JPH0677140B2 - Processing method of silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for processing a silver halide photographic light-sensitive material for an infrared laser scanner, and more specifically, processing with an automatic processor (hereinafter referred to as an automatic processor). The present invention relates to a simple treatment method that does not require complicated preparation of the treatment solution when performing.

(Prior Art) Conventionally, as one of the exposure methods of a photographic light-sensitive material, an original image is scanned, and a silver halide photographic light-sensitive material is exposed on the basis of the image signal, and a negative image or an image corresponding to the image of the original image is exposed. An image forming method using a so-called scanner method for forming a positive image is known. There are various types of recording apparatuses that have practically used the image forming method using the scanner system, and the conventional glow lamp is used as the recording light source of these scanner type recording apparatuses.
Xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, etc. have been used. However, each of these light sources has a practical drawback that the output is weak and the life is short. To compensate for these shortcomings, He-Ne
There are scanners and laser printers that use a coherent laser light source such as a laser, an argon laser, and a He-Cd laser as a scanner-type light source to perform exposure with high illuminance. These are high output, but the device is large, expensive, requires a modulator,
Further, since visible light is used, the safelight of the light-sensitive material is limited, and there are drawbacks such as poor handling.

On the other hand, a semiconductor laser is small, inexpensive, easy to modulate, and has a longer life than the above lasers. Further, since it emits light in the infrared region, a bright safelight can be used, which has the advantage of improving the handling workability. Therefore, the importance of developing a photosensitive material in this field is increasing more and more.

On the other hand, black-and-white silver halide photographic light-sensitive materials are generally processed in the steps of post-exposure development-fixing-washing (or stabilizing). When this development process is processed in an automatic processor,
The replenisher for each processing solution, such as developer and fixer, is prepared by diluting and mixing a processing agent consisting of multiple parts with water and stored in the replenisher stock tank to process the photosensitive material from the replenisher stock tank. A certain amount of developer, depending on
The fixer is replenished in the developing tank and fixing tank of the developing machine.

(Problems to be Solved by the Invention) Although the above-mentioned automatic processing system is a completed system which has been used for many years, nowadays the progress of development of electronic equipment has progressed and the silver halide photosensitive material is now wet-processed. There are some drawbacks to the basic system of doing so.

That is, the developer and fixer are diluted and mixed with water,
The major drawback is that a stock tank for that purpose must be installed. Although chemical mixers have become widespread in recent years, there is no fundamental change in the point that preparation of a treatment agent composed of multiple parts and that the space of the chemical mixer is outside the space of the automatic processing machine.

Further, in order to impart further suitability for rapid processing, it has been customary to carry out a dura mater reaction during the processing step. Glutaraldehyde, which is commonly used in developing solutions, has an irritating odor and is not very safe when attached to the body.
In addition, in the case of hardeners made of aluminum salts that are commonly used in fixers, the fixer is set in the pH range where the hardening reactivity is highest in order to reduce swelling in washing water and reduce the drying load. It must be. That is, its pH range is 4.2 to 4.6. However, in this pH range, a part of the thiosulfate, which is the main component of the fixer, is decomposed to generate sulfurous acid gas and acetic acid gas, which is generally used as a pH buffering agent, is generated. Contamination with an unpleasant odor remains a major problem. In addition, this sulfurous acid gas may corrode not only the automatic processing machine but also the peripheral equipment for a long period of time, which is a bigger problem now.

One of the roots of the problems associated with the above-mentioned development processing is that the film is hardened during the processing, that is, in the developing solution, glutaraldehyde is generally used, and in the fixing solution, an aluminum salt is generally used. Is in use. The former does not apply at all, and the latter does not affect the pH of the fixer.
It was found that many of the above problems can be solved by applying it as a weak dura reaction with a value of 4.65 or more.

However, in order to carry out development processing that does not rely on such processing hardening, it is essential to sufficiently harden the silver halide photosensitive material in advance.

If the silver halide light-sensitive material is sufficiently hardened in advance, for example, in a light-sensitive material system that requires high sensitivity and high density such as medical melee photography, a large amount of coated silver is required, which is not preferable from the viewpoint of resource conservation and cost. .

Therefore, it is common knowledge in the art to increase the density with fine particles as much as possible, that is, to increase the density (covering power) per unit amount of silver at the expense of photographic sensitivity.

On the other hand, with recent advances in the field of mechatronics, speeding up of photographic processing combined with such hardware is becoming more and more important.

Under such circumstances, it is highly desired to sufficiently increase the sensitivity and the processing speed in the photosensitive material processing system for infrared laser scanners.

Generally, when the halide composition of a light-sensitive material contains a large amount of chloride, the developing speed increases, but the sensitivity is low. Further, silver chloride is liable to be eluted in the developer due to sulfite in the developer,
As a result, it causes the problem of silver sludge precipitation. If a compound such as those described in JP-A-56-24347, U.S. Pat. No. 3,173,789, and British Patent No. 940169 is added to the developer as an anti-sludge agent in an attempt to avoid the precipitation of this silver sludge, The sensitivity of the material processing system is further reduced, which means that the development is fast and the time is short, and a certain gradation can be obtained, but the sensitivity is low.

On the other hand, when the amount of iodide is large, the sensitivity is high, but the developing speed is low and the gradation is low, so that the ratio of iodide is also limited.

Furthermore, in order to make the light-sensitive material have color sensitivity in the near infrared region, the silver halide grain must have a high (100) face / (111) face ratio. There is a limit to the ratio of iodide in order to increase the (100) face / (111) face ratio. In this way, the emulsion design of a light-sensitive material having a high sensitivity in the near infrared region requires a special technique because the technique in this field is very new.

Therefore, an object of the present invention is to provide a sensitive material processing system for an infrared laser scanner, firstly to obtain higher sensitivity to the sensitive material / processing system, and secondly to obtain an image by rapid development processing and reduce the size of the developing machine. Third, to facilitate liquid preparation work and maintenance of the developing machine, and fourth, to reduce odors from the development work environment. In addition, it is necessary to reduce the generation of harmful gas to prevent the equipment from corroding, and fifth, to make it possible to perform completely pipeless processing and to place no restrictions on the installation location.

(Means for Solving the Problems) The above object of the present invention is to provide a halogenated infrared laser scanner comprising a support and at least one hydrophilic colloid layer containing at least one silver halide emulsion layer. In the method of processing a silver photographic light-sensitive material using an automatic developing machine, the silver halide emulsion layer has an iodine content of 0 to 2
It contains silver chloroiodobromide grains having a mol% and a chlorine content of 0 to 30 mol%, the swelling percentage of the hydrophilic colloid layer is 200% or less, and a developer used in the developing step of an automatic processor is as follows. It has been found to be achieved by a method of processing a silver halide photographic light-sensitive material, which comprises replenishing and using a one-part developer containing a 3-pyrazolidone-based developing agent of the formula (I).

General formula (I) (Here, R represents a phenyl group which may be substituted with a methyl group, a hydroxyl group or a methoxy group. R ₁ , R ₂ ,
R ₃ and R _{4, which} may be the same or different, each represents a hydrogen atom or a methyl group which may be substituted with a hydroxyl group or a morpholino group. However, when R represents an unsubstituted phenyl group, R ₁ , R ₂ , R ₃ and R ₄ are not all hydrogen atoms at the same time. As a result of intensive studies, the present inventor has processed the specified silver halide light-sensitive material for infrared laser scanner with a highly active developing solution consisting of a one-part solvent to obtain high sensitivity, rapid processing and easy processing. A new system was devised to enable liquid preparation work.

