JP2001066741A - Image-forming method using color filter and photosensitive material having the color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a combination of a color filter and a photosensitive material, capable of obtaining digital image data nearly free of color turbidity and having high image quality at a low cost. SOLUTION: When an image is formed by photographing on a silver halide photographic material through a color microfilter having 9 μm filter pitch (p) or higher, the relation s/p2>=60,000 is satisfied between the filter pitch (p) (μm) of the color microfilter and the photography area(s) (μm2) of the photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method capable of obtaining high-quality digital image data with less color turbidity at low cost by using a combination of a photosensitive material and a color microfilter. The present invention relates to a photosensitive material capable of easily obtaining high-quality digital image data when used in combination.

[0002]

2. Description of the Related Art With the development and diversification of information equipment, the need for digitizing image information is increasing. Digitization makes it possible to process, transfer, filing, and creating a database of image information on a computer. As a means for digitizing image information in general photographing, there is a method using a digital still camera (hereinafter, also referred to as DSC). In general, a DSC converts optical image information into an electric signal using a CCD as an image pickup device and records the electric signal on a medium such as a memory. DSC is excellent in that image information is digitized immediately after shooting. However, for example, increasing the number of pixels of a CCD requires a large-capacity memory, and it is difficult to reduce the size and weight of the camera body. It is difficult to obtain low-cost, high-quality digital image information.

As another means for digitizing image information, there is a method of taking an image using a photosensitive material, reading the image after development, and reading it with various scanners. This method does not require individual cameras to have the function of digitizing image information if the infrastructure such as the development and scanner reading processes is maintained, so that the size and weight of the camera body can be easily reduced. There is an advantage that much image information can be recorded and digitized at low cost.

In general, photosensitive materials (hereinafter, also simply referred to as "sensitive materials") are roughly classified into silver salt-based materials and non-silver salt-based materials. Silver halide materials include silver halide photosensitive materials such as photographic films, photographic papers, and X-ray films. Non-silver salt materials include diazo photosensitive materials such as diazo films, diazo copies, and PS plates, and azide photosensitive materials. Polymer-based photosensitive materials and the like are known. Silver halide photographic materials have higher photographic sensitivity than non-silver halide photographic materials and are suitable for rich gradation expression, and thus have been used for general photography for a long time.

At present, various film scanners are commercially available, and images obtained by photographing and developing with a negative for general photography and a positive film can be digitized. However, there is a problem that these general photographic photosensitive materials do not have a configuration or a function suitable for obtaining high-quality digital image information at low cost. For example, silver halide color photographic light-sensitive materials for general photography have recently developed color reproduction,
In order to meet various needs such as improvement of image quality such as sharpness and granularity and enhancement of sensitivity, it usually has a complicated multilayer structure of 10 layers or more. Some of the functions of such photosensitive materials for general photography are performed by the data processing process after digitization, and the cost can be further reduced by simplifying and optimizing the structure of the photosensitive material itself. It is.

US Pat. No. 4,971,869 discloses that a photosensitive material in which a monochrome emulsion is coated on a support is photographed by using a color microfilter having a repeating pattern of three color stripes of yellow, green and cyan. A technique for extracting information from a scanned image with a scanner has been disclosed. Since the photosensitive material used here can record color image information using a monochrome emulsion, it can have a simpler structure than the above-described multilayer color photographic photosensitive material for general photography.
However, the combination of the color filter and the photosensitive material used here has a problem that color turbidity occurs and a sufficient image quality cannot be obtained.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an image forming method comprising a combination of a color microfilter and a photosensitive material which can obtain high quality digital image data with low color turbidity at low cost. An object of the present invention is to provide a color microfilter used and a monochrome photosensitive material having the color microfilter on a support.

[0008]

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

1. In an image forming method for photographing a photosensitive material through a color microfilter having a filter pitch p of 9 μm or more, a filter pitch p (μm) of the color microfilter and a photographing area s (μm) of the photosensitive material
² ) and s / p ² ≧ 60,000.

[0010] 2. 2. The image forming method according to the above item 1, wherein the photosensitive material is a silver halide photosensitive material.

3. In an image forming method for photographing a silver halide photosensitive material through a color microfilter having a filter pitch p of 9 μm or more, the filter pitch p (μm) of the color microfilter and the most silver halide among the silver halide photosensitive materials An image forming method comprising: p / d ≧ 5 with an average particle diameter d (μm) of silver halide particles contained in a photosensitive layer having a large average particle diameter.

4. In an image forming method for photographing a silver halide photosensitive material through a color microfilter having a filter pitch p of 9 μm or more, the filter pitch p (μm) of the color microfilter and the color development of the silver halide photosensitive material after color development Image formation characterized in that there is a relationship of p / c ≧ 5 between the average particle diameter c (μm) of the dye cloud in the photosensitive layer having the largest average diameter of the dye cloud of the formed color dye and the filter pitch. Method.

5. In an image forming method for photographing a silver halide photosensitive material through a color microfilter having a filter pitch p of 9 μm or more, a filter pitch p (μm) of the color microfilter and a resolution for reading image information by a scanner after image formation. r (μm): p / r ≧ 2.5.

6. A color microfilter used in the image forming methods of the above 1 to 5.

[0015] 7. A silver halide photosensitive material having a color microfilter and at least one silver halide photosensitive layer, and performing photographing by exposing the silver halide photosensitive layer through the color microfilter. The pitch is 9 μm or more,
A silver halide photosensitive material having a relationship of s / p ² ≧ 60,000 between the filter pitch p (μm) and the exposure area s (μm ² ).

8. A silver halide photosensitive material having a color microfilter and at least one silver halide photosensitive layer, and performing photographing by exposing the silver halide photosensitive layer through the color microfilter. The pitch is 9 μm or more,
There is a relationship of p / d ≧ 5 between the filter pitch p (μm) and the average particle size d (μm) of silver halide particles contained in the photosensitive layer having the largest average silver halide particle size. A silver halide light-sensitive material, characterized in that:

9. A silver halide photosensitive material having a color microfilter and at least one silver halide photosensitive layer, and performing photographing by exposing the silver halide photosensitive layer through the color microfilter. The pitch is 9 μm or more,
The filter pitch p (μm) and the average particle diameter c (μm) of the dye cloud in the photosensitive layer in which the average particle diameter of the dye cloud of the coloring dye formed after color development of the silver halide photosensitive material is the largest.
A silver halide light-sensitive material having a relationship of p / c ≧ 5 between m) and a filter pitch.

Hereinafter, the present invention will be described in detail.

The color microfilter used in the present invention is designed to correctly separate subject information to be photographed into colors.
It is preferable to use a combination of blue, green, and red whose spectral transmission characteristics are three primary colors of light by the additive method, and a combination of yellow, magenta, and cyan by the subtractive method, but US Pat. No. 4,971,8.
A combination of saturated colors and unsaturated colors as in the filter described in No. 69 may be used. Further, a black matrix portion may be provided in addition to the above.

In the present invention, the arrangement of each color of the filter can take various configurations. For example, a method of arranging yellow, magenta and cyan filters in a mosaic or stripe shape, or a method of arranging blue, There is a method of arranging three color filters of green and red in a mosaic shape or a stripe shape. Examples of a method of arranging the filters in a mosaic form include a lattice arrangement method represented by a Bayer arrangement, and an arrangement in which triangles, hexagons, and circles are spread. The arrangement of each color may be regular or may be arranged completely at random, but it is possible to arrange stripes regularly or mosaic in which each filter is rectangular or square and uniform in size. Filters are preferred for obtaining clearer image information.

The filter pitch referred to in the present invention is an average value of the width of the filter region of each color and a value in a direction showing the minimum when measured on one straight line on the filter surface. For example, in the case of a filter arranged in a stripe shape, it means the average value of the width of each color in the direction perpendicular to the stripe, and the shape of the filter region of each color is rectangular and arranged in the same direction. In the case of the mosaic filter described above, it is the average value of the width of each color in the direction of the shorter side of the rectangle.

The filter pitch can be measured using a normal magnifying glass. The number of measurements of the width of the filter region of each color is set to 500 or more, and the obtained values are averaged.

In the present invention, the filter pitch is 9 μm
That is all. If the thickness is less than 9 μm, color turbidity occurs, which is not preferable. Although the details of the mechanism of the occurrence of color turbidity are not clear, a color forming unit of the photosensitive material (for example, in the case of a silver halide photosensitive material, developed silver halide particles) straddles filters of different colors. This is considered to be because the probability increases and colors that are not originally exposed are also exposed.

The exposure screen or the photographing screen referred to in the present invention is
The portion where one screen (one frame) on the photosensitive material is exposed is shown. In the present invention, the area s of the photographic screen of the photosensitive material
(Μm ² ) and the filter pitch p (μm) of the color microfilter have a correlation represented by s / p ² ≧ 60,000, preferably s / p ² ≧ 500,
000, and more preferably s / p ² ≧ 10,000
It is 0000.

If the area s of the photographic screen is within a practical range in which the photosensitive material can be loaded into the camera and the image information can be read by the scanner, the larger the photographic area per screen, the better the image quality. Is preferred. Also,
The filter pitch p must be 9 μm or more as described above.
Is too large, the image quality deteriorates.
the value of p ² is not preferable less than 60,000.

In the present invention, the shape of the photographing screen is not particularly limited, but is preferably a quadrilateral, and its aspect ratio is preferably 1: 5 to 5: 1.

In the present invention, the light-sensitive material may be any of the above-mentioned silver salt-based materials and non-silver salt-based materials. However, silver halide light-sensitive materials are preferred because of their high sensitivity. It is preferably a silver halide photosensitive material having a silver halide emulsion layer.

The filter pitch p (μm) of the color microfilter of the present invention and the average particle size d (of the silver halide particles contained in the photosensitive layer having the largest average silver halide particle size in the silver halide photosensitive material) μm) and p /
It has a relationship represented by d ≧ 5. Preferably, p / d ≧
10, and more preferably p / d ≧ 20. If the average grain size d of the silver halide grains is too small, the sensitivity is lowered, and if it is too large, the graininess is deteriorated. If the average grain size d of the silver halide is too large with respect to the filter pitch p, color turbidity occurs as described above. Therefore, it is not preferable that this value is less than 5.

In the present invention, the average particle diameter c (μm) of the color dye cloud after development is observed with a high magnification optical microscope. This is also observed for 500 or more pieces, and the obtained value is defined as the average particle size. If the filter pitch p (μm) of the color microfilter for this c becomes small, the probability that the dyed pigment cloud crosses the filter increases, so that it is impossible to display an accurate color and the color reproduction is reduced.
The value of c needs to be 5 or more.

In the present invention, the reading resolution when image information after development is read by a scanner can be obtained by calculation. For example, a CCD having 2000 × 2000 pixels has a resolution of 20/2000 = 0.01 mm = 10 μ when reading the entire area of a 20 mm × 20 mm sample at one time.

In the present invention, silver halide contained in the light-sensitive material includes silver bromide, silver iodobromide, silver chloride, silver chlorobromide,
Any halogen composition such as silver chloroiodobromide or silver iodochloride may be used. Generally, when sensitivity is important, silver iodobromide,
Silver bromide, silver chloroiodobromide, and silver chloride, silver chlorobromide, etc. are preferably used when processing speed is important. A silver halide emulsion containing these grains was prepared by Simmy & Physics Photographic (Paul Grafkides)
Montel, 1967); Photographic Emulsion Chemistry by G. F. Duffin (published by The Focal Press, 1966).
Year); Making co-authored by V. El Jerikhman
And Coating Photographic Emulsion (published by The Focal Press, 1964)
Year), JP-A-51-39027,
No. 55-142329, No. 58-113928, No. 54-48521 and No. 58-4938, No. 60-
138538, etc., and can be prepared by the method described in page 88 of the Abstracts of the 58th Annual Meeting of the Photographic Society of Japan. That is,
Any of an acidic method, a neutral method, an ammonia method, etc. may be used. The method of reacting a soluble silver salt and a soluble halide is a one-sided mixing method, a double-mixing method, a combination thereof, or a method in which the grains are mixed under excess silver ions. (Reverse mixing method), a method of supplying a soluble silver salt and a soluble halide salt to a fine seed crystal and growing the same.

In the present invention, the particle size of a silver halide grain is a diameter when a projected image of the grain is converted into a circular image having the same area. The projected area of a particle can be determined from the sum of the particle areas. In any case, a silver halide crystal sample distributed on a sample table to such an extent that the grains do not overlap can be obtained by observing with an electron microscope. The average projected area diameter of the tabular silver halide grains is represented by a circle-equivalent diameter of the projected area of the grains, and is preferably 0.30 μm or more, more preferably 0.30 to 5 μm, and still more preferably 0.40 μm. ２2 μm. The particle size can be obtained by projecting the particles at a magnification of 10,000 to 70,000 times with an electron microscope and actually measuring the projected area on the print. The average particle diameter (φ) can be obtained by the following equation, where n is the number of measured particle diameters and ni is the frequency of particles having the particle diameter φi.

