JPH10333311A - Liquid supply type thermal developing device and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent color image on a photographic material by performing an easy and simple thermal developing processing by a compact thermal developing device. SOLUTION: The device is provided with a container part 12 for packing developer, and a developer supply part (slit opening part) 16A to which the developer stored in the developer container part 12 is supplied. The developer is carried through a liquid junction 14 by a pump 18, then, the developer is heated up to the prescribed extent of 60 deg.C-100 deg.C by a heater 14A, then, reaches the slit opening part 16A so as to be applied on the photosensitive material 20. The photosensitive material 20 is provided with a photosensitive layer containing at least planar photosensitive particles of silver halide, color developing main chemical, coupler and binder on a transparent supporting body, and after the photosensitive material is exposed, the material is heated at 60 deg.C-100 deg.C for 5-60 sec so as to form an image of non-diffusion coloring matter on the photosensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a liquid supply type heat development apparatus and a method for forming an image using the liquid supply type heat development apparatus.

[0002]

BACKGROUND OF THE INVENTION In a process known as conventional color photography, so-called color negatives are usually
It includes a layer that records yellow light to form a yellow dye image, a layer that records green light to form a magenta dye image, and a layer that records red light to form a cyan dye image. The developer is oxidized in the process of reducing silver halide grains containing an image to silver, and a dye image is formed by a reaction (coupling) between the oxidized product and a coupler. Undeveloped silver halide and developed silver are removed in the subsequent desilvering steps (bleaching, fixing, bleach-fixing), and the color paper is exposed through the obtained negative dye image, followed by the same developing, bleaching and fixing steps. To obtain a color print.

Further, there is also known a method of photoelectrically reading image information contained in the above-mentioned color negative, performing image processing to obtain image information for recording, and obtaining a color image on another print material by using this image information. Have been. In particular, development of digital photo printers, in which the above-mentioned image information is converted into digital signals, and a photosensitive material such as color paper is scanned and exposed by a recording light modulated in accordance with the digital signals to produce a finished print, an example of which is disclosed in No. 15593. The above methods are used for normal wet development, bleaching,
It is premised on establishment, and the process is complicated.

On the other hand, as a method for processing a photosensitive material using silver halide, a simple and quick method using heat development has been developed. Examples of such products include a product such as a pictrograph and a pictrostat manufactured by Fuji Photo Film Co., Ltd. However, these are color print materials, and no known photosensitive materials for photography by thermal development have been known.

As a form of heat development, a method of performing heat development in the presence of a small amount of water and a base and / or a base precursor is known. For example, Japanese Patent Publication No. 2-51494 discloses such an example. ing. However, the image forming method described therein uses a dye-providing substance that is reducible to photosensitive silver halide and reacts with the photosensitive silver halide by heating to release a hydrophilic dye. The dye released during heat development is transferred to an image receiving material, and the transfer side is used as a color print.

The inventors of the present invention have disclosed a method for producing a photosensitive material which comprises at least a tabular photosensitive silver halide particle, a color developing agent, a coupler and a binder on a transparent support, a photosensitive wavelength region, and a dye formed from the color developing agent and the coupler. A photosensitive material having at least three types of photosensitive layers having different absorption wavelength ranges from each other, wherein after imagewise exposure of the photosensitive material, the photosensitive material is heated and developed in the presence of a base and / or a base precursor to form at least 3 photosensitive layers. A silver halide color photographic light-sensitive material (hereinafter, referred to as a dry color negative light-sensitive material) for forming a color image based on a color non-diffusible dye has been proposed. This dry color negative photosensitive material has an excellent feature that a high-quality image can be obtained much more easily and quickly than conventional photosensitive materials in conventional photography.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid supply type heat developing apparatus capable of performing heat development by a compact apparatus using a photosensitive material for photography by simple thermal development processing, and a liquid supply type heat developing apparatus. An object of the present invention is to provide an image forming method that can easily perform a process including thermal development using a mold heat developing apparatus.

[0008]

The above object is achieved by the present invention described below. That is, the present invention provides: (1) a processing liquid container section for filling a processing liquid, and a photosensitive material for bringing the processing liquid into contact with the photosensitive material in the vicinity of the processing liquid supply section to which the processing liquid in the processing liquid container section is supplied. A liquid comprising: a contact portion; a liquid junction for communicating the photosensitive material contact portion with the processing liquid container; and a heating means for heating the processing liquid in the vicinity of the processing liquid supply portion. Supply type thermal developing device. (2) The liquid supply type heat developing apparatus according to (1), wherein the processing liquid container section and the liquid junction section are detachably connected to each other. (3) The liquid supply type thermal developing apparatus according to (1), further comprising a mechanism for adjusting a supply amount of the processing liquid in the processing liquid container to the processing liquid supply unit. (4) The liquid supply type thermal developing apparatus according to (1), wherein the processing liquid supply section comprises a slit-shaped opening. (5) The liquid supply type thermal developing apparatus according to (1), further comprising a liquid evaporation preventing means between the processing liquid container section and the processing liquid supply section. (6) The liquid supply type thermal developing apparatus according to (1), wherein the heating means is formed of a metal conductive block. (7) The solution according to any one of (1) to (6), after exposing a photosensitive material having a photosensitive layer containing at least tabular photosensitive silver halide grains, a color developing agent, a coupler and a binder on a transparent support. Image forming characterized in that a processing liquid is supplied by using a supply type thermal developing device and heated at a temperature of 60 ° C to 100 ° C for 5 seconds to 60 seconds to form an image based on a non-diffusible dye on a photosensitive material. Method. (8) The image forming method according to (7), wherein a color image is obtained on another recording material based on the image information of the image obtained in (7). (9) The image forming method according to (7), wherein the width of the long side of the slit-shaped opening of the developer supply section in the liquid supply type thermal developing device is smaller than the width of the long photosensitive material. . (10) The image forming method according to (8), wherein after the color image is obtained, desilvering, stabilizing, and drying are performed. (11) A processed photosensitive material in which a photosensitive material having a color image obtained by the method of 10) is housed in a cartridge having a door which can be opened and closed at a film insertion opening.

[0009]

FIG. 1 is a schematic front view showing a preferred embodiment of a liquid supply type thermal developing apparatus according to the present invention.
FIG. 2 is a schematic perspective view of a main part in FIG. The liquid supply type thermal developing device 10 includes a container 12 filled with a developing solution.
, A liquid junction portion 14 and a photosensitive material contact portion 16. The container 12 and the photosensitive material contact portion 16 are connected by a liquid junction portion 14. The liquid junction portion 14 is formed of a metal or the like having good heat conductivity.
Are arranged. As the pump 18, for example,
It is possible to use a bimorph pump capable of supplying a very small amount (for example, about 0.1 cc / sec) of the developing solution to the photosensitive material contact portion 16 by vibrating the piezoelectric element or the like, or a tubular pump using a thin rubber tube. .

As shown in FIG. 2, the liquid junction portion 18 gradually increases in width from the vicinity of the pump 18 to the photosensitive material contact portion 16 side, and is formed of a flow path having a uniform width in the middle thereof. A heater 14A is installed on the outer surface of the flow path, and can be energized by an energizing means (not shown). The photosensitive material contact portion 16 is formed in an arc shape and is made of a metal having good heat conductivity, and has a slit-like opening 16A as a liquid supply portion communicating with the liquid junction portion 14 on its outer surface. I have. In the slit-shaped opening 16A, the width (L ₁ ) on the long side is smaller than the width (L ₂ ) of the photosensitive material 20 indicated by a two-dot chain line. That is, since both ends in the width direction of the photosensitive material 20 are areas where no image is formed, the developing solution from the slit-shaped opening 16A is applied to a part except for these areas.

The width (T ₁ ) of the short side of the slit-shaped opening 16A is 0.1 to 5 mm, preferably 0.2 to 5 mm.
3 mm. It is desirable that the width (T ₁ ) on the short side of the slit-shaped opening 16A is wide when the conveying speed of the photosensitive material is high, and narrow when the conveying speed of the photosensitive material is low. However, if T ₁ is too large, the processing solution to be supplied protrudes from the photosensitive material, and
_{When 1} is too narrow, supply of the processing liquid becomes substantially difficult.

Three guide rolls 22A, 22B and 22C are disposed on the front side of the photosensitive material contact portion 16, and a pressing cloth 24 is stretched between these guide rolls. A heater 16A and a heater 16B are provided on the surface side of the section 16, and can be energized by an energizing means (not shown).

In the liquid supply type heat developing apparatus, the photosensitive material 20 includes, for example, at least a tabular photosensitive silver halide particle, a color developing agent, a coupler and a binder on a transparent support, and has a photosensitive wavelength range and A light-sensitive material having at least three kinds of light-sensitive layers having different absorption wavelength regions of a dye formed from the color developing agent and the coupler is used. This photosensitive material 20 is a photosensitive material contact portion 1
The heater 16B is conveyed along the surface of the photosensitive material contact portion 16 by the rotation of the guide rolls 22A, 22B, and 22C in a state where the heater 16B is held between the presser cloth 6 and the pressing cloth 24.
To about 60 to 100 ° C.

At this time, as the developer in the container 12, for example, a developer consisting of water containing a base and / or a base precursor is used. The developing solution is supplied from the container 12 through the liquid junction 14 via the pump 18 to a pressure of 60 to 10
It is heated to about 0 ° C. and reaches 16 at the photosensitive material contact portion. The developing solution is about 5 to 30 ml /
After the supply of m ² , the photosensitive material 20 is heated by the heater 16B.
At about 60 to 100 ° C. for 5 to 60 seconds.

Thus, an image based on the three non-diffusible dyes is formed on the photosensitive material 20. Thereafter, before the photosensitive material 20 cools, the photosensitive material 20 can be desilvered, stabilized, and dried to obtain a desired image.

In the above-described embodiment, an example in which the pump 16 is used to supply the developer to the photosensitive material contact portion 16 has been described. However, the container 12 is replaced by a flexible container instead of the pump 16, and The developer may be supplied to the photosensitive material contact section 16 by applying an external pressure, or the developer may be supplied to the photosensitive material contact section 16 from the container 12 by surface tension. Therefore, the liquid supply type thermal developing device can be used not only in the embodiment shown in FIG. 1 but also in an inverted state of the configuration in FIG. 1, and can be used in a state where it is arranged in a horizontal direction or inclined at a predetermined angle. It can also be used in the state where it was done.

Next, the container 12 is of a cartridge type, and the container 12 and the liquid junction 14 can be detachably mounted as shown in FIG. That is, in FIG. 3, a cap 32 as a lid is attached to the neck portion 30 of the container 12. On the outer peripheral portion of the neck portion 30, a male screw 36 is formed on the tip side from the flange 34, and this male screw 3 is formed.
The female screw 38 of the cap 32 is screwed into 6.

At the center of the cap 32, a conical through hole 40 whose diameter decreases from the outside to the inside is formed coaxially. The inside diameter of the minimum diameter portion of the through hole 40 is substantially the same as the inside diameter of the mouth of the neck portion 30.