Compounds of the present invention are British Patent Nos. 943928, 1093281,
Although included in the compounds described in U.S. Pat.No. 3221023, there is no mention of a method of automatically developing a specific photographic light-sensitive material element of the present invention, and the constitution and effects of the present invention as described above. I do not teach you anything. The compound of the present invention will find further technical value and progress of high sensitivity and simple and rapid processing only after taking the light-sensitive material processing system as in the present invention.

The general formula (I) will be further described.

In the above general formula, R ₁ is preferably a hydrogen atom, a morpholinomethyl group or a hydroxymethyl group. R ₄ is preferably a hydrogen atom.

More preferably, R ₂ is a hydroxymethyl group and R ₃
Is a hydroxymethyl group or a methyl group.

Examples of the compound represented by the general formula of the present invention are shown below, but the present invention is not limited thereto.

1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone 1-p-tolyl-4,4-dihydroxymethyl-3-pyrazolidone 1-phenyl-4-hydroxymethyl-4-methyl-
3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-2-morpholinomethyl-4,4-dimethyl- 3-pyrazolidone 1-phenyl-2-morpholinomethyl-4-methyl-3-pyrazolidone 1-phenyl-2-hydroxymethyl-4-methyl-
3-Pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-5-methyl-3-pyrazolidone 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1-p-hydroxy Phenyl-4,4-dimethyl-3-
Pyrazolidone 1-m-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1-p-methoxyphenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1- (3,5-dimethyl) phenyl-4 -Methyl-4-
Hydroxymethyl-3-pyrazolidone The compound of the present invention is added to Developer 1 in an amount of 0.1 g to 30 g. More preferably, 0.5 g to 20 g is added. More preferably, 1 g to 15 g is added.

The swelling percentage referred to in the present invention is (a) the photographic material at 38 ° C. 50
Incubation at 3% relative humidity for 3 days, (b)
The thickness of the hydrophilic colloid layer is measured, and (c) the photographic material is
Soak in distilled water at 21 ° C for 3 minutes, and (d) step (b)
It can be determined by measuring the percentage change in the thickness of the layer compared to the thickness of the hydrophilic colloid layer measured in.

In the present invention, the swelling percentage is 20 from the viewpoints of rapid processing (for example, reduction of drying load) and simplification of processing (for example, omission of treatment dura, reduction of the number of parts of the treatment agent).
It should be 0% or less.

Such rapid processing and simplification of processing (in particular, rapid processing)
Even better is achieved by further reducing the swelling percentage.

On the other hand, if the swelling percentage is lowered, the speed of development, fixing, washing with water, etc. is lowered, so it is not preferable to lower it more than necessary.

The preferred swelling percentage is 180% or less and 30% or more, especially 1
It is preferably 50% or less and 50% or more.

In the present invention, a swelling percentage of 200% or less can be easily controlled by those skilled in the art by, for example, increasing the amount of the hardener used in the light-sensitive material.

Aldehyde compounds, compounds having an active halogen described in U.S. Pat. No. 3,288,775, U.S. Pat.
Organic compounds such as halogencarboxaldehydes such as mucochloric acid and compounds having a reactive ethylenically unsaturated group described in 5,718 are known. Of these, vinyl sulfone type hardeners are preferable. Polymeric hardeners can also be preferably used in the present invention.

The polymer hardener used in the present invention is preferably a polymer having an active vinyl group or a group which is a precursor thereof, and particularly vinyl sulfone having a long spacer as described in JP-A-56-142524. A polymer in which an active vinyl group such as a group, or a group serving as a precursor thereof is bonded to a polymer main chain is particularly preferable.

The amount of these hardeners added to achieve the swelling percentage of the present invention depends on the type of hardener used and the type of gelatin.

In the present invention, it is preferable that the emulsion layer and / or the other hydrophilic colloid layer contain an organic substance which can flow out in the development processing step. When the substance to be washed away is gelatin, gelatin species that are not involved in the crosslinking reaction of gelatin with a hardening agent are preferable, and examples thereof include acetylated gelatin and phthalated gelatin, and those having a small molecular weight are preferable. On the other hand, as a high molecular substance other than gelatin, polyacrylamide as described in U.S. Pat.No. 3,271,158, or also polyvinyl alcohol, hydrophilic polymers such as polyvinylpyrrolidone can be effectively used, dextran and saccharose, Sugars such as pullulan are also effective. Among them, polyacrylamide and dextran are preferable, and polyacrylamide is a particularly preferable substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. It is effective that the amount of outflow in the treatment is 10% or more and 50% or less, and preferably 15% or more and 30% or less of the total weight of the applied organic substance other than the silver halide grains.

The layer containing an organic substance which flows out in the treatment of the present invention may be an emulsion layer or a surface protective layer, but when the total coating amount of the organic substance is the same, it is more effective than a layer containing only the emulsion layer as a surface protective layer. It is more preferable to include it in the emulsion layer, and it is more preferable to include it only in the surface protective layer. In a light-sensitive material having a multi-layered emulsion layer, when the total coating amount of the organic substance is the same, it is preferable that the emulsion layer is contained more in the emulsion layer closer to the surface protective layer.

The photosensitive silver halide used in the present invention is, for example, silver bromide,
A silver halide composed of chlorine, bromine and / or iodide such as silver iodobromide, silver chlorobromide and silver chloroiodobromide, which is silver iodide in the case of silver iodobromide or silver chloroiodobromide. Is 0 to 2 mol%, preferably 0 to 0.5 mol%, and silver chloride is 0 to 30 mol%, preferably 0 to 20 mol%.

By specifying the halide composition within the above range, in the rapid and simple processing method using the developing solution consisting of one part according to the present invention, both high sensitivity and rapid processing, which were conventionally difficult to achieve, are achieved with the best balance. I knew I could do it. Furthermore, the occurrence of silver stains can be effectively prevented to a practically acceptable level. In particular, by adopting the constitution of the present invention, as described later, the developing time is within 15 seconds, and the dry to
It is excellent in that it can perform a surprisingly ultra-quick processing with a Dry processing time of 60 seconds or less.

Further, the (100) plane of the silver halide grains used in the present invention /
The ratio of (111) faces is preferably 3 or more, particularly preferably 4
Or more, more preferably 5 or more. The upper limit of the above ratio is 100% for the (100) plane. Where (100)
If the / (111) plane is less than 1, the photosensitivity in the near infrared region will be significantly lost, and even if it is less than 3, the photosensitivity is still insufficient in the present invention, which is not preferable. On the contrary, when the above-mentioned ratio is 3 or more, a high level of photosensitivity in the near-infrared region starts to be secured, and high sensitivity is preferable.

The silver halide grains having a (100) face / (111) face ratio of 3 or more according to the present invention can be prepared by various methods. The most common method is to keep the pAg value during grain formation at a constant value of 8.10 or less and to add silver nitrate aqueous solution and alkali halide aqueous solution at a faster rate than the dissolution rate of particles and at the same time select a large rate without re-nucleation. Method (so-called control double jet method). More preferably, the pAg value is 7.80 or less,
More preferably, the pAg value should be 7.60 or less. When silver halide grain formation is divided into two processes, nucleation and its growth, there is no limitation on the pAg value during nucleation, and the pAg value during growth is 8.10 or less, more preferably 7.80 or less, and further preferably 7.60. The following is good. The method of reacting the soluble silver salt with the soluble halide may be a one-sided mixing method, but the simultaneous mixing method is preferable in order to obtain good monodispersity.