Average particle size (φ) = (Σni · φi) / n (The number of particles to be measured is assumed to be 1,000 or more indiscriminately.) In the present invention, the silver halide particles comprise one photosensitive layer. The average particle size in that case is a value measured by mixing the silver halide grains to be used.

The silver halide grain size distribution of the silver halide emulsion may be either narrow or wide, but is preferably monodisperse with uniform grain sizes. Specifically, when the width of the distribution is defined by the relative standard deviation (coefficient of variation) which can be expressed by (standard deviation of particle size / average particle size) × 100 = width (%) of particle size distribution, 25 %, More preferably 20% or less.

In the present invention, the silver halide grains contained in the silver halide emulsion may have a regular shape such as a cubic, octahedral or tetradecahedral shape, or an irregular shape such as a tabular twin. It may be in a shape or a mixture of both, but preferably contains tabular grains. The tabular silver halide grains preferably used in the present invention have an average value (average aspect ratio) of a ratio of grain diameter / thickness (aspect ratio) of 2 or more, and an average aspect ratio of 3 to 20 is preferable.
More preferably, it is 4 to 15. In these tabular silver halide grains, the outer wall of the crystal may substantially consist almost of {111} planes or may consist of {100} planes. In addition, it may have both the {111} plane and the {100} plane.

When silver iodobromide or silver bromide tabular grains are used, at least 50% of the grain surfaces are {111} faces, more preferably 60% to 90% are {111} faces. In particular, particles having 70% to 95% {111} planes are particularly preferable. It is preferable that the plane other than the {111} plane is mainly the {100} plane. This surface ratio is determined by utilizing the difference in the dependence of the adsorption of the sensitizing dye between the {111} plane and the {100} plane as described in “T. Tani, J. Ima”.
ging Sci. , 29, 165 (1985) ".

The tabular (iodo) bromide grains are preferably hexagonal. Hexagonal tabular grains (hereinafter sometimes abbreviated as hexagonal tabular grains) refer to the main plane (# 1).
(11 ° plane) is hexagonal, and the maximum adjacent side ratio is 1.0 to 2.0. Here, the maximum adjacent side ratio is the ratio of the length of the side having the maximum length to the length of the side having the minimum length forming a hexagon. If the maximum adjacent side ratio is 1.0 to 2.0, the hexagonal tabular grains may have rounded corners, and may have more corners and become substantially circular tabular grains. The length of a side having a rounded corner is represented by the distance between the intersection of the extended straight line portion of the side and the extended straight line portion of the adjacent side. Each side forming the hexagon of the hexagonal tabular grains preferably has a half or more of substantially a straight line, and more preferably has an adjacent side ratio of 1.0 to 1.5.

The tabular (iodo) bromide grains preferably have dislocations. Dislocations of silver halide grains are described, for example, in J. Am. F. Hamilton, Photogr. Sci.
Eng. , 57 (1967); Shiozaw
a, J. et al. Soc. Photogr. Sci. Japan
n, 35, 213 (1972), which can be observed by a direct method using a transmission electron microscope at a low temperature. The dislocation position of the silver halide grains is 0.58 to 1.0 L from the center of the silver halide grains toward the outer surface.
It is desirable that the occurrence occurs in the region up to, but more preferably, it occurs in the region of 0.80 to 0.98 L. The direction of the dislocation line is approximately from the center to the outer surface, but often meanders. Regarding the number of dislocations in the silver halide grains, it is desirable that grains containing one or more dislocations are present in 50% (number) or more, and the higher the ratio (number) of the number of tabular grains having dislocation lines, the more preferable.

In the present invention, silver chloride, silver chlorobromide, silver chloroiodide or silver chloroiodobromide tabular grains can be used. In this case, any of tabular grains having a {100} plane as a principal plane and tabular grains having a {111} plane as a principal plane can be used. For silver chloride tabular grains having {100} faces, see US Pat. No. 5,314,798.
, European Patent Nos. 534,395A and 617,32
No. 1A, No. 617,317A, No. 617,318
No. A, No. 617, 325A, WO94 / 22051
No. 616,255A, U.S. Pat.
Nos. 56,764, 5,320,938 and 5,
275,930, JP-A-5-204073, and 5-
No. 281640, No. 7-225441, No. 6-301
No. 16, etc. Also, mainly $ 11
Various reports have been made on tabular grains composed of 1｝ planes. For example, US Pat.
No. 520 and the like. U.S. Pat. No. 5,250,403 describes so-called ultrathin tabular grains having an equivalent circle equivalent diameter of 0.7 μm or more and a thickness of 0.07 μm or less. No. 4,435,5.
No. 01 discloses a technique for growing a silver salt epitaxially on the surface of tabular grains.

The thickness of silver halide grains can be obtained by observing a sample obliquely with an electron microscope. In the present invention, the preferred thickness of the tabular grains is 0.03 to 1.0 μm, more preferably,
It is 0.05 to 0.5 μm. In the present invention, the tabular silver halide grains preferably have a small thickness distribution. Specifically, when the width of the distribution is defined by (standard deviation of thickness / average thickness) × 100 = width (%) of thickness distribution, it is preferably 25% or less, more preferably 20%. These are:

Further, taking into account the factors of the aspect ratio and the thickness of the grains, the flatness represented by the following formula: A = ECD / b ² is preferably 20 or more. Here, ECD indicates the average projected diameter (μm) of tabular grains, and b is the thickness of the grains. Here, the average projected diameter represents the number average of the diameter of a circle having an area equal to the projected area of the tabular grains.

Further, in the present invention, the distribution of the halogen content of each grain in the tabular silver halide grain emulsion is preferably small. Specifically, (standard deviation of halogen content / average halogen content) ×
When the width of the distribution is defined by 100 = the width (%) of the halogen content, it is preferably 25% or less, more preferably 20% or less.

In the present invention, the silver halide grains may have a core / shell type structure having at least two layer structures having substantially different halogen compositions in the silver halide grains or may have a uniform composition. In the present invention, the average silver iodide content of the silver halide emulsion is preferably at most 20 mol%,
More preferably, it is 0.1 to 10 mol%. In the present invention, so-called halogen conversion type (conversion type) particles may be used. The halogen conversion amount is preferably from 0.2 to 2.0 mol% based on the silver amount, and the conversion may be carried out during physical ripening or after physical ripening. As a method of halogen conversion, an aqueous halogen solution or fine silver halide particles having a solubility product with silver smaller than the halogen composition on the grain surface before the halogen conversion is usually added. The fine particle size at this time is preferably 0.2 μm or less, more preferably 0.02 to 0.1 μm.

Further, during the process of forming and / or growing the silver halide grains, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (including a complex salt),
At least one metal ion selected from a rhodium salt (including a complex salt) and an iron salt (including a complex salt) can be added, and these metal elements can be contained inside the particle and / or in the particle surface layer.

In the present invention, the silver halide photographic emulsion is
Unnecessary soluble salts may be removed at the end of the growth of the silver halide grains, or may remain contained. When removing the salts, a Research Disclosure (hereinafter referred to as R) is used.
(Also referred to as D) 17643 No. II.

In the present invention, two or more types of silver halide emulsions each formed separately can be arbitrarily mixed and used.

The photosensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. For the chemical sensitization of the photosensitive silver halide emulsion according to the present invention, chalcogen sensitization methods such as sulfur sensitization method, selenium sensitization method, tellurium sensitization method, etc., which are well-known in emulsions for normal type photosensitive materials, gold, platinum Noble metal sensitization and reduction sensitization using palladium or the like can be used alone or in combination (for example, see JP-A-3-1105).
No. 55, JP-A-5-241267, etc.).

As the chalcogen sensitizer applied to the silver halide emulsion, a sulfur sensitizer and a selenium sensitizer are preferably used. As sulfur sensitizers, thiosulfate, allyl thiocarbamide thiourea, allyl isothiocyanate,
Examples include cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like. The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like, but 5 × 10 ^{−10 to} 5 × 10 ⁻ per mol of silver halide. A range of ⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferred.

The gold sensitizer can be added as various gold complexes in addition to chloroauric acid, gold sulfide and the like. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but usually 1 × 10 ^-4 to 1 × 10 ^-8 mol per mol of silver halide. It is preferred that More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).
issue). Further, an antifoggant described later can be added after the completion of chemical sensitization. Specifically, Japanese Patent Application Laid-Open No. 5-4583
No. 3, JP-A-62-40446. The pH at the time of chemical sensitization is preferably 5.3 to 1
0.5, more preferably 5.5 to 8.5, and pAg
Is preferably 6.0 to 10.5, more preferably 6.8.
９9.0. The coating amount of the photosensitive silver halide used in the present invention is 1 mg to 10 g / m ² in terms of silver.
Range.

In the preparation of the silver halide used in the present invention, reduction sensitization can be used in combination. By placing the silver halide emulsion in an appropriate reducing atmosphere, a reduction sensitizing nucleus can be provided inside the silver halide grains and / or on the surface of the grains. The reduction sensitization is preferably performed during the growth of silver halide grains described below. As a method of applying during the growth, not only a method of performing reduction sensitization in a state where silver halide grains are growing, but also a method of performing reduction sensitization in a state where growth of silver halide grains is interrupted, and then performing reduction sensitization. The method also includes a method of growing the perceived silver halide grains, specifically, by adding a reducing agent and / or a water-soluble silver salt to the silver halide emulsion.

Preferred examples of the reducing agent include thiourea dioxide, ascorbic acid and derivatives thereof. Another preferred reducing agent is hydrazine,
Examples thereof include polyamines such as diethylenetriamine, dimethylamine borane, and sulfite. The amount of the reducing agent added depends on the type of reduction sensitizer, the particle size of the silver halide grains,
It is preferable to change the composition depending on environmental conditions such as composition, crystal habit, temperature of reaction system, pH, pAg and the like. For example, in the case of thiourea dioxide, 0.01 mol per mol of silver halide is used.
A range of ２2 mg is preferred. In the case of ascorbic acid, the range is preferably 0.2 to 50 g per mol of silver halide. Conditions for the reduction sensitization are as follows: temperature is 40 to 80 ° C., time is 10 to 200 minutes, pH is 5 to 11, pAg is 1 to 1
A range of 0 is preferred.

It is preferable to use silver nitrate as the water-soluble silver salt. By adding a water-soluble silver salt, so-called silver ripening, which is a kind of reduction sensitization technique, is performed. PAg at the time of silver ripening is 1
-6 is suitable, more preferably 2-4. The conditions such as temperature, time and pH are preferably in the above ranges.

Further, the action of the reducing agent added at the desired point in time of the formation of the particles is such that the oxidizing agent such as hydrogen peroxide (water) and its adduct, peroxoacid salt, ozone, I ₂ , thiosulfonic acid, etc. It is preferable to deactivate the compound by adding it, and to suppress or stop the reducing agent. The oxidizing agent may be added at any time from when the silver halide grains are formed to before the addition of a gold sensitizer (or a chemical sensitizer if no gold sensitizer is used) in the chemical sensitization step.

In the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like in order to impart color sensitivity such as green sensitivity and red sensitivity to the photosensitive silver halide. If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Specifically, US Patent No. 4,617,257
No. JP-A-59-180550, JP-A-64-13546
And sensitizing dyes described in JP-A-5-45828 and JP-A-5-45834.

These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is particularly used for the purpose of adjusting the wavelength of supersensitization or spectral sensitization. Often used. Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. , 615,641
And those described in JP-A-63-23145). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening.
Nos. 6,225,666 before and after the nucleation of silver halide grains. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion such as gelatin, or one solution of a surfactant. The amount of addition is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the present invention, hydrophilic protective colloids used for preparing silver halide emulsions and silver halide photosensitive materials include those described in "Products Licensing Index", Vol. In addition to the gelatins used in ordinary silver halide emulsions as described, gelatin derivatives such as acetylated gelatin and phthalated gelatin, water-soluble cellulose derivatives and other synthetic or natural hydrophilic polymers are included.

In the present invention, an organic metal salt can be used as an oxidizing agent together with the photosensitive silver halide. Among such organic metal salts, an organic silver salt is particularly preferably used. Organic compounds that can be used to form the above-described organic silver salt oxidizing agents include US Pat.
There are benzotriazoles, fatty acids and other compounds described in No. 0,626, columns 52 to 53 and the like. The acetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Two or more organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 1 mol per mole of the photosensitive silver halide.
10 mol, preferably 0.05 to 3 mol, can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is 0.05 to 10 g / m ^{2 in} terms of silver, preferably 0.1 to 0.1 g / m ² .
４4 g / m ² is suitable.