Between the distal end of the neck portion 30 and the bottom portion 32A inside the cap 32, a circular closing member 42 is sandwiched near its outer periphery, whereby the mouth of the neck portion 30 is closed. The closing member 42 is formed of a flexible (synthetic resin, rubber, or the like) sheet having excellent chemical resistance. In the present embodiment, a foamed vinyl chloride resin sheet punched out in a circular shape is used. .

On the other hand, on the bottom of the liquid junction 14, an opening projection 44 as an opening means is provided upright at a position eccentric downward from the center by a predetermined amount. The opening protrusion 44 has a cross shape perpendicular to the axis and has a tapered tip.

When such a cartridge type container 12 is used, the container 12 filled with the developing solution is pushed up to the side of the opening projection 44 provided at the bottom of the liquid junction 14 so that the opening projection 44 is located above the closing member 42. When the closing member 42 is opened by pushing the inside of the container 12, the liquid junction 14 communicates with the inside of the container 12,
The developer in the container 12 is supplied to the liquid junction 14 through the opening protrusion 44.
Can be supplied to

Here, the maximum diameter of the opening projection 44, the contact range of the tip of the opening projection 44, the effective opening diameter (the maximum diameter of the through hole 40), the eccentric amount for making the opening constant, and the opening direction are made constant. FIG. 4 shows the relationship between the eccentricity margins for
When the tip of the opening projection 44 is pressed into the contact area of the tip of the opening projection, the closing member 42 can always be opened from the same direction. The minimum diameter portion and the maximum diameter portion of the through hole 40 are not necessarily required to be coaxial, and the minimum diameter portion of the through hole 40 may be deviated downward. As a result, the tip of the opening projection 44 is moved to the position shown in FIG.
Can be reliably led to the contact area of the opening protrusion tip shown in FIG.

Next, in the above-described embodiment, a heater is merely exemplified as the heating means in the liquid junction 14 and the photosensitive material contact portion 16, but the liquid junction 14 and the photosensitive material contact portion 16, especially the liquid junction 14 Although not particularly shown, for example, a cast-type metal heat conduction block can be adopted as the heating means in (1).

The cast-type metal heat-conducting block is cast in a state that it contains both a flow pipe (liquid junction 14) of a developer and a heat source, and transfers heat from the heat source to the liquid junction 14. Such a cast metal heat conducting block is described in JP-A-5-80479.

When this cast-type metal heat conducting block is employed, the metal heat conducting block is heated by the heat source. The heat held by the heat guide block is transmitted to the flow pipe (liquid junction 14) of the developer penetrating the heat guide block.
Therefore, the developer flowing through the flow pipe (liquid junction 14) is heated to a predetermined temperature by the heat held by the heat guide block. Since the heat guide block is made of metal, it has a large heat capacity and does not need to have a high surface temperature as in a normal heater, and can heat the developer to a predetermined temperature at a relatively low temperature, so that the developer is partially heated. The liquid does not deteriorate due to high temperature. Further, since the entire amount of the developer flowing in the heat guide block is heated by the heat guide block, the photosensitive material contact portion 16 is heated.
The temperature distribution of the developing solution supplied to the device is likely to be uniform, and stable temperature adjustment is possible. The temperature may be controlled by installing a temperature sensor at the photosensitive material contact portion or the liquid junction.

FIG. 5 is a schematic front view showing another preferred embodiment of the liquid supply type thermal developing apparatus of the present invention. The liquid supply type heat developing apparatus differs from the apparatus shown in FIG. 1 in that a buffer section 46 having an enlarged liquid flow path is provided in the middle of the liquid junction section 14, and the other components are Since they are substantially the same as those shown in FIG. 1, they are denoted by the same reference numerals.

The developer filled in the container 12 is supplied to the pump 16
When the developer filled in the flexible container is supplied to the liquid junction 14 due to a change in external pressure with respect to the container, for example, when the developer is supplied to the liquid junction 14, the developer in the liquid junction 14 May occur. When this pulsating flow occurs, the supply amount of the developing solution applied to the photosensitive material 20 changes, and it becomes difficult to form a desired image. But,
By interposing the buffer section 46 in the liquid junction section 14, the pulsating flow is eliminated in the buffer section 46, and the developer can be uniformly supplied to the photosensitive material 20.

Next, when the processing of the photosensitive material 20 is temporarily interrupted, the developing solution in the liquid junction 14 volatilizes, and the composition of the developing solution may change. In such a case, the liquid junction 1
It is necessary to prevent the developer in 4 from volatilizing. In FIG. 6, a recess 14 </ b> B is formed in the middle of the liquid junction 14 along the long side (in the vertical direction in the drawing) of one wall of the liquid junction 14, and the length of the other wall of the liquid junction 14 is long. A plate-like sliding member 48 slidable along the side (vertical direction in the drawing) in the direction indicated by the arrow in the drawing is provided, and the flow path of the liquid junction 14 is opened during the development processing. During the development process,
The sliding member 48 moves to the left in the drawing, and its tip fits into the concave portion 14B to close the flow path. The sliding member 48 normally closes the flow path, detects the start of the developing process in which the photosensitive material 20 is conveyed to the photosensitive material contact portion 16 by a sensor, and controls the sliding member 48 based on the detection signal. When activated, the flow path can be opened.

Further, in order to prevent the developer in the liquid junction 14 from volatilizing, the spherical body 5 is placed in the buffer 46 shown in FIG.
Zeros may be filled. If the spherical body 50 is made of a material whose specific gravity is slightly larger than that of the developing solution and whose diameter is slightly larger than the width of the flow path communicating with the buffer 46, the pump 18 can be used.
When the developer is supplied to the buffer 46 from the
Is suspended in the buffer 46 by the liquid flow and does not hinder the supply of the developer. When the supply of the developer from the pump 18 is stopped, the spherical body 50 sinks to the bottom of the buffer 46 and closes the flow path. I do. Therefore, when the supply of the developing solution from the pump 18 is stopped, the flow path is closed, so that the volatilization of the developing solution is prevented.

FIG. 7 is a schematic diagram showing a preferred embodiment of a photosensitive material processing apparatus using the liquid supply type heat developing apparatus of the present invention. In FIG. 7, a liquid supply type thermal developing device 52 and a liquid supply type desilvering device 54 are provided side by side.
Although not shown in FIG. 7, a liquid supply-type stabilization device composed of a device similar to these devices may be provided in parallel, and the stabilization device can be processed by a separate device.

In the liquid supply type thermal developing apparatus 52, the liquid supply type desilvering processing apparatus 54, and the liquid supply type stabilization processing apparatus, each configuration on the apparatus can adopt any of the above-described embodiments. . However, in the photosensitive material processing apparatus shown in FIG. 7, since the photosensitive material 20 is conveyed in a straight line, the photosensitive material contacting portion 56 in the liquid supply type thermal developing device 52 and the liquid supply type desilvering processing device 54, Material contact part 58
Are not formed in an arc shape, but are formed in a plane shape.

In this photosensitive material processing apparatus, the container 12 of the liquid supply type thermal developing apparatus 52 is filled with a developing solution, and the container 12 of the liquid supply type desilvering apparatus 54 is bleached or fixed or bleached. -A processing solution for fixing is filled. The guide roll on the upper surface of the photosensitive material 20 and the pressing cloth stretched on the guide roll are not shown. In this photosensitive material processing apparatus, a compact apparatus can easily perform the heat development processing and the desilvering processing.

FIG. 8 is a schematic diagram showing another preferred embodiment of a photosensitive material processing apparatus using the liquid supply type heat developing apparatus of the present invention. In FIG. 8, a liquid supply type thermal developing device 64, a liquid supply type desilvering device 66, and a liquid supply type stabilization device 68 are arranged on the outer peripheral surface of the heater drum 56 at predetermined intervals. Each component on these devices can adopt any of the above-described embodiments. However, in this photosensitive material processing apparatus, the photosensitive material contact portions 5 of the liquid supply type thermal developing device 64, the liquid supply type desilvering processing device 66, and the liquid supply type stabilization processing device 68
The arc-shaped concave portions are formed so that 8, 60 and 62 substantially correspond to the curvature of the heater drum 56.

The container 12 of the liquid supply type thermal developing device 64 is filled with a developing solution, and the liquid supply type desilvering device 66 is filled with a developing solution.
A processing solution for bleaching or fixing or bleaching / fixing is filled, and the liquid supply type stabilizing device 68 is filled with a stabilizing processing solution. In this photosensitive material processing apparatus, the respective photosensitive material contact portions of a liquid supply type thermal developing device 64, a liquid supply type desilvering device 66, and a liquid supply type stabilization processing device 68 disposed on the outer periphery of the heater drum 56. 58, 6
0, 62 while contacting the photosensitive material 20 with the photosensitive material 2.
Since 0 can be processed, the photosensitive material 20 can be easily processed by an apparatus having a compact configuration.

The image forming method of the present invention comprises the steps of: exposing a photosensitive material having a photosensitive layer containing at least tabular photosensitive silver halide grains, a color developing agent, a coupler and a binder on a transparent support; A processing liquid is supplied using a liquid supply type heat developing apparatus, and heated at a temperature of 60 ° C. to 100 ° C. for 5 to 60 seconds to form an image based on a non-diffusible dye on the photosensitive member.

In the image forming method of the present invention, a photosensitive member containing a color developing agent and a coupler having extremely high stability especially in the absence of a base, and a small amount of water containing a base and / or a base precursor are used. When an image based on a non-diffusible dye is formed on a photosensitive member by heating and developing, an image with excellent granularity and sharpness is obtained. Based on this image information, another recording such as a color paper or a heat-developed color print material is performed. It is based on the discovery that very good color images are obtained when output on materials. In addition, since the photosensitive material and the base are isolated until the development, rapid development processing can be performed while satisfying the high storage stability required for the photographic material.

When a colorless color developing agent and a coupler are used, the sensitivity is extremely important as a photographic material, as compared with the case where a dye releasing compound is used. In addition, when non-tabular silver halide grains such as cubic crystals are used, the sensitivity is low and the granularity is not good. However, by using the tabular grains and the developing method of the present invention using basic water, the basic water can be used. As a result of the limited supply, both granularity and high sensitivity can be achieved.

In the image forming method of the present invention, after forming a color image by thermal development, the remaining silver halide and / or developed silver may or may not be removed.
In addition, as a method of outputting to another material based on the image information, normal projection exposure may be used, or image information may be photoelectrically read by measuring the density of transmitted light, and output using the signal. The material to be output need not be a photosensitive material, and may be, for example, a sublimation type thermosensitive recording material, an inkjet material, an electrophotographic material, a full-color direct thermosensitive recording material, or the like.