The silver halide emulsion used in the present invention is (100) plane /
The silver halide grains having a (111) face ratio of 3 or more, preferably 4 or more, more preferably 5 or more are contained in an amount of preferably 50 wt% or more, more preferably 60 wt% or more, and particularly 80 wt%. % Or more is preferable.

These emulsions may be coarse grains or fine grains, or mixed grains thereof, but preferably have an average grain size (measured by, for example, a projected area method or a number average method) of about 0.
Desirably, the emulsion grains are composed of 04 μ to 1.0 μ, and more preferably 0.2 μ to 0.7 μ. The particle shape is preferably cubic, but if it satisfies the surface index condition of the present invention, it may be potato-like, spherical, plate-like, or tabular with a particle size of 5 times or more of the particle thickness (see RESEARCH DISCLOSURE for details. ) Item No.22534 p.20 ~ p.58 (19
(January 1983)} and anomalous crystal forms. A substantially non-photosensitive emulsion (for example, an internally fogged fine grain emulsion) may be mixed with these photosensitive emulsions. Needless to say, emulsions having different grain sizes, halide compositions, etc. may be separately coated in different layers to increase the exposure latitude. Particle size 0.1-2.0
μm is preferred.

Further, as the particle size distribution, a narrow particle size, that is, a so-called “monodisperse” particle size is preferably used. As a monodisperse emulsion, more specifically, the average grain size is ± 40
An emulsion containing 90% or more of all grains within%, preferably 90% or more of all grains within ± 20% is preferably used.

Further, even if the crystal structure of the silver halide grains is uniform to the inside, it has a layered structure in which the inside and the outside are different, and it is described in British Patent No. 635,841 and U.S. Patent No. 3,622,318. Such a so-called conversion type may be used. Further, it may be of a type in which a latent image is mainly formed on the surface or an internal latent image type in which the latent image is formed inside the particles.

The sensitive material of the present invention may contain iridium ions.

Inclusion of iridium ions is achieved by adding a water-soluble iridium compound (eg hexachloroiridium (III) or hexachloroiridium (IV) salt) in the form of an aqueous solution during preparation of a silver halide emulsion. . It may be added in the form of the same aqueous solution as the halide for grain formation, may be added before grain formation, during grain formation, or after grain formation until chemical sensitization. This is a preferable addition when forming particles.

In the present invention, the iridium ion is preferably used in an amount of 10 ^-8 to 10 ^-5 mol per mol of silver halide, more preferably 5 × 10 ^{-7 to} 5 × 10 ^-6 mol, particularly preferably 10 ^-7 to 10 mol.
^-6 mol.

Here, if the iridium ion is less than 10 ^-8 mol, it is not preferable in that the high-illuminance photosensitivity cannot be further improved. On the other hand, if it exceeds 10 ^-5 mol, desensitization with respect to infrared photosensitivity occurs. It is not preferable because it has drawbacks such as

In the present invention, the water-soluble iodine compound (for example, potassium iodide, sodium iodide, ammonium iodide, etc.) is used in the middle and late stages of grain formation, immediately after desalting and before chemical sensitization,
It may be at any time immediately after the chemical sensitization and before the infrared sensitizing dye is added, or immediately after the infrared sensitizing dye is added and immediately before the coating, but it is particularly preferable between the latter stage of grain formation and the before chemical sensitization. Further, the water-soluble iodine compound is 5 × 10 ⁻⁵ mol to 2 × per mol of silver halide.
It is 10 ^-2 mol, preferably 2 x 10 ^-4 mol to 5 x 10 ^-3 mol, and more preferably 5 x 10 ^-4 mol to 3 x 10 ^-3 mol. If the amount of the water-soluble iodine compound is less than 5 × 10 ^-5 mol, the storage stability cannot be improved, which is not preferable. On the other hand, if it exceeds 5 × 10 ^-2 mol, fog is generated to give a softened photographic property. Not preferable.

The water-soluble iodine compound used in the present invention does not include a spectral sensitizing dye.

The ratio of the water-soluble iodine compound to the infrared sensitizing dye is preferably 2: 1 to 100: 1 (molar ratio), more preferably 4: 1 to 50: 1.
(Molar ratio).

Both may be added at the same time, or one may be added first and then the other.

As a silver halide solvent for controlling the growth of the silver halide grains during formation of the silver halide grains, for example, ammonia, rhodan potassium, rhodan ammon, and thioether compounds (e.g., U.S. Patent Nos. 3,271,157 and 3,574,628).
No. 3, No. 3,704, 130, No. 4,297, 439, No. 4,276, 37
No. 4, etc.) thione compound (for example, JP-A-53-144,319)
No. 53-82,408, No. 55-77,737, etc.), amine compounds (for example, JP-A No. 54-100717, etc.) and the like can be used. In addition to the silver halide solvent, a compound that is adsorbed on the grain surface to control the crystal habit, such as a cyanine sensitizing dye, a tetrazaindene compound, or a mercapto compound, can be used during grain formation.

The (100) face / (111) face ratio of the particles can be measured by the Kubelka-Munk color adsorption method (hereinafter referred to as “Kbelka-Munk method”). In this method, (100) plane or (111) plane
A dye that is preferentially adsorbed on one of the faces and has a spectrally spectrally different association state of the dyes on the (100) face and the (111) face is selected. The (100) plane / (111) plane ratio can be determined by adding such a dye to the emulsion and examining the spectral spectrum with respect to the added amount of the dye in detail.

For the detailed ratio of the (100) plane of the surface of silver halide grains, see Tadaaki Tani, "Identification of Crystal Phase of Silver Halide Fine Particles in Photographic Emulsions by Utilizing Dye Adsorption Phenomenon", Japan Chemical Journal 6 , 942-946. It can be determined by the method described in (1984).

The silver halide photographic emulsion is prepared by a commonly used chemical sensitization method such as gold sensitization (US Pat. Nos. 2,540,085 and 2,3.9.
9,083), sensitization with Group VIII metal ions (US Pat. Nos. 2,448,060 and 2,598,079, etc.), sulfur sensitization (US Patents 1,574,944, 2,278,947, and 3,021,21).
5, No. 3,635,717), reduction sensitization (US Patent No. 2,
518,698, Research Disclosure
Sclosure) Vol.176 (1978.12) RD-17643, item III, etc.), sensitization with thioether compounds (e.g., U.S. Patent Nos. 2,521,926, 3,021,215, and 3,046,133,
No. 3,165,552, No. 3,625,697, No. 3,635,717
No. 4,198,240, etc.) or various sensitizing methods combined therewith.

More specific chemical sensitizers include sodium thiosulfate, Allyl thiocarbamide,
Sulfur sensitizers such as thiourea, thiosulfate, thioethers and cystine; precious metal sensitizers such as potassium chloroaurate, aura thiosulfate and potassium chloro palladate;
Examples thereof include reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.

In the present invention, as an infrared sensitizing dye, Japanese Patent Application No. 61-235
It is preferred to use at least one tricarbocyanine dye and / or a 4-quinoline nucleus-containing dicarbocyanine dye as described in No. 515.

The above infrared sensitizing dye used in the present invention is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 1 mol per mol of silver halide.
It is contained in the silver halide photographic emulsion at a ratio of x10 ^-6 mol to 1 x 10 ^-3 mol, particularly preferably 2 x 10 ^-6 mol to 5 x 10 ^-4 mol.

The above infrared sensitizing dye used in the present invention can be directly dispersed in an emulsion. In addition, these are first a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. The dye is usually added after chemical sensitization in many cases, but it may be added during grain formation or before chemical sensitization. Ultrasonic waves can also be used for dissolution.