In the present invention, various antifoggants or photographic stabilizers and precursors thereof can be used in the light-sensitive material. As a specific example, Research Disclosure, Vol. 176, Item / 1764
3 (December 1978), Volume 184, Item / 184
31 (August 1979), Volume 187, Item / 187
16 (November 1979) and 308, Item / 3
08119 (December 1989); U.S. Pat.
No. 9,378, No. 4,500,627, No. 4,6
14,702, JP-A-64-13564 (7)-
Pages (9), (57) to (71) and (81) to (9)
7), U.S. Patent Nos. 4,775,610 and 4,6.
Nos. 26,500 and 4,983,494;
2-174747, 62-239148, JP-A-1-150135, 2-110557, and 2-1
78650, RD17643 (1978) (2
Compounds described on pages 4) to (25) are exemplified. These compounds are used in an amount of 5 × 10 ^-6 to 1 × 10 ^-1 per mole of silver.
Mole is preferable, and 1 × 10 ⁻⁵ to 1 × 10 ⁻² mole is more preferably used.

In the present invention, the photosensitive layer containing a silver halide emulsion is preferably spectrally sensitized over the entire visible light region. Further, the silver halide photosensitive layer forms a monochrome image, and the image may be a silver image obtained by monochrome development processing or a dye image formed by color development.

Various techniques and additives known in the art can be used in the silver halide photographic light-sensitive material according to the present invention, if necessary. For example, a photosensitive silver halide emulsion layer,
Protective layer, the filter layer, various intermediate layers other than the antihalation layer, undercoat layer, crossover light cut layer,
Various auxiliary layers, such as a backing layer, can be provided.
Specifically, an undercoat layer described in U.S. Pat. No. 5,051,335, JP-A-1-1677838, JP-A-61678
An intermediate layer having a solid pigment as described in US Pat.
JP-A Nos. 1-120553, 5-34884 and 2
An intermediate layer having a reducing agent or a DIR compound as described in US Pat. No. 6,646,634, or an electron transfer agent as described in U.S. Pat. Nos. 5,017,454 and 5,139,919 and JP-A-2-23544. Having an intermediate layer, JP-A-4-249
In these layers such as a protective layer having a reducing agent as described in No. 245 or a layer obtained by combining them, various chemical sensitizers, noble metal sensitizers, photosensitive dyes, supersensitizers, couplers, Boiling solvents, antifoggants, stabilizers, development inhibitors,
Bleaching accelerators, fixing accelerators, color mixture inhibitors, formalin scavengers, colorants, hardeners, surfactants, thickeners, plasticizers, slippers, ultraviolet absorbers, antiirradiation dyes, filter light absorbing dyes, Anti-blocking agents, polymer latex, heavy metals, antistatic agents, matting agents and the like can be contained by various methods.

The above-mentioned additives are described in more detail in Research Disclosure, Vol. 176, Item.
/ 17643 (December 1978), 184 Volume
m / 18431 (August 1979), same volume 187 Ite
m / 18716 (November 1979) and 308 I
tem / 308119 (December 1989).

The types of compounds and the locations described in these three Research Disclosures are shown in Table 1 below.

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[Table 1]

As the binder for the constituent layers of the photosensitive material, hydrophilic binders are preferably used. Examples are the above-mentioned Research Disclosure and JP-A-64-135.
No. 46, pages (71) to (75). Specifically, transparent or translucent hydrophilic binders are preferable, for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, starch, gum arabic, dextran, pullulan, natural compounds such as polysaccharides such as carrageenan, and polysaccharides. Synthetic polymer compounds such as vinyl alcohol, polyvinylpyrrolidone, and acrylamide polymer are exemplified. No. 4,960,681.
No. superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with (For example, sodium methacrylate, ammonium methacrylate, potassium acrylate, etc.) are also used. These binders can be used in combination of two or more kinds. Particularly, a combination of gelatin and the above binder is preferable. Gelatin is also
According to various purposes, it may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin having a reduced content of calcium and the like, and it is also preferable to use them in combination. In the present invention, the coating amount of the binder is 1 m ^2.
It is preferably 20 g or less, and particularly preferably 10 g or less.

The light-sensitive material according to the present invention is preferably hardened with a hardener. Examples of hardeners include U.S. Pat. Nos. 4,678,739, column 41, and 4,791,04.
No. 2, JP-A-59-116655 and JP-A-62-2452.
No. 61, No. 61-18942, No. 61-249054
No. 61-245153, JP-A-4-218044
And the like. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol hardeners (dimethylolurea, etc.), boric acid, metaboric acid and polymer hardeners (compounds described in JP-A-62-234157). Among these hardeners, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the hydrophilic binder.

The support used for these light-sensitive materials is
Polyolefins such as polyethylene and polypropylene,
Synthetic plastic films such as polycarbonates, cellulose acetate, polyethylene terephthalate, polyethylene naphthalates, and polyvinyl chloride can also be preferably used. Syndiotactic polystyrenes are also preferred. These are disclosed in JP-A-62-1117708.
And JP-A-1-46912. Further, supports that can be used in the light-sensitive material of the present invention include paper supports such as photographic base paper, printing paper, baryta paper, and resin-coated paper, and supports in which a reflective layer is provided on the above-mentioned plastic film. No. (pp. 29-31) as the support. Those described on page 28 of RD17643, page 647, right column to page 648, left column of 18716 and page 879 of page 307105 can also be preferably used. Syndiotactic polystyrenes are also preferred. These are disclosed in JP-A-62-117.
No. 708, JP-A-1-46912 and 1-178050
It can be obtained by polymerization according to the method described in No. 5. These supports include U.S. Pat.
By performing a heat treatment of Tg or less as in 1,735,
It is possible to use a material having a hard curl. The surface of these supports may be subjected to surface treatment for the purpose of improving the adhesion between the support and the emulsion undercoat layer. In the present invention, glow discharge treatment, ultraviolet irradiation treatment, corona treatment, and flame treatment can be used as the surface treatment. Further, the supports described in the publicly known technique No. 5 (Aztec Co., Ltd., March 22, 1991), pp. 44 to 149 can also be used. A transparent support such as polyethylene dinaphthalenedicarboxylate or a support on which a transparent magnetic substance is applied can be used.

When a monochrome image of a dye image formed by color development is formed on the photosensitive material, a dye is formed in the photosensitive material by a coupling reaction with an oxidized color developing agent. A color forming agent called a coupler, which is a compound that forms, is incorporated in the photosensitive material. In this case, it is preferable to use a plurality of couplers so that the formed image is monochrome (neutral gray). In the present invention, the following couplers are preferably used as a coupler used for forming a monochrome image.

The compound which forms a dye by coupling reaction with an oxidized form of the above color developing agent as a coupler will be described in detail. Although various types of these are known, couplers preferably used in the present invention include compounds having structures represented by the following general formulas Cp-1 to Cp-12. These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol and naphthol, respectively.

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The general formulas Cp-1 to Cp-4 represent couplers called active methylene couplers, wherein R ²⁴ represents an acyl group, a cyano group, a nitro group or an aryl group which may have a substituent. , A heterocyclic group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group.

In the general formulas Cp-1 to Cp-3, R ²⁵
Is an alkyl group, an aryl group, or a heterocyclic group which may have a substituent. In the general formula Cp-4, R ²⁶ is an aryl group or a heterocyclic group which may have a substituent. Examples of the substituent which R ²⁴ , R ²⁵ and R ²⁶ may have include:
For example, an alkyl group, a cycloalkyl group, an alkenyl group,
Alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, cyano group, halogen atom, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylamino group, aryl Examples include various substituents such as an amino group, a hydroxyl group, and a sulfo group. Preferred examples of R ²⁴ include an acyl group, a cyano group, a carbamoyl group, and an alkoxycarbonyl group.

In the general formulas Cp-1 to Cp-4, Y is a hydrogen atom or a group which can be eliminated by a coupling reaction with an oxidized developing agent. As an example of Y, groups acting as an anionic leaving group of the 2-equivalent coupler include a halogen atom (eg, chloro group, bromo group), an alkoxy group (eg, methoxy group, ethoxy group), an aryloxy group (eg, phenoxy group, 4-cyanophenoxy group, 4-
Alkoxycarbonylphenyl group), alkylthio group (eg, methylthio group, ethylthio group, butylthio group), arylthio group (eg, phenylthio group, tolylthio group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl) Group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (for example, phenylcarbamoyl group, methylphenylcarbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group ( For example, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl Yl group, piperidyl sulfamoyl group, morpholinocarbonyl Rusuru sulfamoyl group), an aryl sulfamoyl group (e.g., phenyl sulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkylcarbonyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group), arylcarbonyloxy group (eg, benzoyloxy group, toluyloxy group, anisyloxy group), Examples include a nitrogen heterocyclic group (for example, an imidazolyl group and a benzotriazolyl group).

Examples of the group acting as a cationic leaving group of the 4-equivalent coupler include a hydrogen atom, a formyl group, a carbamoyl group and a methylene group having a substituent (substituents include an aryl group, a sulfamoyl group, a carbamoyl group, An alkoxy group, an amino group, a hydroxyl group, etc.), an acyl group,
And a sulfonyl group.

In the general formulas Cp-1 to Cp-4, R ²⁴
And R ²⁵ , and R ²⁴ and R ²⁶ may combine with each other to form a ring.

The general formula Cp-5 represents a coupler called a 5-pyrazolone magenta coupler, wherein R ²⁷ represents an alkyl group, an aryl group, an acyl group, or a carbamoyl group. R ²⁸ represents a phenyl group or a phenyl group substituted by one or more halogen atoms, an alkyl group, a cyano group, an alkoxy group, an alkoxycarbonyl group, or an acylamino group. For Y, general formulas Cp-1 to Cp-4
Is the same as

Among the 5-pyrazolone-based magenta couplers represented by the general formula Cp-5, those wherein R ²⁷ is an aryl group or an acyl group and R ²⁸ is a phenyl group substituted by one or more halogen atoms are preferred.

To describe these preferred groups in detail, R ²⁷ is phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro-5- (3-octadecenyl-1-succinimide) Phenyl, 2-chloro-5-octadecylsulfonamidophenyl or 2-chloro-5- [2
-(4-hydroxy-3-t-butylphenoxy) tetradecanamido] aryl group such as phenyl, acetyl, pivaloyl, tetradecanoyl, 2- (2,4-
Di-t-pentylphenoxy) acetyl, 2- (2,4
Acyl groups such as -di-t-pentylphenoxy) butanoyl, benzoyl, and 3- (2,4-di-t-amylphenoxyacetamido) benzoyl; these groups may further have a substituent; Is an organic substituent or a halogen atom connected by a carbon atom, an oxygen atom, a nitrogen atom, or a sulfur atom.

R ²⁸ is 2,4,6-trichlorophenyl,
Substituted phenyl groups such as 2,5-dichlorophenyl and 2-chlorophenyl groups are preferred.

The general formula Cp-6 represents a coupler called a pyrazoloazole coupler, wherein R ²⁹ represents a hydrogen atom or a substituent. Z represents a nonmetallic atom group necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring). Y is the same as in general formulas Cp-1 to Cp-4.

Among the pyrazoloazole-based couplers represented by the general formula Cp-6, the imidazo [1, 1] described in US Pat.
2-b] pyrazoles, U.S. Pat. No. 4,540,654
[1,5-b] [1,2,4] triazoles described in US Pat. No. 3,725,067, and pyrazolo [5,1-c] [1,2,4] triazole described in US Pat. No. 3,725,067. Are preferred, and among these, pyrazolo [1,5-b] [1,2,4] triazole is preferred from the viewpoint of light fastness.

For details of the substituents on the azole ring represented by the substituents R ²⁹ , Y and Z, see, for example, US Pat.
No. 540,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61
Pyrazoloazole couplers in which a branched alkyl group is directly linked to the 2, 3 or 6 position of the pyrazolotriazole group as described in JP-A-65245;
Pyrazoloazole couplers containing a sulfonamide group in the molecule described in JP-A-61-147254
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
No. 01443 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

The general formulas Cp-7 and Cp-8 are couplers called phenol couplers and naphthol couplers, respectively, wherein R ³⁰ is a hydrogen atom or —NHCO
_{^{R 32, -SO 2 NR 32 R}} 33, -NHSO 2 R 32, -NHC
^{OR 32, -NHCONR 32 R 33,} -NHSO 2 NR 32 R
Represents a group selected from ³³ . R ³² and R ³³ represent a hydrogen atom or a substituent. In the general formulas Cp-7 and Cp-8, R
³¹ represents a substituent, p represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. For Y, the general formula C
Same as p-1 to Cp-4. Examples of R ^{31 to} R ³³ include those described above as the substituents for R ^{24 to} R ²⁶ .

