of the present invention as a photography unit which is packaged in a photographable state since anyone can enjoy infrared photography easily. . The photographing unit main body does not need to be changed in any way from the color film photographing unit, and a known technique can be applied.

[0180]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Photosensitive Silver Halide Emulsion >> Photosensitive silver halide emulsions EM-1 to EM-3 were prepared according to the following method.

[Preparation of photosensitive silver halide emulsion EM-1] [Nucleation step] The following reaction mother liquor (Gr-1) in a reaction vessel
While maintaining the temperature at 30 ° C. and stirring at 400 rpm using a mixing and stirring apparatus described in JP-A-62-160128, and adjusting the pH to 1.9 with 0.5 mol / L sulfuric acid.
Adjusted to 6. Then, using the double jet method (S
The nucleation was performed by adding 180 ml each of the liquid -1) and the liquid (H-1) at a constant flow rate for 1 minute.

(Gr-1) Alkali-treated inert gelatin (average molecular weight 100,000) 40.50 g Potassium bromide 12.40 g Finish up to 16.2 L with distilled water (S-1) 862.5 g of silver nitrate 4. Finishing to 06 L (H-1) 604.5 g of potassium bromide Finishing to 4.06 L with distilled water [Aging step] After the above nucleation step, add the solution (G-1) and take 30 minutes to 60 ° C. The temperature rose. During this time, the silver potential of the emulsion in the reaction vessel (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled at 6 mV using a 2 mol / L potassium bromide solution. Subsequently, the pH was adjusted to 9.3 by adding an aqueous ammonia solution, and after further holding for 7 minutes, the pH was adjusted to 6.1 using an aqueous acetic acid solution. During this time, the silver potential was controlled at 6 mV using a 2 mol / L potassium bromide solution.

(G-1) Alkali-treated inert gelatin (average molecular weight 100,000) 173.9 g Surfactant (* EO-1) 10% by mass methanol solution 5.80 ml * EO-1: HO (CH ₂ CH) ₂ O) _m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) Finish to 4.22 L with distilled water [Growth step] Using a double jet method, the remaining liquids of the liquids (S-1) and (H-1) were
The addition was performed for 37 minutes while accelerating the flow rate (the ratio of the addition flow rate at the start to the end was about 12 times). (G-
2) The solution was added and the stirring speed was adjusted to 550 rpm, followed by 2.11 liters of the solution (S-2) and (H).
-2) The solution was added for 40 minutes while accelerating the flow rate (the ratio of the addition flow rate at the start to the end was about twice). During this time, the silver potential of the emulsion was adjusted to 6 m using a 2 mol / L potassium bromide solution.
V. After the addition was completed, the emulsion temperature in the reaction vessel was lowered to 40 ° C. over 15 minutes. Then, (Z
-1) Solution and then (SS) solution were added, the pH was adjusted to 9.3 using an aqueous potassium hydroxide solution, and iodine ions were released while aging for 4 minutes. Thereafter, the pH was adjusted to 5.0 using an aqueous acetic acid solution, and then the silver potential in the reaction vessel was adjusted to −39 mV using a 3 mol / L potassium bromide solution. The remaining liquid and the liquid (H-3) were added over 25 minutes while accelerating the flow rate (the ratio of the flow rates at the start and end was about 1.2 times).

(S-2) Silver nitrate 2.10 kg Finished to 3.53 L with distilled water (H-2) Potassium bromide 808.5 g Potassium iodide 98.1 g Finished to 2.11 L with distilled water (H-3) Potassium bromide 582.6 g Potassium iodide 12.4 g Finished to 1.42 L with distilled water (G-2) Ossein gelatin 284.9 g 10% by mass methanol solution of EO-1 7.75 ml Distilled water to 1.93 L Finish (Z-1) 83.4 g of sodium p-iodoacetamidobenzenesulfonate Finish to 1.00 L with distilled water (SS) 29.0 g of sodium sulfite Finish to 0.30 L with distilled water A desalting treatment was performed according to the method described in JP-A-72658, gelatin was added and dispersed, and the mixture was adjusted to pH 5.80 and pAg at 40 ° C. Was adjusted to 8.06 to prepare a light-sensitive silver halide emulsion EM-1 which is a silver iodobromide emulsion having an average silver iodide content of 5.00 mol%.