U.S. Pat.Nos. 2,912,345 and 3,342,6 are added to the emulsion.
Methods described in No. 05, No. 2,996,287, No. 3,429,835, etc. can also be used. The above infrared sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but as described above, it may be dispersed in any step of preparation in the silver halide emulsion. Can be dispersed.

The sensitizing dye according to the present invention may be used in combination with other sensitizing dyes. For example, U.S. Pat.No. 3,703,377,
No. 2,688,545, No. 3,397,060, No. 3,615,635
No. 3,628,964, British Patent No. 1,242,588, No. 1,
No. 293,862, Japanese Patent Publication No. 43-4936, No. 44-14030, No. 43-107
73, U.S. Patent No. 3,416,927, Japanese Patent Publication No. 43-4930, U.S. Patent Nos. 3,615,613, 3,615,632 and 3,617,295.
No. 3,635,721 and the like can be used in combination.

In the present invention, Japanese Patent Application No. Sho 61-23551 together with the sensitizing dye described above is used.
The compounds described in No. 5 can be used for the purpose of further enhancing the supersensitizing effect and / or further enhancing the preservability.

In the present invention, Japanese Patent Application No. 61-235 is used together with the above-mentioned sensitizing dye.
Photosensitivity storage stability improvers such as those described in No. 515 can be used in amounts of from about 0.01 to 5 grams per mole of silver halide in the emulsion.

The ratio (weight ratio) of the above-mentioned infrared sensitizing dye and the above-mentioned sensitizing material storability improving agent is advantageously used in the range of 1/1 to 1/300,
Particularly, the range of 1/2 to 1/50 is advantageously used.

The supersensitizer or sensitizer preservative improving agent used in the present invention can be directly dispersed in the emulsion, and a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, Acetone etc.) or a mixed solvent containing a plurality of these solvents may be dissolved and added to the emulsion. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of addition.

The infrared sensitizing dye and the light-sensitive material storage stability improver may be added to the emulsion prior to the addition of the infrared sensitizing dye described above,
It may be added later. Further, these may be dissolved separately from the infrared sensitizing dye, and these may be separately added to the emulsion at the same time, or may be mixed and then added to the emulsion.

Antihalation dye and / or used in the present invention
Alternatively, a dye having substantial absorption at a long wavelength of 750 nm or more is used as the anti-irradiation dye. Here, the antihalation dye is used in the intermediate layer, the undercoat layer, the antihalation layer, the back layer, the emulsion layer and the like, and the antiirradiation dye is used in the intermediate layer and the like in addition to the emulsion layer. Further, these dyes are preferably used in an amount of 10 ^{−3 to 1} g / m ² , more preferably 10 ^{−3 to} 0.5 g / m ² . For example, U.S. Patent Nos. 2,895,955, 3,177,078, and 4,581,
No. 325, dyes described in JP-A-50-100,116, and Japanese Patent Application No. 61-
The dyes described in 162987 and Japanese Patent Application No. 61-235515 are preferably used.

These dyes may be used alone or in combination of two or more.

Further, instead of the above-mentioned dye, or these dyes may be used in combination. Examples of the dyes used instead or in combination include pyrazolone oxonol dyes described in U.S. Pat.No. 2,274,782 and U.S. Pat.
Diarylazo dyes described in 6,879, U.S. Pat.
3,207, No. 3,384,487 styryl dyes and butadienyl dyes described, U.S. Patent No. 2,527,583 merocyanine dyes, U.S. Patent No. 3,486,897, No. 3,652,284.
And the oxonol dyes described in U.S. Pat. No. 3,718,472, and the enaminohemioxonol dyes described in U.S. Pat. No. 3,976,661.

Various compounds can be added to the photographic light-sensitive material of the present invention in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material. These compounds include many heterocyclic compounds including nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene, 1-phenyl-5-mercaptotetrazole, and the like. An extremely large number of compounds such as mercury compounds, mercapto compounds and metal salts have long been known. An example of a compound that can be used is CE
“The Theory of the Photographic Process” by K. Mees
(3rd edition, 1966), pp. 344 to 349, with reference to the original literature. For example, U.S. Pat.No. 2,131,038 and U.S. Pat.
Thiazolium salts described in 94,716, etc .; Azaindenes described in US Pat. Nos. 2,886,437 and 2,444,605, etc .; Urazoles described in US Pat. No. 3,287,135; US Pat. Sulfocatechols described in US Pat. No. 623,
Oximes described in US Pat. No. 448; US Pat. No. 2,4
03,927, 3,266,897, 3,397,987 and other mercaptotetrazoles, nitrones;
Nitroindazoles; Polyvalent metal salts described in US Pat. No. 2,839,405
s); thiuronium salts described in US Pat. No. 3,220,839; US Pat. No. 2,566,26
No. 3, and No. 2,597,915, etc., include salts of palladium, platinum, and gold.

In the present invention, as a matting agent, US Pat.
Nos. 2,701,245, 4,142,894, and homopolymers of polymethylmethacrylate as described in 4,396,706 or polymers of methylmethacrylate and methacrylic acid,
Fine particles of organic compounds such as dendritic powder and inorganic compounds such as silica, titanium dioxide, sulfuric acid, strontium, and barium can be used. Particle size is 1.0 to 10μ
m, and particularly preferably 2 to 5 μm.

Silicone compounds described in U.S. Pat.Nos. 3,489,576 and 4,047,958 as slipping agents in the surface layer of the photographic light-sensitive material of the present invention, in addition to colloidal silica described in JP-B-56-23139, paraffin wax, high-grade Fatty acid ester,
Denden powder derivatives and the like can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer of the photographic light-sensitive material of the present invention.

Furthermore, the hydrophilic colloid layer of the photographic light-sensitive material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid, a copolymer with acrylic acid, a styrene-butadiene copolymer, or a polymer or copolymer comprising a monomer having an active methylene group can be preferably used.

The silver halide photographic light-sensitive material of the present invention may have a non-light-sensitive layer such as a surface protective layer, an intermediate layer and an antihalation layer in addition to the light-sensitive silver halide emulsion layer.

The number of silver halide emulsion layers may be two or more, and the sensitivity and gradation of the two or more silver halide emulsion layers may be different.
Further, it may have one or more silver halide emulsion layers or a non-photosensitive layer on both sides of the support.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in smoothness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

Examples of the antistatic agent include U.S. Pat.No. 4,201,586, JP-A-60-80849, JP-A-59-74554, and Japanese Patent Application No. 60-249021.
Fluorine-containing surfactant or polymer described in 61-32462, JP-A-60-76742, 60-80846, 60-80848,
No. 60-8083, No. 60-76741, No. 58-208743, Japanese Patent Application No. 61
No. 13398, No. 61-16056, No. 61-32462, and the like, or JP-A-57-57
The conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in JP-A-204540 and Japanese Patent Application No. 61-32462 can be preferably used. As the inorganic antistatic agent, conductive tin oxides, zinc oxides or complex oxides obtained by doping these metal oxides with antimony or the like described in JP-A-57-118242 can be preferably used.

In the silver halide photographic emulsion layer or intermediate layer used in the present invention, in addition to gelatin as a protective colloid, acylated gelatin such as phthalated gelatin or malonated gelatin,
Cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; soluble starch such as dextrin; hydrophilic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide and polystyrene sulfonic acid can be added.
Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

Also U.S. Pat.Nos. 3,411,911, 3,411,912, and 3,
No. 142,568, No. 3,325,286, No. 3,547,650, Japanese Patent Publication No. 45-5311 etc., alkyl acrylate, alkyl methacrylate, acrylic acid, polymer latex made of homopolymer or copolymer of glycidyl acrylate, etc. Improved dimensional stability of
It may be contained for the purpose of improving the physical properties of the film.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may contain a plasticizer, a brightening agent, an air fog preventive agent, a toning agent and the like.