In a preferred embodiment of the present invention, after a color image is formed by thermal development, the image information is diffused by a diffused light and a CCD image sensor without additional processing for removing the remaining silver halide and developed silver. After reading photoelectrically by the transmission density measurement used and converting it to a digital signal,
The image processing is performed, and the image is output by a heat development color printer, for example, a Pictography 3000 manufactured by Fuji Photo Film Co., Ltd. In this case, a good print can be obtained quickly without using any processing solution used in conventional color photography. Also, in this case,
Since the digital signal can be arbitrarily processed and edited, the photographed image can be freely modified, deformed, processed and output.

The photosensitive silver halide which can be used in the present invention includes silver iodobromide, silver bromide, silver chlorobromide, silver iodochloride, silver chloride,
Any of silver iodochlorobromide may be used. The size of the silver halide grains is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm, in terms of the diameter of a sphere having the same volume.

As the silver halide grains used in the present invention, those having a hexagonal or rectangular tabular shape can be used. Among them, tabular grains having an aspect ratio of 2 or more, preferably 8 or more, more preferably 20 or more are used. Particles are preferred,
It is preferable to use an emulsion occupying 50% or more, preferably 80% or more, and more preferably 90% or more of the projected area of all the grains in such tabular grains.

Further, US Pat. No. 5,494,789,
Nos. 5,503,970, 5,503,971, 5,536,632 and the like.
Particles thinner than 07 μm and having a higher aspect ratio can also be preferably used. Also, U.S. Pat.
Nos. 0, 463, 4, 713, 323, 5, 21
No. 7,858, and the like, high silver chloride tabular grains having a (111) plane as a main plane, and US Pat.
Nos. 64, 337, 5, 292, 632, 5, 31
High silver chloride tabular grains having a (100) plane as a main plane described in JP-A No. 0,635 or the like can also be preferably used.

Examples of actually using these silver halide grains are disclosed in Japanese Patent Application Nos. 8-46822 and 8-97344.
No. 8-238672. In the present invention, the emulsion is usually preferably subjected to chemical sensitization and spectral sensitization.

As the chemical sensitization, a chalcogen sensitization method using a sulfur, selenium or tellurium compound, a noble metal sensitization method using gold, platinum, iridium or the like, or a compound having an appropriate reducing property during grain formation is used. Thus, a so-called reduction sensitization method for obtaining high sensitivity by introducing a reducing silver nucleus can be used alone or in various combinations.

As the spectral sensitization, cyanine dyes, merocyanine dyes, composite cyanine dyes, composite merocyanine dyes, holopolar dyes, hemicyanine dyes, which are adsorbed on silver halide grains and have sensitivity in the absorption wavelength range of the silver halide grains, are provided. A so-called spectral sensitizing dye such as a styryl dye or a hemioxonol dye is used alone or in combination, and is preferably used together with a supersensitizer.

The silver halide emulsion used in the present invention contains azaindenes, triazoles, tetrazoles, and the like for the purpose of preventing fog and increasing the stability during storage.
It is preferable to add various stabilizers such as nitrogen-containing heterocyclic compounds such as purines, mercaptotetrazoles, mercaptotriazoles, mercaptoimidazoles, and mercapto compounds such as mercaptothiadiazoles.

Photographic additives for silver halide emulsions are described in Research Disclosure Magazine (hereinafter abbreviated as “RD”) No. 17643 (December 1978), No. 1
No. 8716 (November 1979), No. 307105
No. (November 1989) and No. 38957 (199
(September 2006) can be preferably used. The photosensitive silver halide is 0.05 in terms of silver.
It is preferable to use 用 い る 20 g / m ² , more preferably 0.1 to 10 g / m ² .

The binder is preferably hydrophilic, and examples thereof include RD described in the preceding section and JP-A-64-1.
No. 3,546, pp. 71-75. Among them, gelatin and a combination of gelatin with another water-soluble binder such as polyvinyl alcohol, modified polyvinyl alcohol, cellulose derivative, acrylamide polymer and the like are preferable. The coating amount of the binder is preferably from 1 to 20 g / m ^2, more preferably 2 to 15 g / m ^2, yet more preferably 3~12g / m ^2. Among them, 50% to 100% as gelatin
%, Preferably 70% to 100%.

As the color developing agent, p-phenylenediamines or p-aminophenols may be used, but compounds represented by the following general formulas (1) to (5) are preferably used.

[0050]

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The compound represented by the general formula (1) is a compound generally called sulfonamidophenol. Where R
_{1 to} R ₄ are each 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, a t-butyl group),
Aryl groups (eg, phenyl, tolyl, xylyl), alkylcarbonamide groups (eg, acetylamino, propionylamino, butyroylamino),
Arylcarbonamide group (eg, benzoylamino group), alkylsulfonamide group (eg, methanesulfonylamino group, ethanesulfonylamino group), arylsulfonamide group (eg, benzenesulfonylamino group, toluenesulfonylamino group), alkoxy group (eg, methoxy Group, ethoxy group, butoxy group), aryloxy group (eg, phenoxy 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), arylcarbamoy Group (e.g., phenylcarbamoyl group, a methyl phenylcarbamoyl group, an ethyl phenylcarbamoyl group, a benzyl phenylcarbamoyl group), a carbamoyl group,

Alkylsulfamoyl groups (for example, methylsulfamoyl, dimethylsulfamoyl, ethylsulfamoyl, diethylsulfamoyl, dibutylsulfamoyl, piperidylsulfamoyl, morpholylsulfamoyl) Moyl 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), Alkoxycarbonyl 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, an alkylbenzoyl group) or an acyloxy group (eg, an acetyloxy group, a propionyloxy group, a butyroyloxy group). R _{1 to} R
_{In 4} , R ₂ and R ₄ are preferably a hydrogen atom. The sum of the Hammett constant σp values of R _{1 to} R ₄ is 0.
It is preferable that the above is satisfied.

R ₅ is an alkyl group (for example, methyl, ethyl, butyl, octyl, lauryl, cetyl,
A stearyl group), an aryl group (for example, 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).

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, R ₅ is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group, 4-methoxyphenyl group, dodecylphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, nitrochlorophenyl group, triisopropylphenyl group, 4-dodecyloxyphenyl group, 3,5-di (methoxy) carbonyl group), or Represents a ring group (for example, a pyridyl group).
Z represents an atomic group forming an aromatic ring. The aromatic ring formed by Z imparts silver developing activity to the present compound.
It must be sufficiently electron-attracting. 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 quinoxaline ring and the like are preferred.

When Z represents a benzene ring, examples of the substituent include an alkylsulfonyl group (for example, a methanesulfonyl group and an ethanesulfonyl group), a halogen atom (for example, a chloro group and a bromo group), and an alkylcarbamoyl group (for example, a 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 group, dimethylsulfamoyl group, ethylsulfamoyl group, diethylsulfamoyl group, Butylsulfamoyl group, piperidyl sulfamoyl group, morpholinocarbonyl Rusuru sulfamoyl group),
Arylsulfamoyl group (for example, phenylsulfamoyl group, methylphenylsulfamoyl group, ethylphenylsulfamoyl group, benzylphenylsulfamoyl group), sulfamoyl group,

A cyano group, an alkylsulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group), an arylsulfonyl group (eg, phenylsulfonyl group, 4-chlorophenylsulfonyl group, p-toluenesulfonyl group), an alkoxycarbonyl group (eg, methoxycarbonyl group) , An ethoxycarbonyl group, a butoxycarbonyl group), an aryloxycarbonyl group (eg, a phenoxycarbonyl group), an alkylcarbonyl group (eg, an acetyl group, a propionyl group, a butyroyl group), or an arylcarbonyl group (eg, a benzoyl group, an alkylbenzoyl group) Wherein the sum of Hammett constant σ values of the substituents is 1 or more.

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 ₅ is an alkyl group (for example, methyl group, ethyl group, butyl group, octyl group, lauryl group, cetyl group, stearyl group), an aryl group (for example, phenyl group, tolyl group, xylyl group, 4-methoxyphenyl group, dodecylphenyl group, chlorophenyl group, dichlorophenyl group, trichlorophenyl group, nitrochlorophenyl group, triisopropylphenyl group, 4-dodecyloxyphenyl group, 3,5-di (methoxy) carbonyl group), or Represents a ring group (for example, a pyridyl group).
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 and R ₈ represent a hydrogen atom or a substituent,
R ₇ and R ₈ 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 present invention is of course not limited thereto.

[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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As the color developing agent, one or a combination of a plurality of the above compounds is used. Separate developing agents may be used for each layer. The total amount of these developing agents used is 0.05 to 20 mmol / m ² , preferably 0.1 to 1 mmol / m ² .
0 mmol / m ² . As the photosensitive material, a coupler that forms a dye by coupling reaction with an oxidized form of the color developing agent is used. Preferred examples thereof include active methylene, 5-pyrazolone, pyrazoloazole, phenol,
Compounds generally referred to as naphthol and pyrrolotriazole are included. The specific example is RDNo. 38957 (1
Those cited on pages 616 to 624 (September 996) can be preferably used. Particularly preferred examples include pyrazoloazole couplers described in JP-A-8-110608 and JP-A-8-12299.
4, pyrrolotriazole couplers described in Japanese Patent Application No. 8-45564. These couplers are preferably 0.05 to 10 mmol / m ^{2 for} each color,
More preferably, 0.1 to 5 mmol / m ^{2 is} used.

Further, colored couplers for correcting unnecessary absorption of color-forming dyes, residues of photographically useful compounds by reacting with oxidized developing agents, for example, compounds (including couplers) which release development inhibitors, etc. Can also be used.

The light-sensitive material is usually composed of three or more kinds of light-sensitive layers having different color sensitivity. Each photosensitive layer has at least one
Including a silver halide emulsion layer, a typical example comprises a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is blue light,
A single light-sensitive layer having color sensitivity to either green light or red light. In a multilayer silver halide color photographic light-sensitive material, generally, the arrangement of the single light-sensitive layer is such that the red light-sensitive layer is arranged in order from the support side. The color-sensitive layer, the green color-sensitive layer, and the blue color-sensitive layer are provided in this order. However, even if the above installation order is reversed according to the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. The total thickness of the photosensitive layer is from 1 to 20.
μm is preferred, and more preferably 3 to 15 μm.

The silver halide, the color developing agent and the coupler may be contained in the same photosensitive layer or in different layers. In addition to the photosensitive layer, a non-photosensitive layer such as a protective layer, an undercoat layer, an intermediate layer, a yellow filter layer, and an antihalation layer may be provided, and a back layer may be provided on the back side of the support. The thickness of the entire coating film on the photosensitive layer side is preferably from 3 to 25 μm, more preferably from 5 to 20 μm.

Photosensitive materials include hardeners, surfactants, photographic stabilizers, antistatic agents, slip agents, matting agents for various purposes.
Latex, formalin scavenger, dye, UV absorber and the like can be used. Specific examples of these are described in the aforementioned RD and Japanese Patent Application No. 8-30103. Examples of particularly preferred antistatic agents include ZnO, T
iO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO,
Metal oxide fine particles such as BaO, MoO ₃ and V ₂ O ₅ .