From the electron micrograph of the obtained emulsion particles,
The average particle diameter is 1.51 μm (the average value of the diameter of the projected area in circle), the average aspect ratio is 7.2 (60% of the total projected area is 5 or more in aspect ratio), and the variation coefficient of the equivalent circular diameter is 14.5. % Tabular grains.

[Preparation of Photosensitive Silver Halide Emulsion EM-2] In the preparation of the photosensitive silver halide emulsion EM-1, the silver potential in the [nucleation step] was controlled to 0 mV. Instead of the solution (H-2), the following (H-2)
a) In the same manner except that the solution (a) was used and the silver potential at the time of adding 2.11 liters of the solution (S-2) was changed to 0 mV.
A light-sensitive silver halide emulsion EM-2 was prepared.

(H-2a) Potassium bromide 859.5 g Potassium iodide 24.45 g Finished with distilled water to 2.11 L Photosensitive silver halide emulsion EM prepared as described above
-2 is a silver iodobromide emulsion having an average silver iodide content of 2.00 mol%, and as a result of evaluating the obtained emulsion grains by an electron micrograph, the average grain size was 2.01 μm (projected area converted to circles). Tabular grains having an average aspect ratio of 15.7 (80% or more of the projected area of all grains had an aspect ratio of 5 or more) and an equivalent circular diameter variation coefficient of 15.0%. confirmed.

[Preparation of photosensitive silver halide emulsion EM-3] In the preparation of the photosensitive silver halide emulsion EM-1, (S-1), (S-2),
The addition speed and time of (H-1) to (H-3) and the control silver potential during grain growth were appropriately adjusted, and the following solution (H-2b) was used in place of solution (H-2). Other than that, similarly, it is a silver iodobromide emulsion having an average silver iodide content of 7.90 mol%, an average grain size of 1.38 μm (average value of a projected area in terms of a circle), and an average aspect ratio of 3.9 ( 2 of projected area of all particles
0% or more had an aspect ratio of 5 or more), and a light-sensitive silver halide emulsion EM-3 which was a tabular grain having a variation coefficient of equivalent circular diameter of 13.0% was prepared.

(H-2b) Potassium bromide 747.0 g Potassium iodide 183.9 g Finished to 2.11 L with distilled water << Chemical sensitization and spectral sensitization of each photosensitive silver halide emulsion >> Silver halide emulsions EM-1 to EM-3
Was raised to 52 ° C., and in the combinations shown in Table 1, 5.5 × 10 ^-6 mol of sodium thiosulfate and 3.2 × 10 ^-6 mol of chloroauric acid per mol of silver halide. After adding 3.5 × 10 ⁻⁴ mol of potassium thiocyanate and maintaining for 15 minutes, adding 2.5 × 10 ⁻⁴ mol of novolak type resin (described in Table 1) and increasing after 15 minutes. 1.0 × 10 ⁻⁴ mol of a dye (described in Table 1) was added, and 1 /
The ripening was performed so that the sensitivity and fog density at 100 second exposure were optimized. At the end of the ripening, the stabilizer ST-1 and the antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified to obtain a chemically sensitized infrared-sensitive silver halide emulsion EM-1.
A to 8A were prepared. The adsorption rate of the sensitizing dye in each of the emulsions prepared above was 68% of the adsorption saturated coating amount in the emulsion using EM-1, 42% in the emulsion using EM-2, and E
It was 83% in the emulsion using M-3.

[0191]

[Table 1]

[0192]

Embedded image

<< Preparation of Single Emulsion Layer Sample >> To the infrared-sensitive silver halide emulsions EM-1A to 8A prepared above, a magenta coupler M-1 dissolved in ethyl acetate and tricresyl phosphate was added, and dispersion assisted. Agent (SU-1), a dispersion emulsified and dispersed in an aqueous solution containing gelatin, and a spreading agent (SU-
2) and a hardener (H-1, H-2) were added to prepare a coating solution, and each was coated on a 120 μm-thick transparent triacetylcellulose support having been subjected to a subbing process by a conventional method.
Samples 101 to 10 having the configurations shown in Table 2 were dried after drying.
No. 8 was produced.