The support is preferably a polyethylene terephthalate film or a cellulose triacetate film, and particularly preferably colored blue.

In order to improve the adhesion to the hydrophilic colloid layer, the support is preferably one whose surface has been subjected to corona discharge treatment, glow discharge treatment or ultraviolet irradiation treatment. Alternatively, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex or the like may be provided.
You may further provide a gelatin layer on it.

An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided.

By applying a surface treatment to these undercoat layers, the adhesion with the hydrophilic colloid layer can be further improved.

The exposure for obtaining a photographic image is performed by a tungsten lamp, a cathode ray tube flying spot, a light emitting diode, a laser beam (for example, a gas laser, a YAG laser, a dye laser,
Any of various known light sources including infrared light such as a semiconductor laser) can be used. Exposure time is 1/10 ⁵
Use ~ 1/10 ⁸ seconds. If necessary, the spectral composition of light used for exposure can be adjusted with a color filter. The light-sensitive material of the present invention is particularly suitable for use in a scanner using a semiconductor laser.

The combination of the dihydroxybenzenes and the 1-phenyl-3-pyrazolidones of the present invention is most preferable in that a good performance is easily obtained for the developing agent used in the black-and-white developing solution used in the present invention. Of course, in addition to this, a p-aminophenol-based developing agent may be contained.

As the dihydroxybenzene developing agent used in the present invention, hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5
-Dimethylhydroquinone, etc., but hydroquinone is particularly preferable.

Examples of the p-aminophenol-based developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, and N- (4-hydroxyphenyl) glycine. ,
2-Methyl-p-aminophenol, p-benzylaminophenol and the like are available, but N-methyl-p-aminophenol is preferred.

The developing agent is usually preferably used in an amount of 0.01 mol / l to 1.2 mol / l.

As a preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
and so on. The sulfite is preferably 0.2 mol / l or more, and particularly preferably 0.4 mol / l or more. The upper limit is preferably up to 2.5 mol / l.

The pH of the developer used in the present invention is preferably in the range of 9 to 13. More preferably, the pH is in the range of 10 to 12.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
It contains a pH adjusting agent such as sodium triphosphate or potassium triphosphate.

A buffering agent such as Japanese Patent Application No. 61-28708 (borate), JP-A No. 60-93433 (for example, saccharose, acetoxime, 5-sulfosalicylic acid), phosphate and carbonate may be used.

As additives used in addition to the above components, development inhibitors such as sodium bromide, potassium bromide and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol and methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. A mercapto-based compound, an indazole-based compound such as 5-nitroindazole, and an antifoggant such as a benztriazole-based compound such as 5-methylbenztriazole may be included, and if necessary, a toning agent, a surfactant, an antifoaming agent. , Water softener, JP-A-56-10624
It may include the amino compound described in No. 4 and the like.

In the present invention, a silver stain preventing agent is used in the developer, for example, JP
The compounds described in 56-24347 can be used.

Amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer of the present invention.

In addition, LFA Meson's "Photographic Processing Chemistry", published by Focal Press (1966)
226-229, U.S. Pat.Nos. 2,193,015 and 2,592,3
No. 64, JP-A-48-64933 and the like may be used.

Conventional treating agents usually consist of multiple parts (number of agents) configurations. When it is composed of one part, it is possible that the components deteriorate or change due to the interaction between the components of the treatment agent contained in the treatment agent after the treatment agent is manufactured and before it is used as a solution. This is to avoid it. A treatment agent consisting of multiple parts is usually used as a treatment liquid (use liquid) for the first time by dissolving and mixing each part in water prepared in advance and finally making the volume constant with water. .

Each part of this treating agent is usually a thicker liquid than the so-called working liquid, that is, a concentrated liquid.

In the present invention, the developer concentrate is usually replenished with water for diluting it as the photosensitive material is processed in the automatic processor. In that case, the developer concentrate is composed of one part as in the present invention. It is most preferable from the viewpoint of machine simplicity and replenishment accuracy. Although it is possible to use a method of diluting it with water with a composition of 2 parts, in the case of 2 parts, it is necessary to increase the number of pumps by that amount and to separate it into 2 parts just before use by devising the packaging material. Therefore, there is a problem that the work becomes complicated and the automatic developing machine becomes complicated.

In the present invention, "development time" and "fixing time" are respectively
The time from the immersion of the photosensitive material to be processed in the developing tank solution of the developing machine to the immersion in the next fixing solution, from the immersion in the fixing tank solution to the immersion in the next washing tank solution (stabilizing solution) Tell the time

The "washing time" means the time of immersion in the washing tank liquid.

The term "drying time" is usually 35 ° C to 100 ° C, preferably 40 ° C.
A drying zone to which hot air of ~ 80 ° C is blown is installed in the automatic processing machine, but it refers to the time during which the drying zone enters.

The developing temperature and time are preferably about 25 ° C to about 50 ° C for 6 seconds to 2 minutes, more preferably 30 ° C to 40 ° C for 6 seconds to 30 seconds, and particularly preferably 30 ° C to 40 ° C for 6 seconds to 15 minutes. It is to develop in seconds.

The fixer is an aqueous solution containing thiosulfate, pH 3.8 or above,
Preferably it has 4.2 to 5.5. More preferably pH 4.65 ~
5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which have thiosulfate ion and ammonium ion as essential components, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 6 mol / l.

The fixing solution may contain a water-soluble aluminum salt which acts as a hardening agent, and they include, for example, aluminum chloride, aluminum sulfate and potassium alum.

Tartaric acid, citric acid, gluconic acid or their derivatives may be used alone or in combination of two or more in the fixing solution. These compounds are 0.005 per fixer
Those containing more than 1 mol are effective, especially 0.01 mol / l to 0.03 mol
/ l is especially useful.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, and the like.

Preservatives (eg, sulfites, bisulfites), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, sulfuric acid), chelating agents having a softening effect on water, and Japanese Patent Application The compounds described in JP-A-60-218562 may be included.

The fixing temperature and time are the same as in the case of development.
6 seconds to 2 minutes at about 50 ° C is preferable, but 6 seconds to 30 at 30 ° C to 40 ° C
Second is more preferable, and further preferably at 30 ° C to 40 ° C for 6 seconds to
It takes 15 seconds to settle.

When the fixer concentrate is replenished to the automatic processor by the method of the present invention as the light-sensitive material is processed, along with water to dilute it, the fixer concentrate is most often composed of one agent. The preference is the same as for the developer.

It is at pH 4.5 or higher, more preferably at pH 4.65 or higher, that the fixer stock solution can exist stably as one agent. This is because when the pH is less than 4.5, the thiosulfate is decomposed and finally sulfided, especially when the fixing solution is left for many years until it is actually used. Therefore, when the pH is in the range of 4.5 or higher, the generation of sulfurous acid gas is small and the working environment is improved. The upper limit of pH is not so severe, but if it is fixed at an excessively high pH, the pH of the membrane becomes high even after washing with water, the swelling of the membrane becomes large, and the drying load becomes large.
In the fixing solution in which the aluminum salt is used for hardening, the aluminum salt precipitation / precipitation prevention pH is limited to 5.5.

In the present invention, either the developing solution or the fixing solution may be a so-called working solution which does not require the above-mentioned dilution water (that is, the stock solution is replenished as it is).