As the support of the light-sensitive material, a photographic support described in "Basics of Photographic Engineering-Silver halide photography", edited by The Photographic Society of Japan, Corona Co., Ltd. (1979), pages 223 to 240, is preferred. Specific examples include polyethylene terephthalate, polyethylene naphthalate, polycarbonate, syndiotactic polystyrene, and celluloses (for example, triacetyl cellulose). Among these, a polyester containing polyethylene naphthalate as a main component is particularly preferable, but the polyester referred to herein as “polyethylene naphthalate as a main component” refers to a content of naphthalenedicarboxylic acid contained in all dicarboxylic acid residues. Means 50 mol% or more, more preferably 60 mol% or more, and still more preferably 70 mol% or more.
% Or more. It may be a copolymer or a polymer blend.

In the case of copolymerization, those obtained by copolymerizing units such as terephthalic acid, bisphenol A and cyclohexanedimethanol in addition to the naphthalenedicarboxylic acid unit and the ethylene glycol unit are also preferable. Among these, the most preferred is a copolymer of a terephthalic acid unit from the viewpoint of mechanical strength and cost.

Preferred partners for the polymer blend are polyethylene terephthalate (PET),
Polyarylate (PAr), polycarbonate (P
C) and polyesters such as polycyclohexanedimethanol terephthalate (PCT).
Among them, PET is preferable from the viewpoint of mechanical strength and cost.
And a polymer blend of

Specific examples of preferred polyesters are shown below. Examples of polyester copolymers (numbers in parentheses indicate molar ratios) • 2,6-naphthalenedicarboxylic acid / terephthalic acid / ethylene glycol (70/30/100) Tg = 98 ° C • 2,6-naphthalenedicarboxylic acid / terephthalic acid / Ethylene glycol (80/20/100) Tg = 105
℃ Polyester polymer blend example (numbers in parentheses indicate weight ratio) ・ PEN / PET (60/40) Tg = 95 ° C. ・ PEN / PET (80/20) Tg = 104 ° C.

These supports may be subjected to heat treatment (crystallinity and orientation control), uniaxial and biaxial stretching (orientation control), blending of various polymers, surface treatment, etc. in order to improve the optical and physical properties. It can be carried out.

Further, as a support, for example, JP-A-4-
No. 124645, No. 5-40321, No. 6-3509
It is preferable to record photographic information and the like using a support having a magnetic recording layer described in JP-A Nos. 2 and 6-31875. It is also preferable to coat a water-resistant polymer as described in JP-A-8-292514 on the back surface of the support of the photosensitive material. The polyester support particularly preferably used for the light-sensitive material having the magnetic recording layer is disclosed in Published Technical Report 94-6023 (Invention Association; 1994.3.1).
5) is described in detail. The thickness of the support is 5 to 20
It is preferably 0 μm, more preferably 40 to 120 μm.

Here, “APS” means “Advanc”
e Photographic System ", US Pat. No. 4,848,893, US Pat.
No. 5,355,886, U.S. Pat. No. 5,847,334, and U.S. Pat. No. 3,847,334. No., Japanese Unexamined Patent Publication No.
175282, a film using a thin base having a magnetic layer described in JP-A-6-59357 and the like, using a film having a small width and a small format screen described in JP-A-4-125560 and the like, and JP-A-6-8886
JP-A-6-99908, JP-A-5-293138
And a photographic system using a camera capable of being magnetically recorded and easily loaded as described in JP-A-5-283382, etc., and used alone or in combination. In this system, when developing and printing,
Alternatively, a lab processing device that reads magnetically recorded information recorded on a light-sensitive material described in Japanese Patent Application Laid-Open No. 184835/1999 and prints the information on a photographic print as described in Japanese Patent Application Laid-Open No. 2-184835 may be used.

Water containing a base and / or a base precursor is used as a processing liquid which can be used in the image forming pump method of the present invention. As the base, an inorganic or organic base can be used. As the inorganic base, Japanese Unexamined Patent Publication No.
Hydroxides, phosphates, carbonates, borates, organic acid salts of alkali metals or alkaline earth metals described in JP-A-2-209448, and alkali or alkaline earth metals described in JP-A-63-25208. Acetylide and the like.

Examples of the organic base include ammonia, aliphatic or aromatic amines (eg, primary amines,
Secondary amines, tertiary amines, polyamines, hydroxylamines, heterocyclic amines), amidines, bis or tris or tetraamidine, guanidines, water-insoluble mono or bis or tris or tetraguanidines, And hydroxides of secondary ammonium.

As the base precursor, a decarboxylation type, a decomposition type, a reaction type and a complex salt forming type can be used. Examples of these bases and / or base precursors that can be preferably used in the present invention are described in Japanese Patent Application Laid-Open No. H05-209, issued March 22, 1991, Aztec Co., Ltd.
It is described on pages 5-88.

In the present development processing method, it is preferable to use at least an organic base in a concentration of 0.1 to 10 mol / l. Water containing a base and / or a base precursor is added to the photosensitive material in an amount of 5 cc / m ^{2 to} 30 cc / m ^2.
Is desirably provided. The amount of water provided is 5
If it is less than cc / m ² , the progress of development is hindered and sufficient color formation cannot be obtained. On the other hand, when it is more than 30 cc / m ² , the drying load after development becomes large. In this water,
It may contain an auxiliary developing agent, a preservative, a buffer, a chelating agent, an antifoggant, a development accelerator and the like as described in Japanese Patent Application No. 7-268045.

In the present development processing method, after supplying water containing a base and / or a base precursor, 90%
While maintaining the above conditions, it is desirable to heat at a temperature of 60 ° C. to 100 ° C. for 5 seconds to 60 seconds. The amount of donated water is 9
When less than 0% is maintained, development progress becomes insufficient, and development unevenness is likely to occur. If the temperature condition at this time is lower than 60 ° C., the progress of development is hindered, and sufficient color formation cannot be obtained. On the other hand, if the temperature is higher than 100 ° C., the water boils, so that uneven development tends to occur, which is not preferable. By performing heat development while maintaining the water amount within a certain range, an image having uniform, granular and excellent in sharpness can be obtained.

In the present invention, in order to reduce the load of reading image information and enhance image storability, a desilvering treatment for further removing silver halide and developed silver remaining in the photosensitive material after development. It is preferable to provide a step and / or a stabilization step.

The desilvering process means any of a bleaching process, a fixing process, and a bleach-fixing process.

Examples of the processing solution having bleaching ability include those described in
The compounds and processing conditions described on page 4, lower left column, line 16 to page 7, lower left column, line 6 of -125558 can be applied. The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof are described in JP-A-5-7269.
No. 4, JP-A-5-17312, and especially preferred are 1,3-diaminopropanetetraacetic acid and JP-A-5-17312.
A ferric complex salt of the compound of Example 1 on page 7 of 17312 is preferred. Further, in order to improve the biodegradability of the bleaching agent, JP-A-4-251845 and JP-A-4-26855.
No. 2, EP588,289, EP591,934 and JP-A-6-208213, it is preferable to use a ferric complex salt as a bleaching agent. The concentration of these bleaching agents is preferably from 0.05 to 0.3 mol per liter of the processing solution, and particularly from the viewpoint of reducing the amount discharged to the environment.
It is preferable to design with 1 to 0.15 mol. When the processing solution is a bleaching solution, 0.2 l / liter of the processing solution is used.
It is preferable to contain １1 mol of bromide, particularly preferably 0.3-0.8 mol. Bleaching agents contained in the processing solution include red blood salts, ferric chloride,
In addition to inorganic oxidants such as dichromate, persulfate, bromate and hydrogen peroxide, organic acid iron (III) complex salts are known. From the viewpoints of properties, corrosiveness of metals, etc., organic acid iron (III) complex salts are preferred.

The organic acid iron (III) contained in the treatment liquid of the present invention
) Complex salts include, for example, ethylenediamine-N,
N, N ', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediamine
Organic acid iron (III) complex salts such as N, N, N ', N'-tetraacetic acid, N-methyliminodiacetic acid, N- (hydroxyethyl) iminodiacetic acid, and glycol ether diaminetetraacetic acid;
JP-A-4-12173 including 1,3-propanediamine-N, N, N ', N'-iron (III) tetraacetate complex
No. 9, page 4, lower right column to page 5, upper left column, bleaching agent, carbamoyl bleaching agent described in EP-A-461413, heterocycle described in JP-A-4-174432. A bleaching agent described in European Patent Publication No. 520457, including a bleaching agent having an iron (III) N- (2-carboxyphenyl) iminodiacetate complex, ethylenediamine-N- (2-carboxyphenyl) -N ,
Bleaching agents described in European Patent Publication No. 530828, including N ', N'-iron (III) triacetate complex salts;
Bleaching agents described in EP-A-567126, including N'-bis- (1,2-dicarboxyethyl) ethylenediamineiron (III) complex salt, N- (1-carboxy-2-phenylethyl) asparagine Iron (III) acid
European Patent Publication No. 5 including bleaching agents described in European Patent Publication No. 588,289, including complex salts, and iron (III) N- (1-carboxyethyl) iminodiacetate complex salts.
In addition to the bleaching agent described in JP-A-91934, the bleaching agent described in EP-A-501479, and the bleaching agent described in EP-A-501479.
No. 61670, bleaching agent, European Patent Publication No. 43
No. 0000, a bleaching agent described in JP-A-3-14444.
Aminopolycarboxylate iron (II
I) Complex salts are preferably used. In the present invention, the above-mentioned bleaching agents may be used alone or in combination of two or more. Hereinafter, specific examples of the bleaching agent contained in the processing solution of the present invention are shown, but the bleaching agent contained in the processing solution of the present invention is not limited thereto. Specifically, the compounds described in JP-A-9-3407, page 13, line 9 to page 14, line 11 can be suitably used.

The organic acid iron (II) used in the treatment solution of the present invention
I) The complex salt may be added and dissolved as a complexed iron (III) complex salt, or an organic acid and an iron (III) salt (for example, ferric chloride, iron nitrate) as a complex-forming compound (II
I), ferric sulfate, ferric bromide, iron (III) ammonium sulfate, etc.) may coexist to form a complex in the treatment solution. Organic acids as complexing compounds include iron (III)
The amount may be slightly larger than the amount required for ion complex formation, and when it is added in excess, it is usually preferable to make the amount excessive in the range of 0.01 to 15%. The organic acid iron (III) complex salt contained in the treatment liquid of the present invention may be used as an alkali metal salt or an ammonium salt. As the alkali metal salt, lithium salt, sodium salt, potassium salt, etc.
Examples of the ammonium salt include an ammonium salt and a tetraethylammonium salt. Ammonium salts are preferred from the viewpoint of rapid bleaching properties, but, as described above, sodium salts and potassium salts are preferred from the viewpoint of environmental issues because reduction of the nitrogen atoms discharged to nature is desired. As the bleaching agent contained in the treatment liquid of the present invention, in addition to the above-mentioned bleaching agent comprising an organic iron (III) complex salt, the above-mentioned inorganic oxidizing agent may be used in combination as a bleaching agent.