Hereinafter, a method for preparing a single emulsion layer sample will be described. (Coating prescription) In order from the support side [First layer: infrared-sensitive silver halide emulsion layer] Each infrared-sensitive silver halide emulsion (described in Table 2) Coating amount of silver 1.5 g / m ² magenta coupler (M-1) 0.33 g / m ² tricresyl phosphate 0.50 g / m ² gelatin 3.5 g / m ² [second layer: surface protective layer] PM-1 0.15 g / m ² gelatin 0.65 g / M ²

[0195]

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<< Evaluation of Characteristics of Each Sample >> Each of the samples prepared as described above was passed through a Kenko black-and-white R-1 filter manufactured by Kenko Co., Ltd. using a light source at 5400 ° K.
/ 100 seconds for wedge exposure.
The color development processing was performed according to the development processing steps described in paragraphs [0220] to [0227] of No. 123652.

[0197] Each developed sample obtained (measurement sensitivity), the magenta density measured by X-rite Co. densitometer, to prepare a characteristic curve consisting of density D- exposure LogE, minimum density (D _min1 ) And sensitivity. The sensitivity is
It is defined as the reciprocal of the exposure amount that gives an optical density of the minimum density of magenta density + 0.10, and is shown as a relative value with the sensitivity of sample 101 being 100.

(Measurement of Granularity) The granularity was determined by measuring the RMS granularity (density of fog density + 0.20) of each developed sample through a green filter with an opening scanning area of 250 μm.
m 1000-fold value of the variation of the density values occurring when scanned at ² Konica Corp. microdensitometer) were measured,
The RMS granularity of the sample 101 is shown as a relative value with 100 being set. The smaller the numerical value, the better the granularity.

(Evaluation of Storage Property) A part of each of the prepared samples was stored in an atmosphere at 40 ° C. and a relative humidity of 80% for 7 days, subjected to a forced deterioration treatment, and then exposed by the same method as described above. , Development and minimum density (D _min2 ) were measured. The evaluation of the storage stability is as follows: [D _min2 after forced degradation treatment-D
_min1 = ΔD _min ], and the smaller the value, the better the storage stability.

Table 2 shows the results obtained as described above.

[0201]

[Table 2]

As is clear from Table 2, it can be seen that the samples 104 to 108 according to the present invention have higher sensitivity than the comparative samples 101 to 103 and are excellent in graininess and storage stability.

Example 2 << Preparation of photosensitive silver halide emulsion EM-4 >> In the photosensitive silver halide emulsion EM-1 prepared in Example 1,
The amount of potassium bromide and potassium iodide (H-2) and (H-3) in [Growing step] was changed to obtain a silver iodobromide emulsion having an average silver iodide content of 9.85 mol%. A light-sensitive silver halide emulsion EM-4 was prepared.

From the electron micrograph of the obtained emulsion particles,
The average particle diameter is 1.48 μm (the average value of the circle-converted diameter of the projected area), the average aspect ratio is 6.9 (58% of the total projected area is 5 or more in aspect ratio), and the variation coefficient of the equivalent circular diameter is 16.5. % Tabular grains.