The supply amount of each concentrate to the treatment tank liquid and the mixing ratio with the diluting water can be variously changed depending on the composition of the concentrating liquid, but in general, the ratio of the condensing liquid to the diluting water is 1 to 0-8. The total amount of each of the developing solution and the fixing solution is preferably 50 ml to 1500 ml per 1 m ² of the light-sensitive material.

In the present invention, the light-sensitive material is developed, fixed and then washed with water or stabilized.

For the washing or stabilizing treatment, any method known in the art can be applied, and water containing various additives known in the art can also be used as washing water or a stabilizing solution. By using anti-mildew water as washing water or stabilizing solution, it is possible not only to save water with a replenishment amount of 3 l or less per 1 m ^{2 of} light-sensitive material, but also to eliminate the need for pipes installed in the developing machine. It is possible to reduce the stock tank. That is, the preparation diluting water for the developing solution and the fixing solution and the washing water or the stabilizing solution can be supplied from the common one stock tank, and the automatic developing machine can be made more compact.

When water treated with antifungal means is used in combination with washing water or a stabilizing solution, generation of scale can be effectively prevented.
A water-saving treatment of 0 to 3 liters, preferably 0 to ¹ per m ² can be performed.

Here, when the amount of replenishment is 0, the replenishment amount is 0, and the replenishment amount is not replenished except that the amount of the wash water in the wash tank decreased by natural evaporation or the like is appropriately replenished. It refers to the case where a processing method is performed.

As a method for reducing the replenishment amount, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the light-sensitive material after fixing is gradually processed in a cleaner direction, that is, the processing solution which is not contaminated with the fixing solution is sequentially processed, so that the efficiency is further improved. Washed with water. According to this, unstable thiosulfate and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and a more remarkable stabilizing effect is obtained. The amount of flush water is much smaller than before.

When washing with a small amount of washing water in the method of the present invention, it is more preferable to provide a squeeze roller washing tank described in Japanese Patent Application No. 61-163217.

Further, a part or all of the overflow liquid from the washing or stabilizing bath produced by replenishing the washing or stabilizing bath with antifungal means depending on the treatment is disclosed in JP-A-60-235133.
It can also be used for a processing solution having a fixing ability, which is the previous processing step as described in No. This is more preferable because the stock water can be saved and the waste liquid can be reduced.

As the antifungal means, an ultraviolet irradiation method described in JP-A-60-263939, a method using a magnetic field described in 60-263940, and an ion exchange resin described in 61-131632 are used. How to make pure water, Japanese Patent Application No. 60/53807, 60-295894
Nos. 61-63030 and 61-51396 can be used.

Furthermore, LEWest “Water Quality Criteria” Photo Sci
& Eng. Vol. 9 No. 6 (1965), MWBeach “Microbiolog
ical Growths in Motion-Picture Processing "SMPTE J
ournal Vol.85, (1976), RODeegan, “Photo Processi
ng Wash Water Biocides "J.Imaging Tech.Vol 10, No.6
(1984) and JP-A-57-8542, 57-58143, and 58-10.
5145, 57-132146, 58-18631, 57-97530
No. 57-157244 and the like, antibacterial agents, antifungal agents, surfactants and the like can also be used in combination.

Furthermore, RTKreiman's J.Image, Tech10,
(6) Isothiazoline compounds described in 242 (1984), RESEARCH DISCLOSURE Volume 205, Item 20526 (1981)
, May issue), isothiazoline compounds described in Vol. 228, Item 22845 (April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. Can also be used as a bacteriostatic agent (Microbiocide).

Further, specific examples of the antifungal agent include phenol, 4-chlorophenol, pentachlorophenol, cresol,
O-phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloroacetamide, p-hydroxybenzoic acid ester, 2-
(4-thiazolyl) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium chloride, N- (fluorodichloromethylthio) -phthalimide, 2,4,4'-trichloro-
2'-hydroxydiphenyl ether and the like.

Others, "The Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (5
7), "Handbook of Antibacterial and Antifungal Technology" may also include chemicals as described in Japan Antibacterial and Antifungal Society, Gihodo (Showa 61).

It is preferable that the water stored in the water stock tank after being subjected to the mildew proofing is used both as the diluting water for the stock solution of the processing solution such as the developing solution fixing solution and as the rinsing water because it requires a small space. However, it is also possible to separately store the preparation diluting water and the washing water (or the stabilizing solution) which have been subjected to the mildew-proofing method and store them in separate tanks, or only one of them may be directly taken from tap water.

When stored separately in different tanks, various additives can be added to the washing water (or stabilizing bath) in addition to the antifungal means of the present invention.

For example, a chelate compound having a chelate stability constant log K value with aluminum of 10 or more may be contained. These are effective in preventing whitening in the wash water when the fixing solution contains an aluminum compound as a hardening agent.

Specific examples of the chelating agent include ethylenediaminetetraacetic acid (log K = 16.1, the same applies hereinafter), cyclohexanediaminetetraacetic acid (17.6), diaminopropanoltetraacetic acid (13.8),
Diethylenetriamine pentaacetic acid (18.4), triethylenetetramine hexaacetic acid (19.7), etc. and their sodium salts,
There are potassium salts and ammonium salts, and the addition amount thereof is preferably 0.01 to 10 g / l, more preferably 0.1 to 5 g / l.

Further, JP-A-58-434542, JP-A-58-114035 and JP-A-61-83534
It is also possible to incorporate a silver image stabilizer as described in Japanese Patent Laid-Open Publication No. 1994-0923 into the wash water.

Further, various surfactants can be added to the washing water of the present invention for the purpose of preventing unevenness of water droplets. As the surfactant, any of cation type, anion type, nonionic type and amphoteric type may be used. Specific examples of the surfactant include compounds described in "Surfactant Handbook" published by Engineering Book Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing an image. For example, adjust membrane pH (eg pH 3-8)
Various buffers for (eg borate, metaborate,
Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Typical examples include aldehydes such as polycarboxylic acid used in combination) and formalin.
In addition, various additives such as chelating agents, bactericides (thiazole-based, isothiazole-based, halogenated phenols, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, hardeners, etc. can be used. Of course, the same or different target compounds may be used in combination of two or more kinds.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as a film pH adjuster after the treatment in order to improve the image storability.

Washing by the above method or stabilizing bath temperature and time is 0 ° C
6 seconds to 2 minutes at ~ 50 ° C is preferred, but 6 seconds at 15 ° C to 40 ° C
It is more preferably 30 seconds, and further preferably treated at 15 ° C to 40 ° C for 6 seconds to 15 seconds.

According to the method of the present invention, the developed, fixed and washed photographic material is squeezed out of washing water, that is, dried through a squeeze roller. Drying is performed at about 40 ° C to about 100 ° C, and the drying time can be appropriately changed depending on the ambient conditions.
Usually about 5 seconds to 1 minute, but more preferably 40 ° C
It is about 5 to 30 seconds at -80 ° C.

According to the method of the present invention, the so-called Dry to Dry processing time before developing, fixing, washing and drying is within 3 minutes and 30 seconds, preferably within 100 seconds, and most preferably within 60 seconds. That is. As the treatment of the infrared laser scanner light-sensitive material of the present invention, it is particularly preferable to control the development time.
It should be within 15 seconds and the processing time for Dry to Dry should be within 60 seconds. In addition to such shortening of the processing time, simplification of liquid preparation work and simplification of maintenance can be achieved at the same time by the replenishing liquid which is a one-part constitution of the developing liquid and the fixing liquid.