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid and adipic acid. Also, Japanese Unexamined Patent Publication No.
No. 95630, RDNo. 17129, USP 3,8
It is also preferable to use a known bleaching accelerator described in U.S. Pat. The bleaching solution, 50 per light-sensitive material 1 m ²
It is preferable to replenish 1000 ml of the bleaching replenisher, particularly 80 to 500 ml, more preferably 10 to 500 ml.
It is preferred to replenish between 0 and 300 milliliters.
Further, it is preferable to perform aeration on the bleaching solution.

For the processing solution having a fixing ability, the compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied. . In particular, in order to improve the fixing speed and the preservability, JP-A-6-301169 discloses the general formulas (I) and (II).
It is preferable to include the compound represented by the formula (1) alone or in combination in a processing solution having a fixing ability. Further, in addition to p-toluenesulfinic acid salt,
It is also preferable to use the sulfinic acid described in No. 2 in order to improve the preservability.

It is preferable to use an ammonium salt in a processing solution having a bleaching ability or a processing solution having a fixing ability, from the viewpoint of improving the desilvering property, but from the viewpoint of preventing environmental pollution, it is preferable to use an ammonium salt. Is preferred.

Among the fixing agents that can be used in the present invention, thiosulfate, which is frequently used in ordinary immersion treatment, generally has a large fixing action, but has a slightly slower scattering and disappearance rate of silver halide. When performing a coating treatment, thiocyanate, cysteine, thiourea, a thiourea derivative, and KI are particularly preferable. These are small in the effect of removing silver thiosulfate from the emulsion film like the thiosulfate, but are effective in that they remain in the emulsion film and quickly eliminate the scattering of silver halide.

The stabilization treatment includes a treatment for suppressing the dye-forming reaction (hereinafter sometimes simply referred to as “suppression treatment”) and a silver halide stabilization treatment. When it is provided in a step different from the developing step, the processing step of suppressing the dye formation reaction may be performed subsequently to the heat developing step or may be performed after the desilvering processing. Further, it may be performed after reading image information formed on the photosensitive member after the heat development step.

Examples of the compound which inhibits the dye-forming reaction include a compound which reacts with the active site of the coupler to deactivate the dye-forming reaction activity, a compound which reacts with a developing agent to lose the developing activity, or a compound which reacts with the coupler. Compounds that reduce the ring activity are mentioned. Specifically, formalin,
N-methylol compounds, hexamethylenetetramine adducts or sulfite adducts of aldehydes such as glutaraldehyde can be used. For example, JP-A-2
Aldehyde sulfite adduct described in No. -220052, 4
Hexamethylenetetramine adducts of aldehydes described in JP-A-51237, N-methylol compounds, hexahydrotriazine adducts, compounds described in JP-A-4-313375, and the like can be used. In addition, US Patent No. 5,270,14
No. 8, British Patent 1350296, JP-A-48-473
No. 38, JP-A-4-214556 and JP-A-5-34889
Compounds and treatment methods described in the above items can be used.

Further, a nucleophilic reaction reagent such as sulfinic acid, acid anhydride, active ester and epoxy compound may be used. Further, an acid precursor which releases an acid upon heating and an electrophilic compound which undergoes a substitution reaction with a coexisting base upon heating can also be used.
No. 29, pages (31) to (32).

A surfactant, a chelating agent, and a bactericide can be added as a bactericidal and fungicide to the deterring solution containing a compound that suppresses the pigment formation reaction. The concentration of the compound that inhibits the dye formation reaction is preferably 10 ^{-1 to} 1M. When a suppression processing solution containing a compound for suppressing a dye formation reaction is used, a method similar to the stabilization processing step used in a normal development processing step of a silver halide color photosensitive member can be used.

The stabilization process used in the ordinary development process of a silver halide color photosensitive member is described, for example, in paragraph No. 0285 of JP-A-7-152129. The temperature of the suppression treatment liquid is preferably from room temperature to 60 ° C. Processing time ranges from 5 seconds to 5 minutes, 10 seconds to 1
A range of minutes is preferred. It is not necessary to control the pH of the suppression processing solution. Depending on the dye formed in the photosensitive member used in the present invention, the hue may be changed by making it acidic. Is preferably 7 to 9. The photosensitive member that has been immersed in the suppression processing liquid may be washed with water, but is not necessarily washed with water.

The photosensitive member after the development processing may be subjected to a silver halide stabilization processing. The above-described suppression treatment for suppressing the dye-forming reaction and the stabilization treatment of silver halide can be performed in any order, or may be performed simultaneously. When the silver halide stabilization treatment is performed prior to the treatment for suppressing the dye formation reaction after thermal development, the silver halide stabilization treatment can be performed simultaneously with the thermal development treatment.

The silver halide stabilization treatment may be a treatment for preventing printout of the silver halide or a treatment for causing a development terminator to act. A part or all of the silver halide may be treated with a silver halide solvent. The fixing step may be a dissolving step or a step of removing part or all of the dissolved silver complexing agent salt from the photosensitive member. Alternatively, a combination of these may be used.

A development terminator is a compound that neutralizes a base or reacts with a base to reduce the concentration of base in a film and stop development immediately after proper development, or to interact with silver or a silver salt to effect development. It is a compound that suppresses. Specific examples include an acid precursor that releases an acid when heated, an electrophilic compound that undergoes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For details, see (31) of JP-A-62-190529.
To (32). Examples of the printout inhibitor include JP-B-54-164 and JP-A-53-460.
No. 20, No. 48-45228, Japanese Patent Publication No. 57-8454
No. 1,005,
No. 144, 1-phenyl-5-mercaptotetrazole compounds, and JP-A-8-184936, viologen compounds.

Known silver halide solvents can be used. For example, thiosulfates, sulfites, thiocyanates, thioether compounds described in JP-B-47-11386, uracils described in JP-A-8-179458, compounds having 5- to 6-membered imide groups such as hydantoin, and the like. The carbon-sulfur 2 described in JP-A-53-144319
Compound with heavy bond, analytica chemica acta
(Analytica Chimica Acta) 248, 604-614 (1991
And the like, and meso-ion thiolate compounds such as trimethyltriazolium thiolate. Further, compounds capable of fixing and stabilizing silver halide described in JP-A-8-69097 can also be used as a silver halide solvent. The silver halide solvent may be used alone or in combination with a plurality of silver halide solvents.

The desilvering / stabilizing treatment may be carried out by immersing the photosensitive material in a processing solution. However, the desilvering / stabilizing treatment may be performed by a coating apparatus having a processing roller rotating in the same direction as the photosensitive material transport direction. It is preferable to perform a desilvering / stabilizing process by generating a vortex at a contact portion with the photosensitive material by high-speed rotation, and a method of applying a processing agent described in Japanese Patent Application No. 8-89977. It can also be based on a step of performing a heat treatment together with the sheet.

In a preferred embodiment of the present invention, after an image is obtained on a photosensitive material, a color image is obtained on another recording material based on the information. As a method, a photosensitive material such as color paper may be used, and normal projection exposure may be used. It is preferable to output to another recording material. The material to be output may be a sublimation type thermosensitive recording material, a full color direct thermosensitive recording material, an ink jet material, an electrophotographic material, or the like, in addition to a photosensitive material using silver halide.

In this development processing method, as described in European Patent Publication No. 210,660 and US Pat. No. 4,740,445, a basic metal compound which is poorly soluble in water as a base precursor and It is effective to employ a method of generating a base by a combination of a compound capable of forming a complex with a metal ion constituting the reactive metal compound and water as a medium (referred to as a complex forming compound). In this case, it is desirable that the basic metal compound which is hardly soluble in water is added to the light-sensitive material and the complex-forming compound is added to the processing material, and vice versa.

The amount of base or base precursor used is
0.1 to 20 g / m ² preferably from 1 to 10 g / m ^2. As the binder of the processing layer, a hydrophilic polymer similar to the photosensitive material can be used. The processing material is preferably hardened with a hardening material like the photosensitive material. The same hardening agent as that used in the photosensitive material can be used.

The processing material may contain a mordant for the purpose of transferring and removing the dye used in the yellow filter layer and antihalation layer of the light-sensitive material as described above. As the mordant, a polymer mordant is preferable. Examples include polymers containing secondary and tertiary amino groups,
Polymers having a nitrogen-containing heterocyclic moiety, polymers containing quaternary cation groups, etc., having a molecular weight of 5,000 to 20,000
0, especially 10,000 to 50,000. Specifically, U.S. Pat. Nos. 2,548,564 and 2,484,
No. 430, No. 3,148,061, No. 3,756,8
No. 14, 3,625,694, 3,859,09
Nos. 6, 4,128,538 and 3,958,995
No. 2,721,852, No. 2,798,063
No. 4,168,976, 3,709,690
Nos. 3,788,855 and 3,642,482
No. 3,488,706 and 3,557,066
No. 3,271,147, 3,271,148
No. 2,675,316, 2,882,156
No., UK Patent No. 1277453, JP-A-54-1152
No. 28, No. 54-145529, No. 54-12602
No. 7, 50-71332, 53-30328, 52-155528, 53-125, 53-1
024, etc. The amount of the mordant added is 0.1 g / m ^{2 to} 10 g / m ² , preferably 0.1 g / m ² .
A ^{5g / m 2 ~5g / m 2} .

The processing material may contain a physical development nucleus and a silver halide solvent, solubilize the silver halide of the light-sensitive material and fix it to the processing layer simultaneously with the development. As the reducing agent necessary for physical development, those known in the field of photosensitive materials can be used. In addition, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent or heat in the process can be used. As the reducing agent, a developing agent which has not been used for development in the photosensitive material diffused from the photosensitive material can be used, or the reducing agent may be contained in the processing material in advance. In the latter case, the reducing agent contained in the processing material may be the same as or different from the reducing agent contained in the photosensitive material.

Examples of the reducing agent include those described in US Pat.
Columns 49-50 of 00,626, 4,483,91
No. 4, columns 30 to 31, No. 4,330,617, No. 4,590,152, JP-A-60-140335, pages (17) to (18), JP-A-57-40245, and JP-A-57-40245. 56-13
Nos. 8736, 59-178458 and 59-538
No. 31, No. 59-182449, No. 59-18245
No. 0, No. 60-119555, No. 60-128436
No. to No. 60-128439, No. 60-1985
No. 40, No. 60-181742, No. 61-25925
No. 3, 62-444044, 62-131253
No. 62-131256, EP 2207
46A2, pages 78 to 96, etc., can be used. US Patent 3,0
Combinations of various reducing agents disclosed in JP 39,869 can also be used.

When a diffusion-resistant developing agent is used,
If necessary, an electron transfer agent and / or a precursor of the electron transfer agent may be used in combination. The electron transfer agent or its precursor can be selected from the aforementioned reducing agents or its precursors. When the reducing agent is added to the processing material, the amount added is 0.01 to 10 g / m
² , preferably 1/1 of the number of moles of silver in the light-sensitive material.
It is 0 to 5 times.