<< Chemical sensitization of each photosensitive silver halide emulsion,
Spectral sensitization >> The photosensitive silver halide emulsion EM-
After using EM-1 and EM-3 prepared in Example 4 and EM-3, respectively, the temperature was increased to 52 ° C., and in the combinations shown in Table 3, the compound of the general formula (2) was used per mole of silver halide. 2.5 × 10 ^-5 mol and sodium thiosulfate in 5.
After adding 5 × 10 ^-6 mol, 3.2 × 10 ^-6 mol of chloroauric acid and 3.5 × 10 ^-4 mol of potassium thiocyanate and keeping the mixture for 15 minutes, 2.5 parts of the novolak resin NR-1 was added. × 10 ^-4 mol, and 15 minutes later, a sensitizing dye (Exemplified Compound 1-6)
1) was added in an amount of 1.0 × 10 ⁻⁴ mol, and ripening was performed so that sensitivity and fog density at 1/100 second exposure were optimal. At the end of ripening, the stabilizer ST-1 and the antifoggant AF-1 were added, the temperature was lowered, and the mixture was cooled and solidified, and then chemically sensitized infrared-sensitive silver halide emulsions EM-9A to 17A.
Was prepared. The adsorption rate of the sensitizing dye in each of the emulsions prepared above was 68% of the adsorption saturation coverage in the emulsions using EM-1 and EM-4, and 83% in the emulsion using EM-3.

The EM-15A was obtained immediately before the completion of ripening.
2.0 × 10 ⁻⁵ mol of Exemplified Compound 3-21 represented by the general formula (3) per mol of silver halide, and EM-1
7A, Exemplified Compound P-1, which is a polyvinylpyrrolidone polymer, was added to the first infrared-sensitive silver halide emulsion layer of the first layer in an amount of 2.5 × 10 ⁻⁵ mol per mol of silver halide. In addition, EM-16A was added 2 hours after adding the sensitizing dye.
After 0 minute, ripening was performed in a pattern in which each of the above chemical sensitizers and novolak resin were added.

[0207]

[Table 3]

The order of addition during ripening in Table 3 is as follows: Pattern A: chemical sensitizer → novolak resin → sensitizing dye Pattern B: sensitizing dye → chemical sensitizer → novolak resin.

<< Preparation and Evaluation of Single Emulsion Layer Sample >> In the same manner as in Example 1, as shown in Table 4, EM-9 prepared above as an infrared-sensitive silver halide emulsion for the first layer was prepared.
Single emulsion layer samples 201 to 209 were prepared in the same manner except that A to 17A were used, and the relative sensitivity, granularity, and storage stability were evaluated in the same manner as in Example 1. Also shown in Table 4. In the evaluation, the sensitivity and the granularity were represented by relative values based on the sample 201.

[0210]

[Table 4]

As is clear from Table 4, the samples 204 to 209 according to the present invention have high sensitivity and excellent granularity and storage stability compared to the comparative samples 201 to 203. I understand. Further, it can be seen that the effects are further enhanced by using the polyvinylpyrrolidone polymer or the compound represented by the general formula (3) together in Samples 204 to 209. In addition, in the comparison between Sample 205 and Sample 208, the addition method of each compound at the time of ripening was as follows.
It turns out that is better.

Example 3 << Preparation of multilayer silver halide photographic light-sensitive material sample >> On a 120 μm-thick transparent triacetyl cellulose support provided with an undercoat layer, each layer having the composition shown in Table 5 was successively supported. Sample 301 of multilayer silver halide photosensitive material formed from body side
Was prepared.

In Table 5, unless otherwise specified, the coating amount was g / m ² , the silver halide was converted to metallic silver, and the sensitizing dye was the number of moles added per mole of silver halide. Show.

[0214]

[Table 5]

In addition to the above composition, a coating aid SU-
2, SU-3, SU-4, dispersing aid SU-1, viscosity adjusting agent V-1, stabilizer ST-2, antifoggant AF-1, hardeners H-1, H-2 and preservative D-1 was added. still,
Oil-1 is dioctyl phthalate, and Oil-2 is dibutyl phthalate.

The emulsions used for preparing the above samples are as follows. Emulsion name Average AgI content Average grain size Aspect ratio Silver iodobromide emulsion A 2.0 mol% 0.40 μm twin plane 4.0 Silver iodobromide emulsion B 7.0 mol% 0.65 μm twin plane 5.0 Silver iodobromide emulsion C 3.0 mol% 0.05 μm octahedral-Silver iodobromide emulsions A and B were prepared by using the sensitizing dyes and chemical sensitizers described in the table. Aged according to the method. The infrared-sensitive silver halide emulsion EM-
1A is the emulsion prepared in Example 1.