Here, "Dry to Dry" is processed from the moment the tip of the photosensitive material to be processed enters the film insertion part of the automatic processing machine,
It is the time until the tip comes out of the machine.

(Example) Next, the specific example of an Example is shown. However, the present invention is not limited to these specific examples.

Example 1 (1) Preparation of Monodisperse Silver Halide Emulsion of the Present Invention A suitable amount of ammonia was added to a container containing gelatin, potassium bromide and water and heated to 55 ° C., and pA in the reaction container was then added.
While maintaining the g value at 7.60, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing hexachloroiridium (III) at a molar ratio of iridium to silver of 10 ^-7 mol were added by the double jet method to obtain an average particle size. Size is 0.55
μ monodisperse silver bromide emulsion grains were prepared. In this emulsion grain, 98% of the total grain number was present within ± 40% of the average grain size. Also, in the latter stage of grain formation, 1 × 10 ^-3 per mol of silver
Molar potassium iodide was added. After the emulsion was desalted, the pH was adjusted to 6.2 and the pAg was adjusted to 8.6, and gold / sulfur sensitization was performed with sodium thiosulfate and chloroauric acid to obtain desired photographic properties. The (100) face / (111) face ratio of this emulsion was 93/7 when measured by the Kubelka-Munk method. This emulsion is designated as Emulsion A.

Next, put a very small amount of thioether into a container containing gelatin, potassium chloride and water and heated to 70 ° C, and then add an aqueous solution of silver nitrate and potassium bromide and sodium chloride (molar potassium chloride and potassium chloride) in equimolar amounts. A monodispersed silver chlorobromide emulsion grain having an average grain size of 0.52μ was prepared by simultaneously adding a mixture aqueous solution having a sodium molar ratio of 80/20) by the double jet method. Also in this case, 10 ⁻⁷ mol of iridium ion (trivalent) was added to the added aqueous halide solution in a molar ratio to silver, and 10 ⁻³ mol of potassium iodide was added per 1 mol of silver in the latter stage of grain formation. The (100) / (111) plane ratio was 95/5. Emulsion B was obtained by subjecting these emulsion grains to desalting and optimum chemical sensitization in the same manner as in A. Further potassium bromide and water entered
After adding an appropriate amount of ammonia to a container heated to 60 ° C, keep the pAg value in the reaction container at 7.60 and adjust the molar ratio of iridium to silver nitrate aqueous solution to 10 ^-7 mol of hexachloroiridium. The (III) acid salt was added.
An aqueous solution of potassium bromide and potassium iodide with a molar ratio of 98/2 was added by the double jet method, and the molar ratio to silver was calculated.
Adding 10 ^-3 mol of potassium iodide in the late stage of particle formation,
An optimum chemically sensitized silver iodobromide emulsion C having a monodisperse average grain size of 0.5 μ and a (100) / (111) plane ratio of 91/9 was obtained.

In the preparation method of Emulsion A, grains were formed with a pAg value of 8.10, an average grain size of 0.53μ and a (100) / (111) ratio of 70.
An emulsion of / 30 was made and named Emulsion D.

(2) Preparation of Comparative Silver Halide Emulsion In the method of preparing Emulsion B, the molar ratio of potassium bromide to potassium chloride was 30/70, the average grain size was 0.54μ, and (100) / (111) An emulsion having an aspect ratio of 97/3 was prepared and named Emulsion E.

(3) Preparation of emulsion coating solution 1 kg of each of these emulsions A to E was heated in a weighed container at 40 ° C. to dissolve the emulsion, and the following infrared sensitizing dye in methanol solution (9 X 10 ^-4 mol / l) 70 cc, aqueous solution of the following supersensitizer (4.4 x 10 ^-3 mol / l) 90 cc, methanol solution (2.8 x 10 ^-2 mol) of the following sensitizing agent storability improver / l) 35cc, 4-hydroxy-6-methyl-1,3,3a, 7-
A tetrazaindene aqueous solution, a coating aid dodecylbenzene sulfonate aqueous solution, and an aqueous solution of a thickener polypotassium-p-vinylbenzene sulfonate compound were added to prepare an emulsion coating solution.

(Infrared sensitizing dye) (Supersensitizer) 4,4'-bis [2,6-di (naphthyl-2-oxy) pyrimidin-4-ylamino] stilbene-2,2'-disulfonic acid disodium salt Agent) (4) Preparation of coating liquid for surface protective layer of light-sensitive material layer 10 wt% gelatin aqueous solution heated to 40 ° C., thickening agent sodium styrene sulfonate aqueous solution, matting agent polymethylmethacrylate fine particles (average particle size 3.0 μm) ,
Hardener N, N'-ethylenebis- (vinylsulfonylacetamide), coating aid sodium t-octylphenoxyethoxyethane sulfonate aqueous solution, polyethylene surfactant aqueous solution as antistatic agent, and aqueous solution of fluorine-containing compound having the following structure And were added to obtain a coating solution.

C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK and C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ -O ₁₅ H (5) Preparation of back coating solution To 1 kg of a heated 10 wt% gelatin aqueous solution, a thickening agent sodium polystyrene sulfonate aqueous solution, the following back dye aqueous solution (5 × 10 ^-2 mol / l) 50 cc, a hardening agent N, N′-ethylenebis- (vinyl) Sulfonylacetamide) aqueous solution and a coating aid sodium t-octylphenoxyethoxyethane sulfonate aqueous solution were added to prepare a coating solution.

(Back dye) (6) Preparation of coating liquid for surface protective layer of back layer To 10 wt% gelatin aqueous solution heated to 40 ° C., thickener sodium polystyrene sulfonate aqueous solution, matting agent polymethylmethacrylate fine particles (average particle size 3.0 μm), coating A coating solution was prepared by adding an auxiliary aqueous solution of sodium t-octylphenoxyethoxyethane sulfonate, an aqueous solution of a polyethylene-based surfactant as an antistatic agent, and an aqueous solution of a fluorine-containing compound having the following structure.

C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) CH ₂ COOK and C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) (CH ₂ CH ₂ -O ₁₅ H (7) Preparation of coating sample The coating solution was coated together with the coating solution for the surface protective layer of the back layer on one side of the polyethylene terephthalate support so that the coating amount of gelatin was 4 g / m ^2, and then on the other side of the support (3 Samples in which the emulsion coating solution containing the near-infrared sensitizing dye described above and the coating solution for the surface protective layer therefor were coated such that the silver coating amount was 3.5 g / m ² and the swelling percentage of the coating film was changed. The amount of the hardener in the coating film for the surface protective layer was adjusted variously to prepare the sample, the names of the prepared samples, the names of the emulsions used and the swelling percentages used are as shown in Table 1 below.

(8) Method of measuring swelling rate a) Incubating the coated sample at 38 ° C. and 50% relative humidity, b) measuring the layer thickness, c) soaking in distilled water at 21 ° C. for 3 minutes, and d) The percentage change in layer thickness compared to the layer thickness measured in step b) is measured.

(9) Ordinary sensitometry Seven kinds of samples of (7) are kept at 25 ° C and 65% RH in temperature and humidity, and 7 days after application, the seven kinds of samples are applied at room temperature with a semiconductor laser having a wavelength of 780 nm. A scanning exposure of 10 ^-7 seconds was performed. After exposure, development processing was carried out by each processing method of the following processing steps (I) and (II).