The physical development nucleus is for reducing a soluble silver salt diffused from the light-sensitive material to convert it into physically developed silver and fixing it to the processing layer. Physical development nuclei include zinc, mercury, lead, cadmium, iron, chromium, nickel, tin, cobalt, copper, ruthenium and other heavy metals, or palladium, platinum, gold, silver and other noble metals, or these heavy metals,
Chalcogen compounds such as noble metal sulfur, selenium, tellurium,
Any of known colloid particles and the like can be used. The physical development nuclei preferably have a particle diameter of 2 to 200 nm. These physical development nuclei are contained in the processing layer in an amount of 10 ⁻³ mg to 10 g / m ² .

The total silver halide solvent content in the processing layer
Is 0.01 to 100 mmol / m ^TwoAnd preferably
Is 0.1 to 50 mmol / m^TwoIt is. Coating of photosensitive material
1/20 to 20 times the molar amount of silver cloth
1/10 to 10 times, more preferably 1/4 to 4 times
is there. Silver halide solvents include water, methanol, ethanol
, Acetone, dimethylformaldehyde, methylpro
Solvent such as pill glycol or alkali or acidic water
It may be added as a solution, or it may be dispersed in solid fine particles and coated.
You may add to a cloth liquid. Processing materials are the same as photosensitive materials
Protective layer, undercoat layer, back layer, other various auxiliary layers
There may be.

The processing material is preferably provided with a processing layer on a continuous web. The continuous web here means
The length of the processing material is sufficiently longer than the long side of the corresponding photosensitive material at the time of processing, and the length can be used without processing a part of the photosensitive material to process multiple photosensitive materials. Refers to a form having Generally, it means that the length of the processing material is not less than 5 times and not more than 10000 times the width. The width of the processing material is arbitrary, but is preferably equal to or greater than the width of the corresponding photosensitive material.

It is also preferable that a plurality of photosensitive materials are processed in parallel, that is, a plurality of photosensitive materials are arranged and processed.
In this case, the width of the processing material is preferably equal to or more than the width of the photosensitive material × the number of simultaneous processing. Such continuous web processing is preferably supplied from a delivery roll, wound up on a take-up roll and discarded. Particularly, in the case of a photosensitive material having a large size, disposal is easy. As described above, the handling property of the continuous web processing material is remarkably improved as compared with the conventional sheet member.

The thickness of the support used for the processing material is arbitrary, but is preferably thin, particularly preferably 4 μm.
Not less than 120 μm. It is particularly preferable to use a processing material having a support thickness of 40 μm or less. In this case, since the amount of the processing material per unit volume increases, the above-mentioned processing material roll can be made compact. The material of the support is not particularly limited, and a material that can withstand the processing temperature is used. In general, papers, synthetic polymers (films) described in "Basics of photographic engineering-silver halide photography-" edited by The Photographic Society of Japan, pages 223 to 240, published by Corona Co., Ltd. (1979). Photographic support.

The material for the support can be used alone or as a support coated or laminated on one or both sides with a synthetic polymer such as polyethylene. In addition, JP-A-62-253,15
No. 9, pages 29-31, JP-A-1-161,236
Nos. (14) to (17), JP-A-63-316,848.
JP-A-2-22,651, JP-A-3-56,955
And the supports described in U.S. Pat. No. 5,001,033. In addition, a support mainly composed of a styrene polymer having a syndiotactic structure can also be preferably used.

A hydrophilic binder, a semiconductive metal oxide such as alumina sol and tin oxide, carbon black and other antistatic agents may be coated on the surface of these supports. A support on which aluminum is deposited can also be preferably used.

In the present development processing method, the photosensitive material photographed by a camera or the like is treated with a processing material containing a base and / or a base precursor and one of the amounts required for the maximum swelling of the entire coating film constituting the photosensitive material and the processing material. The photosensitive material and the processing material are superposed on each other in the presence of water equivalent to 1/10 to 1 times in such a manner that the photosensitive layer and the processing layer face each other, and developed by heating at a temperature of 60 ° C to 100 ° C for 5 seconds to 60 seconds. Is preferred. Any water may be used as long as it is generally used. Specifically, distilled water, ion exchange water, tap water, well water, mineral water, and the like can be used. A method in which a small amount of a preservative is added to these waters for the purpose of preventing generation of scale and decay, and circulating and filtering the water with an activated carbon filter, an ion exchange resin filter or the like is also preferably used.

The amount of water required for the maximum swelling is determined by immersing a photosensitive material or a processing material having a coating film to be measured in water to be used, measuring the film thickness when the swelling is sufficient, and calculating the maximum swelling amount. Can be obtained by reducing the weight of the coating film. An example of a method for measuring the degree of swelling is also described in Photographic Science Engineering, Vol. 16, p. 449 (1972).

In the present development processing method, it is desirable that the heater drum shown in FIG. 8 be filled with the following substances in order to stabilize the temperature. FIG. 7 shows a hollow container in which the photosensitive material contact portions 56 and 58 and the liquid junction portion 14 are integrated, and the cavity is filled with the substance 15. This is preferable because the temperature is stabilized. In this case, the heater does not need to be installed on the entire surface as shown in FIG. Needless to say, a temperature sensor for controlling the temperature is not shown, but may be provided in the substance 15. In addition, among the following substances, the substances are not harmful, that the temperature stability is good, and those that are preferable from the viewpoint of the optimum temperature for use in the thermal development of the present invention are indicated by ○, and particularly preferable ones are shown. Indicated by ◎.

Substance name Melting point (° C) ア ル ミ ニ ウ ム Aluminum perchlorate 6H ₂ O 82 Aluminum bromide 98 Aluminum bromide 6H ₂ O 93 Aluminum sulfate 9H ₂ O 74 Sodium aluminum sulfate 12H ₂ O 61 ◎ Potassium aluminum sulfate 12H ₂ O 93 Rubidium aluminum sulfate 12H ₂ O 93 ◎ Thallium sulfate (I) Aluminum · 12H ₂ O 91 ◎ Ammonium aluminum sulfate · 12H ₂ O 94 Gold (III) bromide 98 Triphenylbismuth 78 Thiocarbonyl chloride 74 Ammonium cerium (III) nitrate · 4H ₂ O 74 ○ Cobalt sulfate (II) · 7H ₂ O 97 dodecacarbonyltriruthenium four cobalt 60 ◎ cyclopentadienyl Sik Butadiene Cobalt 89 ○ chromium chloride _{(III) · 6H 2 O 83} ○ chromium nitrate (III) · 9H ₂ O 67 ○ sulfate potassium chromate · 12H ₂ O 89 ○ sulfate ammonium chrome-12H ₂ O 94 hexa aqua chromium (III) chloride Product 95 Tris (allyl) chromium (III) 79 Copper (II) chlorate ・ 6H ₂ O 65 Copper (II) perchlorate ・ 6H ₂ O 82 ◎ Phenyl copper (I) 80 Iron (II) iodide ・ 4H ₂ O 90-98 ◎ chlorodicarbonyl (cyclopentadienyl) iron (II) 87 ◎ (cyclopentadienyl) (acetylcyclopentadienyl) iron (II) 85 ◎ gallium chloride 78

[0127]

EXAMPLES Hereinafter, the effects of the present invention will be described in detail with reference to examples. Example 1 <Preparation method of photosensitive silver halide emulsion> A preparation method of a blue photosensitive silver halide emulsion (1) is described below. 1191 ml of distilled water containing 0.96 g of gelatin having an average molecular weight of 12000 and 0.9 g of potassium bromide was placed in a reaction vessel, and the temperature was raised to 40 ° C. An aqueous solution (A) containing 0.5 g of sodium silver nitrate (10.5 m) while vigorously stirring this solution
aqueous solution (B) containing 10 l and potassium bromide 0.35 g 10 m
was added over 150 seconds. Thirty seconds after the completion of the addition, 12 ml of a 10% aqueous solution of potassium bromide was added, and 30 seconds later, the temperature of the reaction solution was raised to 75 ° C. After adding 35.0 g of lime-processed gelatin together with 250 ml of distilled water,
39 ml of an aqueous solution (C) containing 10.0 g of silver nitrate and 30 ml of an aqueous solution (D) containing 6.7 g of potassium bromide were added over 3 minutes and 15 seconds while increasing the addition flow rate.

Next, 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) (potassium bromide concentration: 26%) containing potassium iodide at a molar ratio of 7:93 to potassium bromide were added. While accelerating, the reaction solution was added for 20 minutes so that the silver potential of the reaction solution became -20 mV with respect to the saturated calomel electrode. Further, 97 ml of an aqueous solution (G) containing 24.1 g of silver nitrate and a 21.9% aqueous solution of potassium bromide (H) were added over 3 minutes so that the silver potential of the reaction solution became 25 mV with respect to the saturated calomel electrode. . After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Then, 15 ml of 1N sodium hydroxide was added. Two minutes later, 100 ml of an aqueous solution (I) containing 5 g of silver nitrate and 200.5 ml of an aqueous solution (J) containing 4.7 g of potassium iodide were added over 5 minutes. After the addition was completed, 7.11 g of potassium bromide was added,
After maintaining at 55 ° C. for 1 minute, 248 ml of an aqueous solution (K) containing 62 g of silver nitrate and 231 ml of an aqueous solution (L) containing 48.1 g of potassium bromide were further added over 8 minutes. Thirty seconds later, an aqueous solution containing 0.03 g of sodium ethylthiosulfonate was added. The temperature was lowered, and the emulsion particles were coagulated and settled using Kao's Demol to desalinate. Dispersion was performed by adding sodium benzenethiosulfonate, phenoxyethanol, water-soluble polymer (10), and lime-processed gelatin.

The chemical sensitization was performed at 60 ° C. After adding the sensitizing dye (12) as a gelatin dispersion before chemical sensitization, a mixed solution of potassium thiocyanate and chloroauric acid is added, and then sodium thiosulfate and selenium sensitizer are added, and The termination of sensitization was performed with a mercapto compound,
The amounts of the sensitizing dye, chemical sensitizer and mercapto compound were optimized for sensitivity and fog. In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 1.07 μm, and an average thickness of 0.38 μm.
m, the equivalent circular diameter was 1.47 μm, and the aspect ratio was 3.9.

[0130]

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[0131]

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The method for preparing the blue-sensitive silver halide emulsion (2) is described below. Gelatin having an average molecular weight of 12,000
Distilled water 119 containing 96 g and 0.9 g of potassium bromide
1 ml was placed in a reaction vessel and heated to 40 ° C. To this solution, 37.5 ml of an aqueous solution (A) containing 1.5 g of silver nitrate and 37.5 ml of an aqueous solution (B) containing 1.051 g of potassium bromide were added over 90 seconds with vigorous stirring. Thirty seconds after the completion of the addition, 12 m
After 30 seconds, the temperature of the reaction solution was raised to 75 ° C. 35.0 g of lime-processed gelatin is added to 250 parts of distilled water.
Then, 116 ml of an aqueous solution (C) containing 29.0 g of silver nitrate and 91 ml of an aqueous solution (D) containing 20 g of potassium bromide were added for 11 minutes 35 while increasing the addition flow rate.
Added over seconds.