Next, in the sample 301 prepared above, the type of the infrared-sensitive emulsion of the fifth layer (high-sensitivity emulsion layer),
Samples 302 to 308 were prepared in the same manner except that the amounts of the couplers in the third to fifth layers and the presence or absence of the DIR coupler (DI-3) were changed to the configurations shown in Table 6.

[0218]

[Table 6]

The structures of the compounds used in the above samples are shown below.

[0220]

Embedded image

[0221]

Embedded image

[0222]

Embedded image

[0223]

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<< Evaluation of Characteristics of Each Sample >> Sample 301 which is a multilayer silver halide photographic light-sensitive material produced as described above
After performing exposure and development treatments on the samples Nos. To 308 by the method described in Example 1, the sensitivity, granularity, preservability, and infrared effect were evaluated by the methods described below.

(Measurement of Sensitivity)
308 compared to K-Black R & D
Wedge exposure for sensitometry evaluation (exposure time: 1/100 second) was performed with white light passing through one filter, and the color development processing described in Example 1 was performed. Then, the density of the obtained processed sample was measured using a densitometer manufactured by X-rite, and the vertical axis: density (D) of three colors of yellow, magenta, and cyan: the horizontal axis: exposure amount (log E). A characteristic curve was determined. In the obtained characteristic curve, the reciprocal of the exposure amount (antilogarithm) necessary to obtain a value of the minimum density of magenta density + 0.3 was obtained as a representative, and this was defined as sensitivity. The sensitivity of each sample was shown as a relative value with the sensitivity value of sample 301 being 100.

(Evaluation of Graininess) The method described in Example 1
The granularity of the magenta-colored image was evaluated, and was expressed as a relative value with the granularity of sample 301 being 100.

(Evaluation of storage stability) One of the samples prepared above
Part for 7 days in an atmosphere of 40 ° C. and 80% relative humidity
After the forced deterioration treatment, the exposure is performed in the same manner as above.
Light, development and magenta minimum density (D_min2) Was measured.
The evaluation of the storage stability is as follows: [Magenta D after forced deterioration treatment _min2−
Unprocessed sample magenta D_min1= ΔD_min]
The smaller the value, the better the storage stability.

(Evaluation of Infrared Effect) Samples 301 to 308
Is cut to a normal 135-size 24-shot film standard and stored in a film cartridge, and then a compact camera "Big Mini Nou" manufactured by Konica Corporation.
135 "for normal landscape photography. Sample 3
At the time of photographing 01 to 308, photographing was performed by attaching a Kenko black and white R-1 filter manufactured by Kenko in front of the lens. The photographed sample was subjected to color negative development using a film processor “V30J” manufactured by Noritz to obtain a monochrome negative image, and then printed on color paper to produce a monochrome print. Evaluation of the infrared effect was performed on the obtained monochrome print.
Ten panelists performed the following four-stage subjective evaluation by visual observation, and the average value was obtained.

×: Little infrared effect is felt in the depiction of trees, etc. Δ: Some infrared effect is recognized in the depiction of trees, etc., but the degree is weak ○: Infrared effect is depressed in the depiction of trees, etc. Recognized A: A remarkable infrared effect is observed in the depiction of trees and the like. Of the above-mentioned evaluation ranks, evaluations of O and A were judged to be practically preferable as infrared-sensitive silver halide photographic materials.

Table 7 shows the results obtained as described above.

[0231]

[Table 7]

As is clear from Table 7, the sample 30 according to the present invention was evaluated in the same manner as in the evaluation of the single-layer sample in Example 1.
4 to 308 are superior to the comparative samples 301 to 303 in sensitivity, granularity, storage stability, and infrared effect. In particular, it can be seen that the effect of the present invention is more exerted by using a DIR compound in the silver halide emulsion layer or by making each coupler ratio of the Y, M, and C coupler-containing layers the same.