<Process (I)><developer formulation (38l for Formulation)> 38l for Part A Potassium 1107g Potassium sulfite 1680g sodium bicarbonate 285g borate 38g hydroxide diethylene 456g Ethylenediaminetetraacetic acid 63.5 g 5-methylbenzotriazole 2.28g hydroquinone 1140g water up to 9.50l Part B glacial acetic acid 416.5g diethylene 644.5G 5-nitroindazole 9.5 g 1-phenyl-3-pyrazolidone 57 g Part C glutaraldehyde 187.3g meth sodium bisulfite 478.8g water Stay up--to 950 ml starter acetate 270g 300g of potassium bromide up to 1.5l with water <Developer preparation method> Add 20l of water to a 50l replenisher stock tank, then add and dissolve Part A, Part B and Part C while stirring, and finally To 38 l with water and used as a developer replenisher (pH 10.
30).

The developer added at a ratio of 20 ml of the starter to the developer replenisher 1 was first filled in a development processing tank of an automatic processor (pH 10.15), and thereafter, the development solution was processed every time the photosensitive material was processed. 60ml / B4 size replenisher (25.7cm x 36.4c
m) replenished.

<Fixer formulation (38l formulation)> Part A Ammonium thiosulfate 70wt / vol% 7.6l Ethylenediaminetetraacetic acid / disodium dihydrate 0.76g Sodium sulfite 570g Boric acid 380g Sodium hydroxide 254.6g Acetic acid 570g Water 9.5l Part B Aluminum sulphate 380g Sulfuric acid 148.2g 1.9l with water <Fixing solution preparation method> Add 20l of water to a stock tank of about 50l of replenisher, then add and dissolve Part A and Part B while stirring, and finally add water. To 38 l and used as fixer replenisher.

The same fixing solution replenisher was first filled into the fixing processing tank of the automatic processor (pH 4.25). Thereafter, each time the light-sensitive material was processed, the fixing solution replenishing solution was replenished with one sheet of 60 ml / B4 size.

Each processing step was performed as follows (dry to dry processing for 96 seconds).

<Process II> The compositions of the concentrated solutions of the developing solution and the fixing solution are as follows.

<Developer concentrate> Potassium hydroxide 56.6g Sodium sulfite 200g Diethylenetriaminepentaacetic acid 6.7g Potassium carbonate 16.7g Boric acid 10g Hydroquinone 83.3g Diethylene glycol 40g 4-Hydroxymethyl-4-methyl-1-phenyl-3
-Pyrazolidone (compound of the invention) 5.5 g 5-methylbenzotriazole 2 g Adjust to 1 with water (adjust to pH 11.00).

Replenisher kit size 5l <Fixing solution concentrate> Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid / disodium dihydrate 0.10g Sodium hydroxide 24g Adjust to 1 with water (adjust to pH 5.10 with acetic acid).

Replenisher kit size 5l (water stock tank liquid) Ethylenediaminetetraacetic acid disodium salt / dihydrate 0.5g / l Automatic developing machine Dry to Dry processing for 60 seconds Development tank (1) 7.5l 35 ℃ x 11.5 seconds Fixing tank ( 2) 7.5l 35 ° C x 12.5 seconds Water washing tank (3) 6.5l 20 ° C x 7.5 seconds Squeeze roller washing tank (7) 200ml Water stock tank (4) 25l Drying 60 ° C However, both developer and fixing tank temperature are maintained A heater was used to do this, but no cooling water was used.

When the development processing was started, each tank was filled with the following processing solutions.

Developing tank: Add 333 ml of the above concentrated developer solution, 667 ml of water and 10 ml of an aqueous solution containing 2 g of potassium bromide and 1.8 g of acetic acid to adjust the pH.
It was 10.50.

Fixing tank: 250 ml of the above fixing solution concentrated solution and 750 ml of water Washing tank and washing tank: The same composition as the above water stock tank solution The above described photosensitive material B4 size (25.7 cm x 36.4 cm) 20 ml developer concentrate and 40 ml water in stock tank Fixer tank 10 ml fixer concentrate and 30 ml stock tank water From the squeeze roller washing tank to the wash tank, add 60 ml of stock tank water (opposite the direction of the film) and run Processing continued. During this time the developer,
When both the fixer and the water are exhausted, a new replenisher is added in the same manner.

The results are shown in Table 2.

As shown in Table 2, the processing system of the present invention speeds up the processing without adversely affecting the photographic performance, simplifies preparation, reduces the space for the automatic developing machine and replenishment tank, and produces odor, especially odor generated from the fixing solution. All reductions have been achieved.

In terms of sensitivity, the lower the ratio of silver chloride, the higher the sensitivity when silver iodide is contained.
However, if the proportion of silver iodide is too high, the sensitivity will be high, but the gradation will be low, so there is a certain limit.

With respect to silver stain, it is better to lower the ratio of silver chloride as in the present invention, but there is a limit to the ratio of silver iodide in relation to the developing speed. The silver halide composition is defined in the present invention in terms of sensitivity, gradation, silver stain, and development speed. Further, in the rapid processing, the drying is one of the major factors controlling the processing time, and it depends on the swelling percentage. If the swelling percentage is 200% or less as in the present invention, rapid treatment can be achieved without treatment hardening, that is, without the disadvantage such as bad odor.

Example 2 The stability of 3-pyrazolidones in an alkaline solution was examined by allowing the composition of the developer concentrate of the treatment (II) to be sealed in a polybin in a stopper at 50 ° C. for 2 weeks. The results are shown in Table 3 below. .

Therefore, in order to use the developer as a single agent to provide a simple processing system as in the present invention, the object of the present invention cannot be achieved unless the 3-pyrazolidones are specified as the compound of the formula (I) of the present invention. I understand.

(Effect of the Invention) According to the present invention, in the processing of the silver halide photographic light-sensitive material for infrared laser scanner using an automatic developing machine,
It can be seen that an image having high sensitivity can be obtained by rapid development processing.

Furthermore, since the rapid processing can be performed by shortening the developing time and the drying time, the automatic developing machine can be downsized.

Further, in the present invention, a sufficiently high photographic performance can be maintained even when the developing solution is a one-part developing solution containing a specific 3-pyrazolidone-based developing agent, and further, the solution preparation work and the automatic developing machine can be performed. It facilitates maintenance and simplifies and downsizes the automatic processing machine.

Further, it is possible to reduce the bad odor from the working environment of the development processing and reduce the generation of harmful gas to suppress the corrosion of the equipment.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A 61-245152 (JP, A) JP-A 61-174540 (JP, A) JP-A 51-101530 (JP, A) JP-B 59- 17821 (JP, B2)

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material for an infrared laser scanner comprising a support and at least one hydrophilic colloid layer containing at least one silver halide emulsion layer is processed using an automatic processor. In the method, the silver halide emulsion layer contains silver chloroiodobromide grains having an iodine content of 0 to 2 mol% and a chlorine content of 0 to 30 mol%, and the swelling percentage of the hydrophilic colloid layer is 200% or less. A silver halide photograph characterized by being supplemented with a one-part developer containing a 3-pyrazolidone-based developing agent of the following general formula (I) as a developer used in the developing step of an automatic processor. Method of processing photosensitive material. General formula (I) (Here, R represents a phenyl group which may be substituted with a methyl group, a hydroxyl group or a methoxy group. R ₁ , R ₂ ,
R ₃ and R _{4, which} may be the same or different, each represents a hydrogen atom or a methyl group which may be substituted with a hydroxyl group or a morpholino group. However, when R represents an unsubstituted phenyl group, R ₁ , R ₂ , R ₃ and R ₄ are not all hydrogen atoms at the same time. ) 2. The silver halide according to claim 1, wherein the (100) face / (111) face ratio of the silver chloroiodobromide grains contained in the silver halide emulsion layer is 3 or more. Processing method of photographic light-sensitive material.