Next, 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) containing potassium iodide at a molar ratio of 3.3: 96.7 to potassium bromide (potassium bromide concentration: 26%) were prepared. Was added over 20 minutes while accelerating the addition flow rate and adjusting the silver potential of the reaction solution to 2 mV with respect to the saturated calomel electrode. Further, 97 ml of an aqueous solution (G) containing 24.1 g of silver nitrate and 21.9% of potassium bromide
The aqueous solution (H) was added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C.

Next, 1N sodium hydroxide 15m
1 was added. Two minutes later, 153 ml of an aqueous solution (I) containing 10.4 g of silver nitrate and 414.5 ml of an aqueous solution (J) containing 9.35 g of potassium iodide were added over 5 minutes. After the addition was completed, 7.11 g of potassium bromide was added, and 5
After keeping at 5 ° C. for 1 minute, 228 ml of an aqueous solution (K) containing 57.1 g of silver nitrate and 201 ml of an aqueous solution (L) containing 43.9 g of potassium bromide were further added over 8 minutes. Thirty seconds later, an aqueous solution containing 0.04 g of sodium ethylthiosulfonate was added. The temperature was lowered, and desalting and dispersion were carried out in the same manner as in the blue-sensitive silver halide emulsion (1). Chemical sensitization was performed in the same manner except that the blue-sensitive silver halide emulsion (1) and the selenium sensitizer were not added. The sensitizing dye and the mercapto compound whose chemical sensitization was stopped were substantially proportional to the surface area of the emulsion grains. In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains,
The average sphere equivalent diameter is 0.66 microns and the average thickness is 0.1
The diameter was 7 μm, the average equivalent circular diameter was 1.05 μm, and the average aspect ratio was 6.3.

The method for preparing the blue-sensitive silver halide emulsion (3) is described below. 1345 ml of distilled water containing 17.8 g of lime-processed gelatin, 6.2 g of potassium bromide and 0.46 g of potassium iodide was placed in a reaction vessel, and the temperature was raised to 45 ° C. To this solution, 70 ml (A) of an aqueous solution containing 11.8 g of silver nitrate and 70 ml (B) of an aqueous solution containing 3.8 g of potassium bromide were added over 45 seconds with vigorous stirring. After maintaining at 45 ° C. for 4 minutes, the temperature of the reaction solution was raised to 63 ° C. After adding 24 g of lime-processed gelatin together with 185 ml of distilled water, 208 ml of an aqueous solution containing 73 g of silver nitrate (C)
And a 24.8% aqueous solution of potassium bromide (D) were added over a period of 13 minutes while accelerating the addition flow rate so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining at 63 ° C. for 2 minutes after completion of the addition, the temperature of the reaction solution was lowered to 45 ° C.

Next, 1N sodium hydroxide 15m
1 was added. Two minutes later, 60 ml (E) of an aqueous solution containing 8.4 g of silver nitrate and 461 ml (F) of an aqueous solution containing 8.3 g of potassium iodide were added over 5 minutes. Further, 496 ml of an aqueous solution containing 148.8 g of silver nitrate (G)
And a 25% aqueous solution of potassium bromide (H) so that the silver potential of the reaction solution becomes 90 mV with respect to the saturated calomel electrode.
Added over 7 minutes. 30 seconds after completion of the addition, 2 g of potassium bromide and 0.1 g of sodium ethylthiosulfonate were added.
An aqueous solution containing 06 g was added. The temperature was lowered, and desalting, dispersion and chemical sensitization were carried out in the same manner as in the case of the blue-sensitive silver halide emulsion (2). The resulting emulsion had an average grain size of 0.44 μm and an average thickness of 0.2 μm expressed in a diameter equivalent to a sphere.
m, average equivalent circular diameter 0.53 μm, and average aspect ratio 2.6.

The preparation method of the green photosensitive silver halide emulsion (4) is shown below. Gelatin having an average molecular weight of 12,000
Distilled water 119 containing 96 g and 0.9 g of potassium bromide
1 ml was placed in a reaction vessel and heated to 40 ° C. To this solution, 17.5 ml of an aqueous solution (A) containing 0.7 g of silver nitrate and 17.5 ml of an aqueous solution (B) containing 1.051 g of potassium bromide were added over 120 seconds with vigorous stirring. Thirty seconds after the completion of the addition, 12 m
After 30 seconds, the temperature of the reaction solution was raised to 75 ° C. 35.0 g of lime-processed gelatin is added to 250 parts of distilled water.
Then, 56 ml of an aqueous solution (C) containing 19.0 g of silver nitrate and 461 ml of an aqueous solution (D) containing 10 g of potassium bromide were added for 7 minutes 35 while increasing the addition flow rate.
Added over seconds.

Next, 302 ml of an aqueous solution (E) containing 96.7 g of silver nitrate and an aqueous solution (F) (potassium bromide concentration: 26%) containing potassium iodide in a molar ratio of 3.3: 96.7 to potassium bromide were used. Was added over 20 minutes while accelerating the addition flow rate and adjusting the silver potential of the reaction solution to 0 mV with respect to the saturated calomel electrode. Further, 97 ml of an aqueous solution (G) containing 24.1 g of silver nitrate and 21.9% of potassium bromide
The aqueous solution (H) was added over 3 minutes so that the silver potential of the reaction solution became 0 mV with respect to the saturated calomel electrode. After maintaining the temperature at 75 ° C. for 1 minute after the completion of the addition, the temperature of the reaction solution was lowered to 55 ° C. Next, 122 ml of an aqueous solution (I) containing 8.3 g of silver nitrate and 332 ml of an aqueous solution (J) containing 7.48 g of potassium iodide were added over 5 minutes. After the addition was completed, 7.11 g of potassium bromide was added, and 55
After maintaining at 1 ° C. for 1 minute, 228 ml of an aqueous solution (K) containing 62.8 g of silver nitrate and 201 ml of an aqueous solution (L) containing 48.3 g of potassium bromide were added over 8 minutes. The temperature was lowered, and desalting and dispersion were carried out in the same manner as in the blue-sensitive silver halide emulsion (1). Chemical sensitization is also carried out by using sensitizing dyes (13), (14) instead of sensitizing dye (12).
Except that a gelatin dispersion of the mixture of (15) was added,
It carried out similarly to the blue photosensitive silver halide emulsion (1). The resulting grains had tabular grains of 9 of the total projected area of all grains.
It accounts for more than 9%, has an average equivalent sphere diameter of 0.85 microns, an average thickness of 0.26 μm, and an average equivalent circular diameter of 1.
The average aspect ratio was 4.8 μm.

[0139]

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The method for preparing the green photosensitive silver halide emulsion (5) is described below. Desalting and dispersion are performed in the same manner as for the blue-sensitive silver halide emulsion except that sodium hydroxide and sodium ethylthiosulfonate are not added during grain formation, and the chemical sensitization is performed using the green-sensitive silver halide emulsion. Same as (4). In the obtained grains, tabular grains account for more than 99% of the total projected area of all grains, have an average equivalent sphere diameter of 0.66 microns, an average thickness of 0.17 μm, an average equivalent circular diameter of 1.05 μm, and an average aspect ratio. The ratio was 6.3.

The method for preparing the green photosensitive silver halide emulsion (6) is described below. Grain formation, desalting and dispersion were carried out in the same manner as for the blue-sensitive silver halide emulsion (3) except that sodium ethylthiosulfonate was changed to 4 mg without adding sodium hydroxide during grain formation. Chemical sensitization was carried out in the same manner as for the green light-sensitive silver halide emulsion (4), except that no selenium sensitizer was added. The obtained emulsion was hexagonal tabular grains having an average particle size of 0.44 μm, an average thickness of 0.2 μm, an average equivalent circular diameter of 0.53 μm, and an average aspect ratio of 2.6, expressed in terms of sphere equivalent diameter.

The method for preparing the red-sensitive silver halide emulsion (7) is described below. The sensitizing dye at the time of chemical sensitization is replaced with a sensitizing dye (1
It was prepared in the same manner as the green light-sensitive silver halide emulsion (4), except that the gelatin dispersion of 6) and the gelatin dispersion of a mixture of the sensitizing dyes (17) and (18) were added.
The resulting grains had tabular grains of 9 of the total projected area of all grains.
It accounts for more than 9%, has an average equivalent sphere diameter of 0.85 microns, an average thickness of 0.26 μm, and an average equivalent circular diameter of 1.
The average aspect ratio was 4.8 μm.

[0143]

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The method for preparing the red-sensitive silver halide emulsion (8) is described below. The sensitizing dye at the time of chemical sensitization is replaced with a sensitizing dye (1
It was prepared in the same manner as for the green light-sensitive silver halide emulsion (5), except that the gelatin dispersion of 6) and the gelatin dispersion of a mixture of the sensitizing dyes (17) and (18) were added.
The obtained grains had tabular grains of 99% of the total projected area of all grains.
The average sphere equivalent diameter is 0.66 microns, the average thickness is 0.17 μm, and the average equivalent circular diameter is 1.05.
μm, and the average aspect ratio was 6.3.

The method for preparing the red-sensitive silver halide emulsion (9) is described below. The sensitizing dye at the time of chemical sensitization is replaced with a sensitizing dye (1
It was prepared in the same manner as the green light-sensitive silver halide emulsion (6) except that the gelatin dispersion of 6) and the gelatin dispersion of a mixture of the sensitizing dyes (17) and (18) were added.
The obtained emulsion was hexagonal tabular grains having an average particle size of 0.44 μm, an average thickness of 0.2 μm, an average equivalent circular diameter of 0.53 μm, and an average aspect ratio of 2.6, expressed in terms of sphere equivalent diameter.

<Method for Preparing Emulsified Dispersion of Color Developing Agent and Coupler> The oil phase component and the aqueous phase component having the compositions shown in Table 1 are each dissolved to form a uniform solution at 60 ° C. Combine the oil phase component and the water phase component in a 1 liter stainless steel container,
The mixture was dispersed at 10,000 rpm for 20 minutes by a dissolver equipped with a 5 cm diameter disperser. To this, warm water in the amount shown in Table 1 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0147]

[Table 1]

[0148]

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[0149]

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<Preparation of Dye Composition for Yellow Filter and Antihalation Layer> The dye composition was prepared and added as an emulsified dispersion as follows. The leuco dye, the developer and, if necessary, the high-boiling organic solvent (1) were weighed, ethyl acetate was added, and the mixture was heated and dissolved at about 60 ° C. to form a uniform solution. ) To 1.
0 g, 6.6% of lime-processed gelatin heated to about 60 ° C
Add 190 cc of the aqueous solution and use a homogenizer for 10 minutes.
Dispersed at 000 rpm. Two types of dye dispersions shown in Table 2 were prepared.