Example 4 In the sample 301 which is the multilayer silver halide photographic light-sensitive material prepared in Example 3, the kind of the infrared-sensitive silver halide emulsion of the fifth layer (high-sensitivity emulsion layer) and the third layer -Samples 401 to 409 were prepared in the same manner as in Example 3 except that the addition amount of each coupler in the fifth layer and the presence or absence of the DIR coupler (DI-3) were changed to the configuration shown in Table 8. After the exposure and development processes were performed by the methods described above, the sensitivity, granularity, storability, and infrared effect were similarly evaluated. Note that the sensitivity was expressed as a relative sensitivity where the sensitivity of the sample 401 was taken as 100.

Table 9 shows the results obtained as described above.

[0235]

[Table 8]

[0236]

[Table 9]

As is clear from Table 9, samples 404 to 409 having the structure according to the present invention were comparative samples 401 to 409, similarly to the evaluation of the single-layer structure sample of Example 2.
It can be seen that the sensitivity, granularity, storage stability and infrared effect are excellent with respect to No. 03. In particular, D is added to the silver halide emulsion layer.
It can be seen that the effect of the present invention is more exhibited by using an IR compound or by making the coupler ratios of all the Y, M, and C coupler-containing layers the same.

[0238]

According to the present invention, an infrared-sensitive silver halide for photography, which has the same development suitability as a color photographic light-sensitive material, has high sensitivity, and is excellent in granularity, infrared effect and long-term storage property. A photographic light-sensitive material and an infrared-sensitive silver halide emulsion used for the same were provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/06 502 G03C 1/06 502 1/12 1/12 1/20 1/20 7/305 7 / 305

Claims (13)