Preferred examples of the phenolic coupler represented by the general formula Cp-7 include US Pat. No. 2,369,
No. 929, No. 2,801,171, No. 2,77
No. 2,162, No. 2,895,826, No. 3,7
2-alkylamino-5-alkylphenols described in U.S. Pat. No. 72,002 and the like, U.S. Pat. No. 2,772,162
No. 3,758,308, No. 4,126,39
No. 6, No. 4,334,011, No. 4,327,1
No. 73, West German Patent Publication No. 3,329,729, 2,5-diacylaminophenols described in JP-A-59-166956 and the like; U.S. Pat. Nos. 3,446,622 and 4,333. No. 999, No. 4,451,559,
And 4-phenylureido-5-acylaminophenols described in 4,427,767 and the like.

Preferred examples of the naphthol coupler represented by the general formula Cp-8 include US Pat.
No. 93, 4,052, 212, 4,146
No. 396, No. 4,228,233, No. 4,29
Examples thereof include 2-carbamoyl-1-naphthol described in US Pat. No. 6,200 and the like and 2-carbamoyl-5-amide-1-naphthol described in U.S. Pat. No. 4,690,889 and the like.

The general formulas Cp-9 to Cp-12 are couplers called pyrrolotriazoles, and include R ⁴² , R ⁴³ and R ⁴⁴
Represents a hydrogen atom or a substituent. For Y, the general formula C
Same as p-1 to Cp-4. As the substituents for R ⁴² , R ⁴³ and R ⁴⁴ , those described above as the substituents for R ^{24 to} R ²⁶ can be mentioned. Preferable examples of the pyrrolotriazole couplers represented by the general formulas Cp-9 to Cp-12 include European Patent Nos. 488,248A1 and 491,1.
No. 97A1, No. 545,300, R ⁴² , R
^A coupler in which at least one of ⁴³ is an electron-withdrawing group.

In addition, fused ring phenol, imidazole,
Pyrrole, 3-hydroxypyridine, active methine, 5,
Couplers having a structure such as a 5-fused heterocycle and a 5,6-fused heterocycle can be used.

Examples of the fused phenol couplers include US Pat. Nos. 4,327,173 and 4,564,586.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

As the imidazole couplers, couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used.

The pyrrole coupler is disclosed in
The couplers described in Nos. 88137 and 4-190347 can be used.

As the 3-hydroxypyridine-based coupler, couplers described in JP-A-1-315736 can be used.

As active methine couplers, couplers described in US Pat. Nos. 5,104,783 and 5,162,196 can be used.

The 5,5-fused heterocyclic couplers include:
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289, pyrroloimidazole couplers described in JP-A-4-174429, and the like can be used.

The 5,6-fused heterocyclic couplers include:
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,70.
The couplers described in No. 0 can be used.

In the present invention, in addition to the couplers described above, West German Patent Nos. 3,819,051A and 3,823,049.
No. 4,840,883, US Pat.
No. 4,930, No. 5,051,347, No. 4,4
No. 81,268, European Patent Nos. 304,856A2, 329,036, 354,549A2, 374,781A2, 379,110A2, 386,930A1, 63-141055
Nos. 64-32260, 64-32261, JP-A-2-29747, JP-A-2-44340, and 2-
No. 110555, No. 3-7938, No. 3-16044
No. 0, No. 3-172839, No. 4-17247,
4-179949, 4-182645, 4-
Nos. 184437, 4-188138, 4-188
No. 139, No. 4-194847, No. 4-204532
And the couplers described in JP-A Nos. 4-207473 and 4-204732 can also be used.

In the silver halide photographic light-sensitive material used in the present invention, compounds generally known as yellow couplers, magenta couplers and cyan couplers can be used. These compounds are used in general color photography, and when developed with a paraphenylenediamine-based color developing agent, each of them has a blue region (wavelength: 350 to 500 nm).
m), a compound having a spectral absorption maximum wavelength in a green region (wavelength 500 to 600 nm) and a red region (wavelength 600 to 750 nm). However, when used in combination with the developing agents of the general formulas (1) to (5), particularly the developing agents of the general formulas (2) to (5), the dye formed by the coupling will have these wavelengths. In some cases, the coupler has a spectral absorption maximum in a wavelength region different from that described above, and accordingly, it is necessary to appropriately select the type of coupler according to the type of developing agent used. Further, the light-sensitive material of the present invention does not necessarily need to be designed so that the coloring dye has a spectral absorption maximum wavelength in the above-mentioned blue, green, and red regions. The coloring dye may have a spectral absorption in an ultraviolet region or an infrared region, or may be used in combination with the absorption in the visible light region.

The coupler which can be used in the present invention may have a diffusion-resistant group forming a polymer chain. Further, either a 4-equivalent coupler or a 2-equivalent coupler can be used, but it is preferable to use different couplers depending on the type of the color developing agent. First, it is preferable to use a 4-equivalent coupler for the developing agents of the general formulas (1), (2) and (3), and to use a 2-equivalent coupler for the developing agents of the general formulas (4) and (5). It is preferred to use couplers. Specific examples of couplers are 4 equivalents,
Two equivalents of both the Theory of the Photographic Process (4th Ed. TH James)
Edited by Macmillan, 1977) pp. 291-33
Page 4, and pages 354 to 361, JP-A-58-123.
No. 53, No. 58-149046, No. 58-14904
No. 7, No. 59-11114, No. 59-124399
Nos. 59-174835 and 59-231439
No. 59-231540, No. 60-2951, No. 60-14242, No. 60-23474, No. 60-
No. 66249, JP-A-8-110608 and 8-14
No.6552, No.8-146578, No.9-20403
No. 1, etc., and the above-mentioned documents and patents.

The light-sensitive material used in the present invention may contain the following functional coupler. As a coupler for compensating unwanted absorption of a coloring dye, European Patent No. 4
No. 56,257A1, a yellow colored magenta coupler described in the European Patent, a yellow magenta colored cyan coupler described in U.S. Pat. No. 4,833,069, and a U.S. Pat.
No. 7,136, (2), and colorless masking couplers represented by the formula (A) in claim 1 of WO92 / 11575 (especially the exemplified compounds on pages 36 to 45). Compounds (including couplers) that react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compounds: EP 378,2
Compounds represented by formulas (I) to (IV) described on page 11 of 36A1, compounds represented by formula (I) described on page 7 of EP 436,938 A2, Japanese Patent Application No. 4-134.
No. 523, a compound represented by the formula (1);
Formulas (I) and (II) described on pages 5 and 6 of No. 40,195A2.
Compound represented by (III), Japanese Patent Application No. 4-325564.
A compound represented by the formula (I) of claim 1, a ligand-releasing compound, a compound represented by LIG-X described in claim 1 of EP 4,555,478.

The couplers used in the present invention can be used alone or in combination of two or more, and can be used in combination with other types of couplers. The coupler is preferably added to the same layer as the developing agent and silver halide of the present invention, and its preferred amount is from 0.05 to 20 mol, more preferably from 0.1 to 20 mol, per mol of the developing agent. It is 10 mol, particularly preferably 0.2 to 5 mol. In the present invention, the coupler is preferably used in an amount of 0.01 to 1 mol per mol of silver halide.
0.02-0.6 mol is more preferred. This range is preferred in that a sufficient color density can be obtained.

A hydrophobic additive such as a coupler or a color developing agent can be introduced into a layer of a light-sensitive material by a known method such as the method described in US Pat. No. 2,322,027. In this case, U.S. Pat. No. 4,555,470,
Nos. 4,536,466, 4,536,467, 4,587,206, 4,555,476, 4,599,296 and JP-B-3-62256. Such a high-boiling organic solvent may be used, if necessary,
It can be used in combination with an organic solvent having a low boiling point of from 1 to 160 ° C. These couplers, high-boiling organic solvents and the like can be used in combination of two or more. The amount of the high boiling organic solvent is 10 g or less, preferably 5 g or less, more preferably 1 g to 0.1 g, per 1 g of the hydrophobic additive used. Further, 1 cc or less, more preferably 0.5 cc or less, particularly 0.3 cc or less is suitable for 1 g of the binder. Dispersion methods using polymers described in JP-B-51-39853 and JP-A-51-59943, and JP-A-62-30
No. 242 or the like and a method of adding it in the form of a fine particle dispersion can also be used. In the case of a compound which is substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, Japanese Patent Application Laid-Open No.
The surfactants described in Research Disclosure, pages 7 to 38, mentioned above, can be used. Also, Japanese Patent Application Nos. 5-204325 and 6-1924.
No. 7 and West German Published Patent No. 1,932,299A can also be used.

Among the above, with respect to a silver halide photosensitive material which forms a monochrome image from a silver image, an image can be obtained by using a well-known ordinary developing process for a monochrome photosensitive material. These use hydroquinone-based, ascorbic acid-based, p-dimethylaminophenol-based, 1-phenylpyrazolidone-based developing agents and the like as a developing agent, and then are fixed in a short time by processing such as fixing, washing and stabilizing. This is a process for obtaining a monochrome silver image, and among these, a rapid processing type black-and-white developing process can also be used. Thus, high-quality digital data can be obtained by a simple method.

In the case of a light-sensitive material containing the above-mentioned coupler, C-41 treatment manufactured by Eastman Kodak Co., Ltd., CNK-4 treatment manufactured by Konica Co., Ltd.
Processing can be performed by color processing using a p-phenylenediamine-based developing agent such as CN-16 processing manufactured by FUJIFILM Corporation.

The light-sensitive material of the present invention can be applied to a system of a type in which a developing agent is incorporated and processed in the presence of water, in which processing is further simplified.

One of the methods is, for example, a method in which a developing agent such as hydroquinone, which is the above-described monochrome developing agent, is incorporated in a photosensitive material, and an alkali or an alkali precursor is used. The alkali precursor is a compound that generates an alkali by heat, and many compounds such as guanidine carbonate are known. That is, these may be incorporated in the photosensitive material together with the developing agent, and a method of giving water in the presence of water (for example, by immersing the photosensitive material in a small amount of water or applying water). Conceivable)
And heat development. By these methods, an image can be easily obtained with only a small amount of water and heating.
Also, in order to ensure the stability of the photosensitive material, the alkali or alkali precursor and the developing agent are placed in separate sheets, and the alkali or alkali precursor is applied to another sheet-like processing material, and the photosensitive material containing the developing agent is treated with this processing sheet. And heat development in the presence of water. In this case, it is advantageous in that the development can be activated in that water is not released during the development.

Among these alkalis and alkali precursors, those that generate an alkali using a sparingly soluble metal compound described later and a complexing agent that forms a complex compound with the metal constituting the sparingly soluble metal compound are stable. It is most preferable from the viewpoint of sex. That is, for example, a hardly soluble metal compound such as zinc hydroxide or zinc oxide is incorporated in a photosensitive material (contained in a silver halide emulsion layer or a separately provided hydrophilic colloid layer), and is contained in a processing material. A method in which a metal constituting the metal compound, in this case, zinc, and a complexing agent such as picolinic acid for forming a complex compound are contained, and the light-sensitive material and the processing material are bonded and heated in the presence of water to heat and develop. It is. The processing sheet may contain an auxiliary developing agent or the like. For details of the processing sheet and the heat development, various technologies described in the section of a photothermographic material for forming a monochrome image from a color image described later will be described. Can be applied.

In the case of such a photosensitive material containing a developing agent, an activator process can be performed in addition to the above-described thermal development. When an activator process is performed on the photosensitive material, an auxiliary developer is preferably used. Here, the auxiliary developer is a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development. The auxiliary developer may be added to the activator processing solution, or may be incorporated in the photosensitive material in advance. The method of developing with an alkaline aqueous solution containing an auxiliary developer is described in RD17643, 28-
Page 29, 18716, 651, left column to right column, and 3
07105, pages 880-881.

Further, as a photosensitive material for forming a monochrome image by combining color images, a color image forming is carried out using the above-mentioned p-aminophenol and p-phenylenediamine based developing agents which are ordinary color developing agents. In addition to the method, a photosensitive material having the following constitution in which a developing agent is incorporated in the photosensitive material as well as a coupler, and a method using the following processing material for processing the photosensitive material are useful.

That is, photosensitive silver halide, at least one of the developing agents represented by the following general formulas (1) to (5):
A silver halide photographic light-sensitive material comprising a plurality of photographic constituent layers containing a compound which forms a dye by a coupling reaction with an oxidized form of the developing agent, a sparingly soluble metal salt compound, and a binder; This is a method in which an image is formed by laminating in the presence of water and a processing material containing a complex forming compound that forms a complex compound with a metal atom constituting the soluble metal salt compound, and heating and developing the resultant.

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As the compound which forms a dye by a coupling reaction with an oxidized form of the developing agent, the same compounds as described above are preferably used.

The general formulas (1), (2), (3), (4),
The compound represented by (5) will be described below.