[0151]

[Table 2]

[0152]

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<Preparation of Support> A support used in the present invention was prepared by the following method. 100% by weight of polyethylene-2,6-naphthalate (PEN) polymer and Tinuvin P. 326 (manufactured by Ciba-Geigy) was dried, melted at 300 ° C., extruded from a T-die, stretched 3.3 times at 140 ° C., and then stretched at 130 ° C. to 3.times. The film is stretched three times in the transverse direction, and further heat-set at 250 ° C. for 6 seconds to form a P having a thickness of 92 μm.
An EN film was obtained. The PEN film has a blue dye, a magenta dye, and a yellow dye (Publication Technical Report: I-1, I-4, I-6, described in Official Technique No. 94-6023).
I-24, I-26, I-27, II-5) with a yellow density of 0.01, a magenta density of 0.08, and a cyan density of 0.
09 was added. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 113 ° C. and 30 hours, thereby providing a support that was not easily curled.

<Coating of Undercoat Layer> The support was subjected to a corona discharge treatment, a UV irradiation treatment, and a glow discharge treatment on both surfaces, and then gelatin (0.1 g / m 2) was applied to each surface.
² ), sodium α-sulfodi-2-ethylhexyl succinate (0.01 g / m ² ), salicylic acid (0.02
5 g / m ² ), PQ-1 (0.005 g / m ² ), PQ
-2 (0.006 g / m ² ) was applied (10 cc / m ² , using a bar coater) to provide an undercoat layer on the high temperature side during stretching. Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were set at 115 ° C.).

<Coating of Back Layer> 1) Coating of Antistatic Layer Dispersion (secondary agglomerated particles) of tin oxide-antimony oxide composite having an average particle size of 0.005 μm and a specific resistance of 5 Ω · cm diameter 0.08μm; 0.027g / m ^2), gelatin ^{(0.03g / m 2), (} CH 2 = CHSO 2 C
H ₂ CH ₂ NHCO) ₂ CH ₂ (0.02 g / m ² ),
Poly (degree of polymerization 10) oxyethylene-p-nonylphenol (0.005 g / m ² ), PQ-3 (0.008 g)
/ M ² ) and resorcinol.

2) Coating of Magnetic Recording Layer Cobalt-γ-iron oxide coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m ² / g) , Major axis 0.14 μm, minor axis 0.03 μm, saturation magnetization 89 emu
/ G, Fe ^{+ 2} / Fe ⁺³ = 6/94, surface treated with silicon oxide aluminum oxide at 2% by weight of iron oxide) 0.06
g / m ² of diacetyl cellulose 1.15 g / m ² (the dispersion of the iron oxide was carried out using an open kneader and a sand mill), PQ-4 as a curing agent (0.075g / m ^2),
PQ-5 (0.004 g / m ² ) was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone, dibutyl phthalate as a solvent, and the film thickness was 1.2.
A μm magnetic recording layer was obtained. C ₆ H ₁₃ CH as slip agent
(OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (50 g / m ² ), silica particles (average particle size 1.0 μm) as a matting agent, and aluminum oxide abrasive (ERC-DBM manufactured by Reynolds Metal Co .; average particle size) 5 mg each with a diameter of 0.44 μm)
/ M ² and 15 mg / m ² . Drying was performed at 115 ° C. for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C.). X- light increase of the color density of D ^B of the magnetic recording layer in the (blue filter) was about 0.
1, and the saturation magnetization moment of the magnetic recording layer is 4.2 em
u / g, coercive force 7.3 × 10 ⁴ A / m, squareness ratio 65%
Met.

3) Adjustment of sliding layer Hydroxyethyl cellulose (25 mg / m ² ), PQ
-6 (7.5 mg / m ² ), PQ-7 (1.5 mg / m ² )
² ) 1.5 mg / m ² of polydimethylsiloxane was applied. This mixture was melted at 105 ° C. in xylene / propylene glycol monomethyl ether (1/1), and propylene monomethyl ether (10-fold amount) was added at room temperature.
And then dispersed in acetone (average particle size: 0.01 μm) and then added. 115 for drying
C. for 6 minutes (115 ° C. for all rollers and conveyors in the drying zone). The sliding layer has a dynamic friction coefficient of 0.10 (5
mmφ stainless steel hard ball, load 100g, speed 6c
m / min), the coefficient of static friction was 0.09 (clip method), and the dynamic friction coefficient between the emulsion surface and the sliding layer was 0.18, which were excellent characteristics. Using the above materials and base, a photosensitive material 101 having a multilayer structure shown in Table 3 was produced.

[0158]

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[0159]

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[0160]

[Table 3]

[0161]

[Table 4]

[0162]

[Table 5]

The prepared photosensitive material 101 was cut and perforated in APS format, housed in an APS compatible cartridge, loaded into an APS camera, and photographed with a person using a Macbeth chart. This sample was subjected to development processing by a liquid supply type thermal development apparatus shown in FIG. As the treatment liquid, the following basic liquid was supplied at 15 cc / m ² , and the temperature of the heater was 80 ° C.
The heat treatment time after application was 20 seconds. The retention of the applied water was 100%.

Basic liquid Tetramethylammonium hydroxide 1 mol / L N, N‘-dimethylguanidine 1 mol / L Sodium bicarbonate was added to adjust the pH to 12.5.

This sample was dried and stored again in the APS cartridge. Thereafter, the sample is taken out of the cartridge, and the obtained negative image is read by a digital image reading device Frontier SP-1000 (manufactured by Fuji Photo Film), and after image processing on a workstation,
When output with a heat development printer (PICTROGRAPHY4000, manufactured by Fuji Photo Film), good prints equivalent to conventional photographs in both graininess and sharpness were obtained.

Example 2 The developed photosensitive material obtained in Example 1 was sent to a desilvering bath and immersed in a desilvering bath having the following formulation at 40 ° C. for 1 minute.
Subsequently, it was sent to a stabilization bath, immersed in a stabilization bath having the following formulation at 40 ° C. for 1 minute, and then dried. Desilverization treatment liquid Iron salt of ethylenediaminetetraacetic acid (III) 20 g Sodium thiocyanate 40 g Water was added to 1000 ml Stabilization treatment liquid potassium carbonate 30 g Water was added to 1000 ml

The light-sensitive material thus obtained has no tackiness, and after being attached to an APS cartridge,
PS Photo Scanner Photoscan-it (Ph
An image was input using an auto-scanner AS-1), and a postcard was prepared on a personal computer. Moreover, a postcard of a preferable photograph was obtained. Further, a color image preservation forced deterioration test at 60 ° C. and 70% RH was performed to check the density deterioration at a magenta density of 1.50. As a result, the magenta density after one week was 1.47.
The density deterioration rate was 2%.

Example 3 In Example 1, development processing was performed using one of a pair of processing apparatuses shown in FIG. 7 instead of the apparatus shown in FIG. In addition, phenyl copper was used as the 15 temperature stabilizing substance. In the present embodiment, since the photosensitive material contact portion is shorter than in the case of the apparatus shown in FIG. 1, the transport speed of the photosensitive material is slower. Stable. Specifically, there was little development unevenness and density unevenness, and there was little processing variation for each processing day.

[0169]

As described above, according to the present invention, a color having excellent granularity and sharpness can be obtained by using a photosensitive material for photography by a simple thermal development process in a compact liquid supply type thermal development apparatus. Rapid image processing is possible while satisfying the high storage stability required for materials for use.

[Brief description of the drawings]

FIG. 1 is a schematic front view showing a preferred embodiment of a liquid supply type thermal developing apparatus of the present invention.

FIG. 2 is a perspective view of a main part of FIG.

FIG. 3 is a schematic sectional view showing a preferred embodiment of a main part of the liquid supply type thermal developing apparatus of the present invention.

FIG. 4 is an explanatory diagram showing conditions for making the opening direction of a closing member in FIG. 3 constant.

FIG. 5 is a schematic front view showing another preferred embodiment of the liquid supply type heat developing apparatus of the present invention.

FIG. 6 is a schematic sectional view showing another preferred embodiment of a main part of the liquid supply type heat developing apparatus of the present invention.

FIG. 7 is a schematic configuration diagram showing a preferred embodiment of an image forming apparatus using the liquid supply type thermal developing device of the present invention.

FIG. 8 is a schematic configuration diagram showing another preferred embodiment of an image forming apparatus using the liquid supply type heat developing apparatus of the present invention.

[Explanation of symbols]

Reference Signs List 12 container 14 liquid junction 14A heater 15 temperature stabilizing substance 16 photosensitive material contact part 16A slit-shaped opening (liquid supply part) 16B heater 18 pump 20 photosensitive material 22A, 22B, 22C guide roll 24 pressing cloth 42 closing member 46 buffer Part 48 sliding member 50 spherical body

Claims (11)

[Claims] 1. A processing liquid container section for filling a processing liquid, and a photosensitive material contact section for contacting the processing liquid with the photosensitive material near a processing liquid supply section in the processing liquid container section to which the processing liquid is supplied. A liquid junction section for communicating the photosensitive material contacting section with the processing liquid container section; and a heating means for heating the processing liquid in the vicinity of the processing liquid supply section. Developing device. 2. The liquid supply type thermal developing apparatus according to claim 1, wherein the processing liquid container section and the liquid junction section are detachably connected to each other. 3. The liquid supply type thermal developing apparatus according to claim 1, further comprising a mechanism for adjusting a supply amount of the processing liquid in the processing liquid container to the processing liquid supply unit. 4. The liquid supply type thermal developing apparatus according to claim 1, wherein said processing liquid supply section comprises a slit-shaped opening. 5. The liquid supply type thermal developing apparatus according to claim 1, further comprising a liquid evaporation preventing means between the processing liquid container and the processing liquid supply. 6. The liquid supply type thermal developing apparatus according to claim 1, wherein said heating means is formed of a metal conductive block. 7. The method according to claim 1, wherein a photosensitive material having a photosensitive layer containing at least tabular photosensitive silver halide grains, a color developing agent, a coupler and a binder on a transparent support is exposed. The processing liquid is supplied by using the liquid supply type thermal developing apparatus described in the above section, and the temperature is 60 ° C to 100 ° C.
An image forming method, wherein an image based on a non-diffusible dye is formed on a photosensitive material by heating for from 60 seconds to 60 seconds. 8. The image forming method according to claim 7, wherein a color image is obtained on another recording material based on the image information of the image obtained in claim 7. 9. The method according to claim 7, wherein the width of the long side of the slit-shaped opening of the processing liquid supply section in the liquid supply type thermal developing device is smaller than the width of the long photosensitive material. Image forming method. 10. The method according to claim 8, wherein a desilvering process, a stabilizing process, and a drying process are performed after the color image is obtained.
2. The image forming method according to 1., 11. A processed photosensitive material comprising a photosensitive material having a color image obtained by the method according to claim 10 stored in a cartridge having a door which can be opened and closed at a film insertion opening.