[Claims] 1. An infrared-sensitive silver halide photographic light-sensitive material for photography having an infrared-sensitive layer and a non-photosensitive layer on a support, wherein at least one of the infrared-sensitive layers is a total projection. 50% or more of the area is tabular silver halide grains having an aspect ratio of 5 or more, and the coefficient of variation of equivalent circle diameter is 20%.
Wherein the photosensitive silver halide emulsion is spectrally sensitized with a sensitizing dye represented by the following general formula (1) and contains a photosensitive silver halide emulsion containing a novolak type resin. Infrared photosensitive silver halide photographic material for photography. Embedded image Wherein Y ₅₁ and Y ₅₂ are each an oxygen atom, a sulfur atom,
Represents a selenium atom or> NR, wherein R represents an alkyl group, an aryl group or a heterocyclic group. R ₅₁ and R ₅₂ each represent an aliphatic group. R ₅₃ and R ₅₄ each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group; R ₅₅ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a halogen atom, an alkoxy group, an alkylthio group, an arylthio group; Group, heteroarylthio group, or amino group. A ₅₁
To A ₅₈ each represent a hydrogen atom or a substitutable group, A ₅₁ ~
A ₅₄ and A _{55 to} A ₅₈ may be combined to form a ring.
M ₅₁ represents an ion required to cancel the charge in the molecule;
m51 represents the number of ions required to cancel the charge in the molecule. ] 2. An infrared-sensitive silver halide photographic light-sensitive material for photography having an infrared-sensitive layer and a non-photosensitive layer on a support, wherein at least one of the infrared-sensitive layers has an average iodine content. It comprises silver iodobromide grains having a silver halide content of 0.5 to 8 mol%, is spectrally sensitized by the sensitizing dye represented by the general formula (1), contains a novolak resin, and An infrared-sensitive silver halide photographic light-sensitive material for photography, comprising a light-sensitive silver halide emulsion containing a compound represented by the following general formula (2). Embedded image [In the formula, Z represents an atomic group necessary for forming a heterocyclic ring. ] 3. An infrared-sensitive silver halide photographic material for photography having an infrared-sensitive layer and a non-photosensitive layer on a support, wherein at least one of the infrared-sensitive layers has an average iodine content. Photosensitive halogen containing silver bromoiodide grains having a silver halide content of 0.5 to 8 mol%, spectrally sensitized by a sensitizing dye represented by the general formula (1), and containing a novolak type resin It contains a silver halide emulsion and has a number average molecular weight of 500 or more and 200
An infrared-sensitive silver halide photographic light-sensitive material for photographing, comprising a vinylpyrrolidone polymer of 00 or less. 4. A photosensitive silver halide emulsion contained in at least one of the infrared-sensitive layers is an infrared sensitizing dye J
The infrared-sensitive silver halide photograph for photography according to any one of claims 1 to 3, wherein the maximum spectral sensitivity wavelength of the aggregate is shifted to a longer wavelength side by 30 nm or more and spectrally sensitized. Photosensitive material. 5. The method according to claim 1, wherein at least one of the infrared-sensitive layers is
A yellow color coupler, a magenta color coupler and a cyan color coupler are contained.
5. The infrared-sensitive silver halide photographic light-sensitive material for photography according to any one of 4. 6. The infrared-sensitive layer comprises a plurality of layers having different sensitivities, and all of the plurality of layers contain a yellow color coupler, a magenta color coupler, and a cyan color coupler. 6. The infrared-sensitive silver halide photographic material for photography according to any one of items 1 to 5, 7. At least one of the infrared-sensitive layers is
3. The color filter according to claim 1, further comprising a yellow color coupler, a magenta color coupler and a cyan color coupler, and a DIR coupler in an amount of 0.3% by mass or more and 5.0% by mass or less based on the total amount of the couplers. Any one of 6
Item 8. An infrared-sensitive silver halide photographic material for photography according to item 1. 8. The infrared-sensitive layer comprises a plurality of layers having different sensitivities, all of the plurality of layers containing a yellow color coupler, a magenta color coupler and a cyan color coupler, and based on the total amount of the coupler. The infrared-sensitive silver halide photographic light-sensitive material according to any one of claims 1 to 7, further comprising 0.3 to 5.0% by mass of a DIR coupler. 9. The infrared-sensitive layer comprises a plurality of layers having different sensitivities, and all of the plurality of layers have a yellow color coupler, a magenta color coupler, a cyan color coupler, and a D color coupler.
The photographing according to any one of claims 1 to 8, comprising an IR coupler, wherein the mass ratios of the yellow coloring coupler, the magenta coloring coupler, and the cyan coloring coupler in the plurality of layers are all the same. Infrared photosensitive silver halide photographic material for use. 10. The infrared-sensitive layer comprises a plurality of layers having different sensitivities, all of the plurality of layers containing a yellow coloring coupler, a magenta coloring coupler, a cyan coloring coupler and a DIR coupler, and DI in layers
The infrared-sensitive silver halide photographic light-sensitive material for photography according to any one of claims 1 to 9, wherein the mass ratio of the total amount of the R coupler / the color coupler is the same. 11. The photosensitive silver halide emulsion according to claim 1, wherein the emulsion comprises a chemical sensitizer, a novolak resin, and a sensitizing dye represented by the general formula (1). An infrared-sensitive silver halide emulsion prepared by a chemical sensitization step of sequentially adding. 12. The method according to claim 11, wherein the content of the sensitizing dye represented by the general formula (1) is 30% or more and 80% or less of the adsorption saturated coating amount with respect to the silver halide emulsion. The infrared-sensitive silver halide emulsion as described in the above. 13. A compound represented by the following general formula (3)
13. Red according to claim 11 or 12, characterized in that it contains
External photosensitive silver halide emulsion. Embedded image[Wherein, R₁, R_Two, R_ThreeAnd R_FourIs a hydrogen atom,
A kill group, an alkenyl group, an alkynyl group, an aryl group or
R represents a heterocyclic group;_Five, R₆, R₇And R₈Is a substituent
Represents L₁And L_TwoEach represents a methine group;₁Is oxygen
Atom, sulfur atom, selenium atom, tellurium atom, -C
(R₉) (R_Ten)-Or -N (R₉)-. R ₉as well as
R_TenRepresents a hydrogen atom, an alkyl group, an alkenyl group,
Represents a rukinyl group, an aryl group or a heterocyclic group. Also, R₁
And R_Two, R_ThreeAnd R_Four, R_FiveAnd R₆, R₇And R₈, R ₉And R_TenIs
You may combine with each other to form a ring. ]