In the general formula (1), Y represents a hydroxyl group, —N (R _a ) (R _b ) group, and R _a and R _b represent an alkyl group, an aryl group or a heterocyclic group. R ^{1 to} R ⁴ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkylcarbonamide group, an arylcarbonamide group, an alkylsulfonamide group, an arylsulfonamide group,
Alkoxy, aryloxy, alkylthio, arylthio, alkylcarbamoyl, arylcarbamoyl, carbamoyl, alkylsulfamoyl, arylsulfamoyl, sulfamoyl, cyano, alkylsulfonyl, arylsulfonyl, Alkoxycarbonyl group, aryloxycarbonyl group, alkylcarbonyl group, arylcarbonyl group,
Or represents an acyloxy group. Among R ^{1 to} R ⁴ , R ² and R ⁴ are preferably a hydrogen atom. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (2), Z represents an atomic group forming an aromatic ring. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (3), R ⁵ represents an alkyl group, an aryl group or a heterocyclic group. R ⁶ represents a substituted or unsubstituted alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom or a substituent, and R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may combine with each other to form a double bond or a ring.

In the general formula (4), Z represents an atomic group forming an aromatic ring. R ⁵ represents an alkyl group, an aryl group, or a heterocyclic group.

In the general formula (5), R ⁵ represents an alkyl group, an aryl group or a heterocyclic group. R ⁶ represents a substituted or unsubstituted alkyl group. X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl-substituted or aryl-substituted tertiary nitrogen atom. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom or a substituent, and R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may combine with each other to form a double bond or a ring.

The general formulas (1), (2), (3), (4),
The compound represented by the formula (5) is a color developing agent. In the present invention, these are incorporated in the photosensitive material, and are themselves oxidized by developing a silver salt, and the oxidized product is described later. Coupling with a coupler produces a dye. Among these, the compound of the general formula (1) or (4) is particularly preferably used. Hereinafter, these compounds will be described in detail.

The compound represented by the general formula (1) is a compound generally called sulfonamidophenol or sulfonamidoaniline. Wherein Y is a hydroxyl group, -N (R
_a ) represents an (R _b ) group, and R _a and R _b represent an alkyl group, an aryl group or a heterocyclic group, and among them, a substituted or unsubstituted alkyl group is preferable. R ^{1 to} R ⁴ each represent a hydrogen atom, a halogen atom (for example, a chloro group or a bromo group), an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, an n-butyl group,
t-butyl group), aryl group (for example, phenyl group, tolyl group, xylyl group), alkylcarbonamide group (for example, acetylamino group, propionylamino group, butyroylamino group), arylcarbonamide group (for example, benzoylamino group) Alkylsulfonamide group (for example, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (for example, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (for example, methoxy group, ethoxy group, butoxy group), aryl Oxy group (for example, phenoxy group), alkylthio group (for example, methylthio group, ethylthio group, butylthio group), arylthio group (for example, phenylthio group,
Tolthio group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group,
Ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group) , Piperidylsulfamoyl group, morpholylsulfamoyl group), arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), Sulfamoyl group, cyano group, alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), Xycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, propionyl group, butyroyl group), arylcarbonyl group (for example, benzoyl group) Group, alkylbenzoyl group) or acyloxy group (eg, acetyloxy group, propionyloxy group, butyroyloxy group)
Represents These substituents include those further having a substituent. Among R ^{1 to} R ⁴ , R ² and R ⁴ are preferably a hydrogen atom. Further, it is preferable that the sum of the Hammett constant σp values of R ^{1 to} R ⁴ is 0 or more.

R ⁵ is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group,
A stearyl group), an aryl group (e.g., phenyl, tolyl, xylyl, 4-methoxyphenyl, dodecylphenyl, chlorophenyl, trichlorophenyl, nitrochlorophenyl, triisopropylphenyl, 4-dodecyloxyphenyl, 3,5-di-
(Methoxycarbonyl) group) or a heterocyclic group (eg, a pyridyl group).

These substituents include those further having a substituent.

The compound represented by the general formula (2) is a compound generally called sulfonylhydrazine. The compound represented by the general formula (4) is a compound generally called carbamoylhydrazine.

In the formula, Z represents an atom group forming an aromatic ring. The aromatic ring formed by Z needs to be sufficiently electron-attracting in order to impart silver developing activity to the present compound. For this reason, an aromatic ring which forms a nitrogen-containing aromatic ring or has an electron-withdrawing group introduced into a benzene ring is preferably used. As such an aromatic ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a quinoline ring, a quinazoline ring, a quinoxaline ring and the like are preferable.

In the case of a benzene ring, the substituent is
Alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group), halogen atom (for example, chloro group,
Bromyl group), alkylcarbamoyl group (eg, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, dibutylcarbamoyl group, piperidylcarbamoyl group, morpholylcarbamoyl group), arylcarbamoyl group (eg, phenylcarbamoyl group, methylphenyl) Carbamoyl group, ethylphenylcarbamoyl group, benzylphenylcarbamoyl group), carbamoyl group, alkylsulfamoyl group (for example, methylsulfamoyl group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, dibutylsulfamoyl group) A famoyl group, a piperidylsulfamoyl group, a morpholylsulfamoyl group), an arylsulfamoyl group (for example, a phenylsulfamoyl group,
Methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group),
Sulfamoyl group, cyano group, alkylsulfonyl group (for example, methanesulfonyl group, ethanesulfonyl group),
Arylsulfonyl group (for example, phenylsulfonyl group,
4-chlorophenylsulfonyl group, p-toluenesulfonyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group), aryloxycarbonyl group (for example, phenoxycarbonyl group), alkylcarbonyl group (for example, acetyl group, Examples thereof include a propionyl group, a butyroyl group) and an arylcarbonyl group (for example, a benzoyl group and an alkylbenzoyl group). The sum of the Hammett constant σp values of the above substituents is 1 or more. These substituents include those further having a substituent.

The compound represented by the general formula (3) is a compound generally called sulfonylhydrazone. The compound represented by the general formula (5) is a compound generally called carbamoylhydrazone.

In the formula, R ⁶ represents a substituted or unsubstituted alkyl group (for example, a methyl group or an ethyl group). X represents an oxygen atom, a sulfur atom, a selenium atom or an alkyl- or aryl-substituted tertiary nitrogen atom, preferably an alkyl-substituted tertiary nitrogen atom. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ represent a hydrogen atom or a substituent, and R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may combine with each other to form a double bond or a ring.

The specific examples of the compounds represented by formulas (1) to (5) are shown below, but the compounds according to the present invention are of course not limited thereto.

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[0142] These developing agents used in the present invention include:
It is preferable to use 0.05 to 10 mmol / m ² per color-forming layer. A more preferable usage is 0.1 to 5 m.
mol / m ² , and a particularly preferred usage amount is 0.2 to
2.5 mmol / m ² .

Next, the complex forming compound will be described. The complex-forming compound reacts with a poorly soluble metal salt compound described later to release an alkali, and both have an effect as a base precursor. However, since a base is released by a two-component reaction, these are used as a photosensitive material. And a base precursor that is excellent in stability because it can be incorporated separately into processing materials.

In the present invention, as the complex-forming compound, a compound which forms a complex salt having a stability constant of 1 or more in log K with a metal ion constituting a sparingly soluble metal salt compound described later can be used. preferable.

In the present invention, as the complex-forming compound, those known as chelating agents in analytical chemistry and water-softening agents in photographic chemistry can be applied. The details are described in A.I. It is also described in Ringbomb, Nobuyuki Tanaka, Translated by Haruko Sugi, “Complexation Reaction” (Sangyo Tosho).

Further, with respect to these complex forming compounds,
For example, co-authored by A. E. Martell and A. E. Martell, RM Smith, "Critical Stability Konstanz (C
literal Stability Constan
ts), Volumes 1-5 ", Plenum Press
mPress).

Specifically, aminopolycarboxylic acids, iminodiacetic acid and derivatives thereof, anilinecarboxylic acids,
Pyridinecarboxylic acids, aminophosphonic acids, carboxylic acids (mono, di, tri, tetracarboxylic acids and also phosphono, hydroxy, oxo, ester, amide,
Compounds having a substituent such as alkoxy, mercapto, alkylthio, and phosphino), hydroxamic acids, polyacrylates, polyphosphoric acids, and the like, and salts with alkali metals, guanidines, amidines, quaternary ammoniums, and the like.

Next, examples of preferred complex forming compounds will be listed (where M ⁺ represents an alkali metal ion, a substituted or unsubstituted guanidinium ion, an amidinium ion or a quaternary ammonium ion). The invention is not limited to this.

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These complex forming compounds can be used alone or in combination of two or more. It can be used in combination with a known base or base precursor described below.

In the present invention, the hardly soluble metal salt compound and the metal ion forming the hardly soluble metal salt compound and the compound which undergoes the above complex formation reaction (hereinafter referred to as a complex forming compound) are
Either the photosensitive material or the processing material is contained, and after exposing the photosensitive material, it is bonded to the processing material in the presence of water and heated to raise the pH of the image forming reaction system.

The image forming reaction system in the present invention means a region where an image forming reaction occurs. Specifically, layers belonging to each of the photosensitive material and the processing material can be mentioned. When two or more layers are present, they may be all or one layer.

Water to be used as a medium can be supplied by a method of supplying water from the outside, a method of supplying capsule-containing water or the like in the image forming reaction system in advance, and breaking the capsule by heating or the like to supply water. .

Examples of the poorly soluble metal salt compound used in the present invention include carbonates, phosphates, silicates, borates having a solubility in water (the number of grams of a substance dissolved in 100 g of water) of 0.5 or less. Double salts of these compounds such as acid salts, aluminates, hydroxides, oxides, and basic salts are included.

Further, those represented by the following general formula (A) are preferable.

Formula (A) T _p Q _q where T is a polyvalent metal ion such as Zn ²⁺ , Ni ²⁺ , C
o ²⁺ , Fe ³⁺ , Mn ²⁺ , Ca ²⁺ , Ba ²⁺ , Mg ²⁺ , Sr
²⁺ , Sn ⁴⁺ , Al ³⁺ , Sb ³⁺ , Bi ^3+, etc., wherein Q can be a counter ion of an ion constituting a complex forming compound in water and shows alkalinity Which can be a counter ion of M described later in the description of the complex-forming compound and which exhibits alkalinity, wherein M is an alkali metal, guanidine, amidine or 4
When it represents a quaternary ammonium ion, it can be a counter ion and preferably shows an alkalinity, such as a carbonate ion, a phosphate ion, a silicate ion, a borate ion, an aluminate ion, a hydroxy ion, or an oxygen atom. . p and q each represent an integer such that the valence of each of T and Q can be balanced.

Preferred specific examples are listed below. Calcium carbonate, barium carbonate, magnesium carbonate, zinc carbonate, strontium carbonate, magnesium calcium carbonate (CaMg (CO ₃ ) ₂ ), magnesium oxide, zinc oxide, tin oxide, cobalt oxide, zinc hydroxide, aluminum hydroxide, magnesium hydroxide , Calcium hydroxide, antimony hydroxide, tin hydroxide, iron hydroxide, bismuth hydroxide, manganese hydroxide, calcium phosphate, magnesium phosphate, magnesium borate, calcium silicate, magnesium silicate, zinc aluminate, calcium aluminate , Basic zinc carbonate (2ZnCO ₃ .3Zn (OH) _2.
H ₂ O), basic magnesium carbonate (3MgCO ₃ .Mg)
_{(OH) 2 · 3H 2 O} ), basic nickel carbonate (NiCO
_{3 · 2Ni (OH) 2)} , basic bismuth carbonate (Bi
₂ (CO ₃ ) O ₂ .H ₂ O), basic cobalt carbonate (2Co
CO ₃ .3Co (OH) ₂ ), aluminum magnesium oxide.

Those preferably used as the hardly soluble metal salt compound are zinc or aluminum oxides, hydroxides and basic carbonates, and more preferably zinc oxide, zinc hydroxide and basic zinc carbonate. In the present invention, one kind of the hardly soluble metal salt compound may be used, or two or more kinds of the hardly soluble metal salt compounds may be used in combination.

In the present invention, it is preferable to use fine particle zinc oxide. Zinc oxide is a preferred compound in that it has higher dispersion stability than zinc hydroxide and basic zinc carbonate, and also enhances the stability over time of the photosensitive material.However, the rate of base generation during thermal development is slow, so that the development time is low. There was a disadvantage that it became longer. However, as in the present invention, the average particle size is 0.1 μm.
By using zinc oxide fine particles having a particle size of m or less, the base generation rate is increased, and heat development can be performed in a short time.

Here, the mechanism for raising the pH of the reaction system in the present invention will be described by taking a combination of potassium picolinate and zinc hydroxide as an example.

The reaction between the two is represented by the following formula, for example.

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That is, when water is present as a medium, picolinic acid ions undergo a complexing reaction with zinc ions, and the reaction represented by the above formula proceeds, resulting in high alkalinity.

In the present invention, the hardly soluble metal salt compound and the complex forming compound are contained in at least one layer on separate supports. For example, a sparingly soluble metal salt compound is used in a photosensitive material,
The complex forming compound is preferably contained in the processing material.

The amount of the sparingly soluble metal salt compound may be adjusted according to the amount of the base required during the heat development. In the present invention, the amount of the sparingly soluble metal salt compound and the complex forming compound is determined based on the amount of the image. PH of the formation reaction system is 8 or more, preferably 9 to 1
It is sufficient that the amount is sufficient to raise the number to 3. More specifically, the amount of the hardly soluble metal salt compound or complex forming compound depends on the type of compound, the particle size of the hardly soluble metal salt compound, the rate of complex formation reaction, etc. It is suitably used in an amount of 50% by weight or less, and more preferably in the range of 0.01% by weight to 40% by weight. Further, in the present invention, the content of the complex-forming compound in the reaction system is 1/1 to the content of the hardly soluble metal salt compound in a molar ratio of 1/1.
It is preferably from 00 to 100 times, particularly preferably from 1/10 to 20 times.

In the photographic constituent layer containing the hardly soluble metal salt compound, the binder is preferably contained in an amount of 0.1 to 10 parts with respect to 1 part of the hardly soluble metal compound. More preferably, 5 parts are contained.

When the preferred addition amount of these hardly soluble metal salt compounds is expressed in terms of the amount per 1 m ² of the photosensitive material, the preferred addition amount is 15 mmol / m ^{2 to} 100 mmol / m ² ,
A more preferred addition amount is from 20 mmol / m ² to 50 mmol / m ² .

In the present invention, the poorly soluble metal salt compound may be contained in either the photosensitive emulsion layer or the non-photosensitive layer, but is preferably contained in the non-photosensitive layer. In particular, it is preferably contained in a protective layer or an intermediate layer.

The poorly soluble metal salt compound is preferably dispersed in fine particles in a hydrophilic binder and contained in a light-sensitive material. The particle size of the fine particles is preferably set in a range in which light scattering during the exposure of the photosensitive material hardly occurs. In particular, when the photosensitive material of the present invention is used as a photosensitive material for photography, it is necessary to pay close attention to light scattering. The range of the average particle size generally used is from 0.001 μm to 0.2 μm, but in the present invention, it is preferable to use hardly soluble metal salt compound fine particles having an average particle size of 0.1 μm or less. A more preferred average particle size is 0.07 μm or less, and 0.05% or less.
It is particularly preferred that it is not more than μm. By using the hardly soluble metal salt compound fine particles having these particle diameters, it is possible to obtain the characteristics required for a photosensitive material for photography in the above amount.

In these light-sensitive materials, various antifoggants or photographic stabilizers and precursors thereof described in the section of the silver halide light-sensitive material can be used in the same manner. As for the additives, the same ones as used in ordinary monochrome or color light-sensitive materials can be mentioned, and further details are described in the above-mentioned RD.

The binder of the constituent layers of these light-sensitive materials,
As for the support and the like, the same materials as those used for the above-mentioned silver halide photosensitive material to be subjected to the liquid treatment can be used. However, when these photosensitive materials are used in a heat development process described later, it is necessary to use a support capable of withstanding the processing temperature among the above-mentioned materials. Further, as a support, for example, JP-A-4-124645,
JP-A-5-40321, JP-A-6-35092, Japanese Patent Application No. 5-
Photographic information and the like can also be recorded using a support having a magnetic recording layer described in No. 58221 and No. 5-106979.

Yes, it can.

It is preferable that these photosensitive materials containing the main agent are also hardened with a hardener. Examples of these hardeners include, as mentioned above, U.S. Pat. No. 4,678,739 No. 41.
No. 4,791,042, JP-A-59-1166.
No. 55, No. 62-245261, No. 61-18942
Nos. 61-249054 and 61-245153
And hardening agents described in JP-A-4-218044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-
Bis (vinylsulfonylacetamide) ethane, etc., N
A methylol hardener (such as dimethylol urea), boric acid, metaboric acid or a polymer hardener (JP-A-62-2);
No. 34157). Among these hardeners, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. These hardeners are used in an amount of 0.001 to 1 g, preferably 0.005 to 0.5 g, per 1 g of the hydrophilic binder.

Examples of the support which can be used for the photosensitive material containing a main drug include the aforementioned RD17643, page 28 and RD308119, page 1009, and Product Licensing Index, Vol. 92, P108, “Supports”. What is described is mentioned.

The light-sensitive material of the present invention containing the above-mentioned various additives and the following processing materials used for thermal development are coated on the above-mentioned or the following support by a method known in the art. You can do it.

One of the preferable processing modes for the photosensitive material containing a developing agent is a heat development processing. In the heat development, it is preferable to use a processing material different from the photosensitive material. Examples of the treatment material include a sheet having a treatment layer containing a base and / or a base precursor on a support (hereinafter also referred to as a treatment sheet). It is preferable that the treatment layer is composed of a hydrophilic binder. After the photosensitive material is imagewise exposed, the photosensitive material and the processing material are bonded on the photosensitive layer surface of the photosensitive material and the processing layer surface of the processing material and heated to form an image. A method of performing color development by supplying water equivalent to 1/10 to 1 time of water required for maximum swelling of the entire coating film constituting the photosensitive material and the processing material to the photosensitive material or the processing material, and then bonding and heating the color development. Is preferably used. Further, it is also possible to use a method in which the auxiliary developer is incorporated in the photosensitive material or the processing material as required, or is applied together with water.

In the case where heat development treatment is carried out by using the above-mentioned method of generating a base by using a combination of a basic metal compound which is hardly soluble in water and a metal ion constituting this basic metal compound and a complex-forming compound as a base precursor. In the photosensitive material and the processing sheet, a basic metal compound and a compound capable of forming a complex with the metal ion constituting the basic metal compound are separated from each other so as not to come into contact with each other until processing, and are incorporated therein as described above. Heat development is performed in the presence of water.

The heat treatment of the photosensitive material is known in the art. For the photothermographic material and the process,
For example, the basics of photo engineering (Corona, 1970)
553-555, April 1978, video information 4
Page 0, Nabletts Handbook of P
photography and Reprograph
y 7th Ed. (Vna Nostrand an
d Reinhold Company) 32-33
, U.S. Patent Nos. 3,152,904 and 3,30
Nos. 1,678, 3,392,020, 3,4
57,075, British Patent Nos. 1,131,108 and 1,167,777, and Research Disclosure, June 1978, pp. 9-15 (RD1702).
9). The heating temperature in the thermal development step is about 5
0 ° C to 250 ° C, but especially 60 ° C to 150 ° C is useful.

As the support and the binder for the processing material, the same materials as those for the photosensitive material can be used. A mordant may be added to the processing material for the purpose of removing the above-mentioned dye or other purposes. As the mordant, those known in the field of photography can be used, and US Pat. No. 4,500,626, Nos. 58-59.
And mordants described in JP-A-61-88256, pages 32 to 41, JP-A-62-244043, and JP-A-62-244036. Further, a dye-receiving polymer compound described in U.S. Pat. No. 4,463,079 may be used. Further, the above-mentioned thermal solvent may be contained.

When heat development is performed using a processing material, it is preferable to use a small amount of water for the purpose of promoting development, promoting the transfer of the processing material, and promoting the diffusion of unnecessary substances. As described above, when a method of generating a base with a combination of a basic metal compound which is hardly soluble in water and a metal ion constituting the basic metal compound and a complex forming compound is employed, it is essential to use water. is there. The water may contain an inorganic alkali metal salt or organic base, a low-boiling solvent, a surfactant, an antifoggant, a complex-forming compound with a poorly soluble metal salt, a fungicide, or a bactericide. Any water may be used as long as it is generally used. Specifically, distilled water, tap water, well water, mineral water and the like can be used. Further, in the thermal developing apparatus using the photosensitive material and the processing material of the present invention, water may be used up, or it may be circulated and used repeatedly. In the latter case, water containing components eluted from the material will be used. Also, JP-A-63-144354
No., No. 63-144355, No. 62-38460,
The apparatus described in JP-A-3-210555 or water may be used. Water can be applied to the photosensitive material, the processing material, or both. The amount used is 1/10 to 1 times the amount required for maximally swelling the entire coating film (excluding the back layer) of the photosensitive material and the processing material. As a method of applying this water, for example,
The method described in JP-A-253159 (5) and JP-A-63-85544 is preferably used. Further, the solvent can be used by being encapsulated in a microcapsule or incorporated in a photosensitive material or a processing material or both in advance in the form of a hydrate. The temperature of the water to be applied is as described in
The temperature may be 30 ° C to 60 ° C as described in, for example, Japanese Patent No. 85544.

In the present invention, when the photosensitive material is thermally developed, a known heating means can be applied, for example, a method of contacting with a heated heat block or a surface heater,
A method of making contact with a heat roller or a heat drum, a method of making contact with an infrared or far-infrared lamp heater, a method of passing through an atmosphere maintained at a high temperature, a method of using a high-frequency heating method, or the like can be used. In addition, a method in which a heat-generating conductive substance such as a carbon black layer is provided on the back surface of the photosensitive material or the image receiving member, and Joule heat generated by energization may be applied. The elements described in JP-A-61-145544 can be used as the heat-generating elements. A method of superposing a photosensitive material and a processing material in such a manner that the photosensitive layer and the processing layer face each other is disclosed in JP-A-62-25.
The method described in pages 3159 and 61-147244 (page 27) can be applied. 70 ℃ -100 ℃ as heating temperature
Is preferred. Any of various heat developing devices can be used for these processes. For example, JP-A-59-75247,
JP-A-59-177747, JP-A-59-181353, JP-A-60-18951, JP-A-62-25944, Japanese Patent Application Nos. 4-277517, 4-2433072, and 4-
No. 244693, No. 6-164421, No. 6-164
No. 422 or the like is preferably used. A commercially available device is Fuji Photo Film Co., Ltd.
PICTROSTAT 100, PICTROSTAT 20
0, Pictrostat 300, Pictrostat 3
30, the same Pictrostat 50, the same Pictography 3000, the same Pictography 2000, etc. can be used.

The processing material can have at least one timing layer. The purpose of this timing layer is to delay the bleaching reaction and the fixing reaction until the reaction between the desired silver halide and the developing agent and further the coupler is substantially completed. The timing layer can be made of gelatin, polyvinyl alcohol, or polyvinyl alcohol-polyvinyl acetate. This layer may also be used, for example, in US Pat. No. 4,056,394,
Nos. 4,061,496 and 4,229,5
A barrier timing layer as described in No. 16 may be used.

In these thermal development processes, two or more processing materials having different functions such as a processing material for performing color development, a processing material for performing bleaching and / or fixing, and a photosensitive material are sequentially superposed and heated. Processing can also be performed. In this case, it is preferable that the processing material for development does not contain a compound having a bleaching or fixing function as described above. After the photosensitive material is superposed on the processing material for development and heat-treated, it is again superposed on the processing material for bleaching with the photosensitive layer and the processing layer facing each other. At this time, the photosensitive material or the second processing material is provided with water equivalent to 0.1 to 1 times the amount required for maximally swelling the entire coating film except for both back layers. In this state, 4
By heating at a temperature of 0 ° C. to 100 ° C. for 5 seconds to 60 seconds, a bleaching process and a fixing process are performed. With respect to the amount of water, the type of water, the method of applying water, and the method of superposing the photosensitive material and the processing material, the same materials as the processing materials for development can be used.

In the present invention, in order to use or store the photosensitive material for a long period of time after processing, it is preferable to perform the above-described bleaching and fixing processes. When the light-sensitive material of the present invention is read by a scanner or the like immediately after processing and is used for conversion into an electronic image, bleaching processing and fixing processing are not necessarily required.
However, it is usually preferable to perform the fixing process. This is because the remaining silver halide has an absorption in the visible wavelength range, which adversely affects an electronic image obtained as a noise source during scanner reading. In order to realize a simple process of development only without performing a fixing process, it is preferable to use the above-mentioned thin tabular silver halide grains or silver chloride grains.

Another preferred processing form of these photosensitive materials incorporating a main ingredient is an activator processing. Activator processing refers to a processing method in which a color developing agent is incorporated in a photosensitive material, and development processing is performed using a processing solution containing no color developing agent. The processing solution in this case is characterized in that it does not contain a color developing agent contained in a normal developing solution component, and may contain other components (for example, an alkali, an auxiliary developing agent, etc.). Activator treatment is described in European Patent Nos. 545,491A1 and 565,1.
This is exemplified in known literature such as 65A1. The pH of the activator treatment liquid used in the present invention is preferably 9 or more, more preferably 10 or more.

When an activator process is performed on these photosensitive materials, an auxiliary developer is preferably used. Here, the auxiliary developer is a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development. The auxiliary developer may be added to the activator processing solution, or may be incorporated in the photosensitive material in advance. When an activator process is performed on these photosensitive materials, the presence of the hardly soluble metal compound and the chelating agent is not essential. A method of developing with an aqueous alkali solution containing an auxiliary developer is described in RD17643, 28-2.
9 pages, 18716, 651, left column to right column, and 30
7105, pages 880-881.

These photosensitive materials and processing materials containing a base agent include coating aids, improved releasability, improved slipperiness, antistatic properties,
Various surfactants can be used for the purpose of accelerating development and the like. Specific examples of the surfactant are known in the art No. 5 (199).
March 22, 2001, Aztec Co., Ltd.) 136-
138, JP-A-62-173463, 62-18
No. 3457 and the like. The photosensitive material may contain an organic fluoro compound for the purpose of preventing slippage, preventing static charge, improving peelability, and the like. Representative examples of the organic fluoro compound include fluorine surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-20944 and JP-A-62-135826, and fluorine oils. And a hydrophobic fluorine compound such as a solid fluorine compound resin such as an tetrafluoroethylene resin.

Various constitutions of the photosensitive material and the processing material (including the back layer) are used for the purpose of improving physical properties of the film such as stabilization of dimensions, prevention of curling, prevention of adhesion, prevention of cracks of the film, and prevention of pressure increase / decrease. A polymer latex can be included. Specifically, JP-A Nos. 62-245258 and 62
Any of the polymer latexes described in JP-A-136648 and JP-A-62-10066 can be used. In particular, when a polymer latex having a low glass transition point (40 ° C. or lower) is used for the mordant layer, cracking of the mordant layer can be prevented,
When a polymer latex having a high glass transition point is used for the back layer, a curl preventing effect can be obtained.

The light-sensitive material and the processing material according to the present invention preferably contain a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5
(Molar ratio)) and polystyrene particles. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrow. It is preferable that 90% or more of the total number of particles be contained between 0.9 and 1.1 times the average particle size. .
It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio) 0.3 μm) ), Polystyrene particles (0.25 μm) and colloidal silica (0.03 μm). More specifically,
No. 1-88256 (29). In addition, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc.
Nos. 44 and 63-274952.
Other compounds described in Research Disclosure can be used.

Next, a film cartridge in which these photosensitive materials can be loaded will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. The preferred plastic material is polystyrene,
Examples include polyethylene, polypropylene, and polyphenyl ether. Further, the patrone may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in JP-A-1-312537.
And No. 1-312538. Especially 25
The resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less.

Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment or the like has been kneaded in order to impart light-shielding properties. The size of the patrone may be the same as the current 135 size, and it is also effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is 30 cm ³ or less, preferably 25 cm ^3.
cm ³ or less. Weight of plastic used for patrone and patrone case is 5g
~ 15 g is preferred.

Further, a patrone for feeding a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are disclosed in U.S. Pat. Nos. 4,834,306 and 5,226,61.
No. 3.

The light-sensitive material according to the present invention can be used by loading it on a commercially available film unit with a lens.

The light-sensitive material according to the present invention is disclosed in
No. 158427, No. 10-170624, No. 10-
It can be preferably used by loading it into a film unit with a lens described in JP-A-188894.

As the film unit with a lens, a film unit loaded with a sheet film can be preferably used instead of a conventional roll film. The sheet-like photographic film is loaded in the unit so that it can be exposed in advance so as to keep a substantially single plane. That is, the film is not wound in a roll. In one embodiment of the lens-equipped film unit of the present invention, when taking a plurality of images, the position of the lens is sequentially moved within a plane parallel to the surface formed by the sheet-like photographic film, and the image is taken. The sheet film is fixed and does not move until all frames have been shot. Therefore, compared to a conventional film unit with a lens using a roll film, since there is no member for winding up, the camera can be designed to be thin.

The exposure area on a photographic film per frame is preferably 50 mm ^{2 to} 300 mm ² . This makes it possible to use a lens with a short focal length. Such a short focal length lens has a large depth of field even when a lens with a small aperture value (that is, a bright lens) is used. It is possible to shoot an in-focus image from a distance close to infinity. Further, since it is possible to take a picture even in a dark place, it is possible to take a picture indoor without a strobe.

In the present invention, the EV value of the film unit with lens is preferably 6.5 or more and less than 11. A more preferred EV value is 7.5 or more and less than 10.
In the present invention, the EV value (exposure value) is the same as a general definition, and refers to a value indicating the ability of a camera to transmit a light amount by a combination of an aperture value (F) and a shutter speed (Tsec). Is represented by the following equation.

2 EV = F ² / T That is, EV = 3.32 log 10 (F ² / T) The aperture value and shutter speed for obtaining the EV value in the above range are as follows. In the present invention, the preferred aperture value is 2 or more and less than 8.5, more preferably 2.5 or more and less than 6.5, and particularly preferably 2.8 or more and less than 5.6. Shutter speed 1/250 second or more 1/25
Seconds or less, particularly preferably 1/100 seconds or more and 1/50 seconds or less. The lens of the film unit with a lens according to the present invention preferably has a focal length of about 5 to 20 mm.

When the light-sensitive material according to the present invention is used as a photographic light-sensitive material, it is common to directly shoot landscapes, people, and the like using a camera or the like. The case where the above-described lens-attached film unit is used by being mounted thereon is similar to this. In addition, the photosensitive material of the present invention is a method of exposing through a reversal film or a negative film using a printer or a stretching machine, a method of scanning and exposing an original image through a slit or the like using an exposing device of a copying machine, etc. A method of scanning and exposing a light emitting diode, various lasers (laser diode, gas laser, etc.) and the like via an electric signal (JP-A-2-129625, JP-A-Hei-5
Nos. 176144, 5-199372, 6-12
No. 7021) and the method of outputting image information to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., and exposing directly or via an optical system.

As a light source for recording an image on a photosensitive material,
As described above, U.S. Pat. No.4, such as natural light, tungsten lamp, light emitting diode, laser light source, CRT light source, etc.
500,626, column 56, JP-A-2-53378,
The light source and the exposure method described in JP-A-2-54672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the nonlinear optical material is
It is a material capable of exhibiting the nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, such as lithium niobate, potassium dihydrogen phosphate (KDP), lithium iodate, and BaB ₂ O ₄ Such as inorganic compounds,
Urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM);
Compounds described in JP-A-53462 and JP-A-62-210432 can be preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type, and the like are known, and any of them is useful.

The above image information is obtained by dividing an image signal obtained from a video camera, an electronic still camera, or the like, a television signal represented by the Nippon Television Signal Standard (NTSC), or an original image into a plurality of pixels such as a scanner. Image signal, C
An image created using a computer represented by G or CAD can be used.

An image obtained by the present invention can be read using a scanner or the like and converted into electronic image information. In the present invention, the scanner is a device that optically scans a photosensitive material and converts reflection or transmission optical density into image information. When scanning, it is common and recommended to scan the required area of the photosensitive material by moving the optical part of the scanner in a direction different from the direction of movement of the photosensitive material. Then, only the optical part of the scanner may be moved, or only the photosensitive material may be moved to fix the optical part of the scanner. Alternatively, a combination of these may be used.

When reading the image information of an image generated in the photosensitive material, the entire surface is irradiated with light in a wavelength region where at least three dyes can be absorbed or slit scanning is performed, and the amount of reflected light or transmitted light is obtained. Is preferable. In this case, it is preferable to use diffused light, because information such as a matting agent and a scratch on the film can be removed as compared with the use of parallel light. Further, it is preferable that a semiconductor image sensor (for example, an area type CCD or a CCD line sensor) is used for the light receiving unit. In the case of performing development using a processing sheet, the presence or absence of the processing sheet at the time of image reading does not matter.

The image data obtained in this way can be viewed using various image display devices. As the image display device, an arbitrary device such as a color or monochrome CRT, a liquid crystal display, a plasma light emitting display, and an EL display is used.

In the present invention, an image signal read in this way can be output to form an image on another recording material. The output material is silver halide photosensitive material,
Various hard copy devices are used. For example, various systems such as an ink jet system, a sublimation type thermal transfer system, an electrophotographic system, a cycolor system, a thermoautochrome system, a method of exposing a silver halide color paper, and a silver halide heat development system are used. The effect of the present invention is sufficiently exhibited by any method.

The purpose of the present invention is to take in image information obtained by development as digital data. However, according to the conventional method, photographed information is converted to a print material such as color paper by an analog optical method. It can also be used after exposure.

[0210]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 Fabrication of Filter Adjustment exposure was performed through a mask filter so that an RGB stripe arrangement pattern was formed.
Japanese Patent Application No. Hei 10-32601 on a base (85 μm thick)
Sample No. 7 of Example 1 of No. 7 After a multi-layer coating of the same coating liquid as that of No. 110 was carried out, a color filter used in the present invention was produced by performing a developing process using a developing process described in Examples of the specification. The filter pitch was changed as shown in Table 2.

The following emulsion layers were provided on the side of the support on which the filter was prepared.

<Preparation of Silver Halide Emulsion> The following silver halide emulsions 1 to 3 having different average grain sizes as shown below were prepared.
5 was prepared.

The preparation method was as follows: 1 mol of silver nitrate solution 500 ml
And 0.3 mol of sodium chloride, 0.68 sodium bromide
And a mixture of 0.02 mol of potassium iodide and 500 ml of a mixed halide solution in 300 ml of a 2% aqueous gelatin solution containing 0.002 mol of adenine at 38 ° C. while stirring.
For 2 minutes to form tabular silver halide grains.

The potential during particle formation was pAg = 8.0, pH
= 2.0. On the basis of this, changes in the aspect ratio and the particle diameter were controlled by changing the supply amounts of pAg, silver nitrate and halide solutions and the mixing temperature.

After the particles are formed, the mixture is desalted by a conventional method, and then 300 ml of water and 32 g of gelatin are added, and pAg = 7.
5. Adjusted to pH = 5.5. This emulsion contains 3.3 × 10 ^-6 mol of chloroauric acid and 4 mol of sodium thiosulfate per mol of silver.
× 10 ^-6 mol was added, and a chemical sensitization treatment was performed at 65 ° C. for 48 minutes. Then 4-hydroxy-6- as a stabilizer
Methyl-1,3,3a, 7-tetraazaindene is converted to silver 1
1.5 × 10 ^-3 mol was added per mol. Thereafter, the emulsion temperature was raised to 40 ° C., and a proper amount of the sensitizing dye was sufficiently adsorbed. Then, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetraazaindene was added in an amount of 1.5 × 10 ⁻³ mol per mol of silver.

Silver halide emulsion Average grain size (μm) Average A / R ratio Coefficient of variation 1 0.30 5.5 12 2 0.65 6.0 14 3 1.00 8.0 16 16 1.80 8. Using the silver halide emulsion 2 (the sensitizing dye used and the amount described in the second layer), the following emulsion layers were formed on the line filters having different pitches. Then, as shown in Table 2, photosensitive material samples 101 to 112 were produced.

[0218]

[Table 2]

However, the amount of addition is expressed in grams per 1 m ² . The silver halide was converted to the amount of silver, and the sensitizing dye (indicated by SD) was shown in moles per mole of silver.

First layer (intermediate layer) OIL-1 0.10 AS-1 0.08 Gelatin 0.9 2 layers (panchromatic emulsion layer) Silver halide emulsion 2 3.30 Sensitizing dye (SD-1) 1.05 × 10 ^-4 sensitizing dye (SD-2) 8.2 × 10 ^-5 sensitizing dye (SD-3) 1.45 × 10 ^-4 sensitizing dye (SD-6) 8.1 × 10 ^-5 Cyan coupler (C-1) 0.3 Magenta coupler (M-1) 0.31 Yellow coupler (Y-1) 1.0 High boiling organic solvent (OIL-2) 0.8 Gelatin 3.00 In addition to the above compositions, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, stabilizer ST-1, S
T-2, antifoggants AF-1, AF-2, AF-3,
AF-4, AF-5, hardeners H-1, H-2, H-3,
H-4 was added.

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Each of the samples 101 to 112 was processed into a 135-size film shape and loaded into a patrone. After that, using a single-lens reflex camera (F4) manufactured by Nikon Corp., a person, flowers, and plants were planted under appropriate sensitivity settings. Green, macbeth chart,
A total of five types of scenes including the sharpness chart were photographed. The area of the film used for photographing was changed by the lens magnification and the photographing distance.

After the photographing was completed, the film was processed in the following color negative film developing process.

<< Color development processing >> (Processing step) Process Processing time Processing temperature Supply amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Fixing 1 minute 30 minutes 38 ± 2.0 ° C. 830 ml Stability 60 seconds 38 ± 5.0 ° C. 830 ml Drying 60 seconds 55 ± 5.0 ° C.-* The replenishing amount is a value per 1 m ² of the photosensitive material.

(Color developing solution composition) Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxyamine sulfate 2.5 g Sodium chloride 0.6 g 4 -Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g diethylenetriaminepentaacetic acid 3.0 g potassium hydroxide 1.2 g Alternatively, the pH is adjusted to 0.06 using 20% sulfuric acid.

(Composition of color developing replenisher) Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3.0 g Potassium sulfite 5.0 g Sodium bromide 0.4 g Hydroxyamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl -N- (β-hydroxyethyl) aniline sulfate 6.3 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 2.0 g Water was added to make up to 1.0 liter, and the pH was adjusted to 1.0 using potassium hydroxide or 20% sulfuric acid. Adjust to 18.

(Bleach liquid composition) Water 700 ml 1,3-diaminopropanetetraacetate ammonium iron (III) salt 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Alternatively, adjust the pH to 4.4 using glacial acetic acid.

(Composition of bleaching replenisher) Water 700 ml 1,3-diaminopropanetetraacetate ammonium iron (III) 175 g ethylenediaminetetraacetic acid 2 g sodium nitrate 50 g ammonium bromide 200 g glacial acetic acid 56 g Adjust to pH 4.4 with water or glacial acetic acid.

(Formulation of Fixing Solution) Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.2 using aqueous ammonia or glacial acetic acid.

(Formulation of Fixing Replenisher) Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g Add water to make up to 1.0 liter, and adjust to pH 6.5 using aqueous ammonia or glacial acetic acid.

(Preparation of Stabilizing Solution and Stable Replenishing Solution) Water 900 ml p-octylphenol / ethylene oxide / 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml Water was added to make up to 1.0 liter, and the pH was adjusted to 8 using ammonia water or 50% sulfuric acid. Adjust to 5.

The obtained developed sample was subjected to a red color separation filter (gelatin filter No. W26 manufactured by Eastman Kodak Co.) using a monochrome CCD using an appropriate optical system,
A green separation filter (No. W99) and a blue separation filter (No. W98) were installed between the light source and the sample.
The BGR image was read using a monochrome CCD (KX4 manufactured by Eastman Kodak Company) of 48 × 2048 pixels. The BGR images were synthesized using Photoshop made by Adobe, and the optimal image correction was performed to obtain RGB image data.

The RGB image data thus obtained was output as color prints on Konica color paper of A4 size (210 × 297 mm) type QAA7 at a resolution of 300 dpi using a Konica LED printer.

These prints were randomly extracted from
Sensory evaluation was performed on the sharpness, roughness, and vividness of the color of the image using 0 as an evaluation panelist. The evaluation was performed on a five-point scale, with 5 points for each item being very good and 1 point being very poor for each item. The average value of each item was taken as the overall evaluation value of the image, and the average of 10 people was taken. did.

The obtained results are shown in Table 3 below.

[0247]

[Table 3]

As is clear from Table 3, digital image information obtained from the photosensitive material using the filter of the present invention has excellent image quality. A small image obtained from the comparative sample was subjected to sharpness due to a small number of pixels, and a large image was poor in separation of color information.

Example 2 A photographic component layer having the composition shown below was sequentially coated on the same side as the filter of the support having the line filters having the filter pitches of 7 μm, 9 μm and 20 μm produced in Example 1. Thus, photosensitive material samples 201 to 209 having a multilayer structure as shown in Table 4 were produced. The amount of each material added is indicated in units of g / m ² as the coating amount per 1 m ^2. The silver halide and sensitizing dye used in Example 1 were used, and the amounts used were expressed in terms of silver.

First layer (undercoat layer) Gelatin 0.8 Ultraviolet absorber (UV-1) 0.2 High boiling point solvent (OIL-2) 0.2 Second layer (silver halide photosensitive layer) Gelatin 5. 0 Silver halide emulsion (Table 4) 8.5 sensitizing dye (SD-1) 2.6 × 10 ^-4 sensitizing dye (SD-2) 2.7 × 10 ^-4 sensitizing dye (SD-3) 3.8 × 10 ^-4 sensitizing dye (SD-6) 1.4 × 10 ^-4 color developing agent (D-24) 1.35 cyan coupler (C-2) 1.5 magenta coupler (M-2) 0.3 Yellow coupler (Y-2) 0.6 High boiling solvent (OIL-1) 1.0 High boiling solvent (OIL-2) 0.25 Antifoggant (AF-6) 0.005 Water soluble polymer ( PS-1) 0.05 Third layer (antihalation layer) Gelatin 0.80 Dye (AI-1) 0.28 Dye (A -2) 0.24 Dye (AI-3) 0.40 4th layer (base generating layer) Gelatin 1.20 Additive (HQ-2) 0.02 High boiling point solvent (OIL-2) 0.06 Water solubility Polymer (PS-1) 0.06 Zinc oxide 1.63 Zinc hydroxide 0.40 Fifth layer (protective layer) Gelatin 0.50 Matting agent (WAX-1) 0.20 Water-soluble polymer (PS-1) 0 .12 In addition to the above composition, coating aids SU-1 and SU-
2, SU-3, dispersing aid SU-4, stabilizer ST-1, S
T-2, antifoggants AF-1, AF-2, AF-3,
AF-4, AF-5, hardeners H-1, H-2, H-3,
H-4 was added. The total amount of F-2, F-3, F-4 and F-5 was 15.0 mg / m ² , 60.0%, respectively.
^{mg / m 2, 50.0mg / m} 2 and 10.0mg / m ²
Was added to each layer. The materials used above are as follows.

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[Table 4]

<Preparation of Processing Sheet> A processing sheet for subjecting the above photosensitive material to heat development was prepared.

Underlined transparent PEN base (85 μm thickness)
A treatment sheet was prepared by sequentially applying layers having the following composition on the top. The amount of each material added is indicated in units of g / m ² as the coating amount per 1 m ^2. The materials used are described above, and those not present are shown below.

First layer Addition amount (g / m ² ) Gelatin 0.46 Water-soluble polymer (PS-2) 0.02 Surfactant (SU-3) 0.023 Hardener (H-6) 36 Second layer gelatin 2.4 Water-soluble polymer (PS-3) 0.36 Water-soluble polymer (PS-1) 0.7 Water-soluble polymer (PS-4) 0.6 High boiling solvent (OIL-3) 2 0.0 Guanidine picolinate 2.4 Potassium hydantoin 0.16 Potassium quinophosphate 0.225 Sodium quinophosphate 0.18 Surfactant (SU-3) 0.024 Third layer Gelatin 2.4 Water-soluble polymer (PS-1) ) 0.7 Water-soluble polymer (PS-3) 0.36 Water-soluble polymer (PS-4) 0.6 Guanidine picolinate 2.15 Surfactant (SU-3) 0.024 Fourth layer Gelatin 0.22 water Water-soluble polymer (PS-3) 0.26 Potassium nitrate 0.012 Antifoggant (AF-7) 0.02 Matting agent (PM-22) 0.01 Surfactant ( SU-3) 0.007 Surfactant (SU-5) 0.007 Surfactant (SU-6) 0.01 Hardener (H-6) 0.37

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Evaluation was performed in the same manner as in Example 1. However, development was performed using the above-mentioned processing sheet. That is, for the photographed film, hot water of 40 ° C. was uniformly applied to the emulsion surface of the photosensitive material at a rate of 15 ml / m ² , and the treated sheet was superimposed on each coating surface. Thermal development was performed at 40 ° C. for 40 seconds.

The sample thus developed was cooled to about 30 ° C. in about 15 seconds, and immediately thereafter, a BGR-decomposed image was read using the same image reading apparatus used in Example 1, and this was read. Evaluation was performed in the same manner as in Example 1.

Table 5 also shows the results of Samples 102 and 103 of Example 1.

[0267]

[Table 5]

As is clear from Table 5, digital image information obtained from a photosensitive material using the filter of the present invention has excellent image quality. Of the comparative samples, those with a small filter pitch had many scenes in which moire occurred, and color reproduction was insufficient. Further, even if the filter pitch was large, those having a large p / d caused color turbidity and the image quality was insufficient, but the image obtained from the sample of the present invention had little color turbidity.

Example 3 A color stripe filter having a different filter pitch was prepared in the same procedure as in Example 1, and the silver halide emulsion 2 used for preparing the sample of Example 1 was changed to a silver halide emulsion 3. The same photosensitive layer as in Example 1 was coated on color stripe filters having different filter pitches. Using this sample, the development time was changed to change the size of the color dye cloud c.
(Μm) was changed, and samples 301 to 313 were produced.
In the same way as above, the relationship with the image quality was observed. This is shown in Table 6.

[0270]

[Table 6]

As can be seen from Table 6, good image quality can be obtained when the filter pitch is 9 μ or more and the p / c value is 5 or more. In many cases, the image quality was different depending on the point of color reproduction. This is because, in the case of Example 2, the color reproducibility is reduced due to the presence of grains across the filter pitch when the silver halide is exposed, whereas in the case of the present embodiment, even when the silver halide does not straddle the filter, It is thought that the reason is that if the coloring pigment generated later is large, the coloring step is performed over the filter pitch, and the color reproduction is reduced.

Example 4 Using the photosensitive material used to prepare the samples 304, 311 and 313 of Example 3, the magnification of the optical system for reading was changed, and the area of the film read by the CCD was changed. The samples 401 to 408 were prepared by changing the reading resolution r (expressed in μm) and reading was performed. The evaluation was performed in the same manner as in Example 1, except that the evaluation was performed only for color reproduction, and the average of 10 persons was averaged. As can be seen from Table 7, it was found that color reproduction was excellent when the value of p / r was 2.5 or more.

[0273]

[Table 7]

[0274]

According to the present invention, the filter of the present invention is applied to a monochrome photosensitive material having a simple structure which can be produced at a lower cost than a photosensitive material for general color photography, and a high quality digital image with less color turbidity is obtained. Data can be obtained. The digitized image data has excellent image quality even when output as a color hard copy (color print) again.

Claims (9)

[Claims] 1. An image forming method for photographing a photosensitive material through a color microfilter having a filter pitch p of 9 μm or more, wherein the filter pitch p (μm) of the color microfilter and the photographing area s (μm) of the photosensitive material
m ² ), wherein s / p ² ≧ 60,000. 2. The image forming method according to claim 1, wherein the photosensitive material is a silver halide photosensitive material. 3. An image forming method for photographing a silver halide photosensitive material through a color microfilter having a filter pitch p of 9 μm or more, wherein a filter pitch p (μm) of the color microfilter and a silver halide photosensitive material are used. An image forming method characterized by having a relationship of p / d ≧ 5 with the average grain size d (μm) of silver halide grains contained in the photosensitive layer having the largest average grain size of silver halide. . 4. An image forming method for photographing a silver halide photosensitive material through a color microfilter having a filter pitch p of 9 μm or more, wherein the filter pitch p (μm) of the color microfilter and the silver halide photosensitive material The average particle size c of the dye cloud in the photosensitive layer having the largest average particle size of the color dye dye cloud formed after the color development of
(Μm) and a filter pitch, wherein p / c ≧ 5. 5. An image forming method for photographing a silver halide photosensitive material through a color micro filter having a filter pitch p of 9 μm or more, wherein a filter pitch p (μm) of the color micro filter and image information after image formation. And a resolution r (μm) for reading the image by a scanner, wherein p / r ≧ 2.5. 6. A color microfilter used in the image forming method according to claim 1. 7. A silver halide light-sensitive material comprising a color microfilter and at least one silver halide light-sensitive layer, wherein the silver halide light-sensitive layer is exposed to light through the color microfilter to perform photographing. Halogenation, wherein the filter pitch of the color microfilter is 9 μm or more, and the relationship between the filter pitch p (μm) and the exposure area s (μm ² ) is s / p ² ≧ 60,000. Silver photosensitive material. 8. A silver halide light-sensitive material comprising a color microfilter and at least one silver halide light-sensitive layer, wherein the silver halide light-sensitive layer is exposed to light through the color microfilter to take a picture. The filter pitch of the color microfilter is 9 μm or more, the filter pitch p (μm) and the average particle size d (μm) of silver halide particles contained in the photosensitive layer having the largest average particle size of silver halide. Has a relationship of p / d ≧ 5. 9. A silver halide light-sensitive material comprising a color microfilter and at least one silver halide light-sensitive layer, wherein the silver halide light-sensitive layer is exposed to light through the color microfilter to perform photographing. The filter pitch of the color microfilter is 9 μm or more, and the filter pitch p (μm) and the dye cloud in the photosensitive layer in which the average particle diameter of the dye cloud of the coloring dye formed after color development of the silver halide photosensitive material are the largest. Average particle size c (μ
A silver halide light-sensitive material having a relationship of p / c ≧ 5 between m) and a filter pitch.