JPS63136043A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an image having high sensitivity by incorporating an iodine atom and a silver chloroiodobromide particle to a silver halide emulsion layer, and by specifying a developer which is used in a processing process using an automatic developing machine. CONSTITUTION:The silver halide emulsion layer contains the silver chloroiodobromide particle contg. 0-2mol% iodine and 0-30mol% chlorine, and a hydrophilic colloidal layer has <=200% percentage of swelling. The developer which is used to the processing process using the automatic developing machine, is used replenishing one part of the developer contg. 3-pyrazolidone type developing agent shown by the formula wherein R is aryl group, R1 is preferably, hydrogen atom or alkyl group substd. with amino group or hydroxyalkyl group, R4 is preferably hydrogen atom. Further preferably, R2 is hydroxyalkyl group, R3 is hydroxyalkyl, alkyl or a substd. alkyl group and R is aryl or a substd. aryl group. Thus, the image having high sensitivity is obtd. by a rapid processing.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention relates to a method for processing halogenated photographic materials for infrared laser scanners, and more specifically, the present invention relates to a method for processing halogenated photographic materials for infrared laser scanners, and more particularly, The present invention relates to a convenient processing method that does not require complicated preparation of a processing solution.

(Prior Art) Conventionally, as one of the exposure methods for photographic light-sensitive materials, an original image is scanned, and the silver halide photographic light-sensitive material is exposed to light based on the image signal, thereby creating a negative image or image corresponding to the image of the original image. 2. Description of the Related Art An image forming method using a so-called scanner that forms a positive image is known. There are various types of recording devices that use image forming methods using a single-scanner type, and the light sources for recording in these single-scanner type recording devices have conventionally been glow lamps,
Xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, etc. have been used. However, all of these light sources have practical drawbacks of low output and short lifespan. To compensate for these shortcomings, He-
There are scanners and laser printers that use a coherent laser light source such as a Ne laser, an argon laser, or a He-Cd laser as a scanner-only light source to expose at high illuminance. Although these devices can provide high output, they are large and expensive, require a modulator, and use visible light, which limits the safelight of photosensitive materials and makes them difficult to handle. There are drawbacks such as.

On the other hand, semiconductor lasers are small, inexpensive, easy to modulate, and have a longer lifespan than the lasers mentioned above. Furthermore, since they emit light in the infrared region, bright safelights can be used, which has the advantage of improving handling and workability, so the development of photosensitive materials in this field is becoming increasingly important.

On the other hand, black and white silver halide photographic materials are generally processed through a process of exposure, development, fixed fixation, and water washing (or stabilization). When this development process is carried out using an automatic processing machine, replenishers for each processing solution, developer and fixer, are usually prepared by diluting and mixing processing agents, each consisting of multiple parts, with water, and stocking replenisher solutions. As the photosensitive material is processed, certain amounts of developer and fixer are refilled from the replenisher stock tank into the developer tank and fixer tank of the automatic processing machine, respectively.

(Problems to be Solved by the Invention) Although the automatic processor processing system described above is a complete system that has been used for many years, in today's world with advances in electronic equipment, it is now possible to process silver halide photosensitive materials by wet processing. Several shortcomings in this basic system have also been highlighted.

In other words, the developer and fixer are diluted and mixed with water,
A major drawback is that a stock tank must be installed for this purpose. Although chemical mixers have become popular in recent years, there is no fundamental change in the fact that liquids are prepared using processing agents made up of multiple parts, and that the space for chemical mixers is outside the processor space.

Furthermore, in order to impart suitability for rapid processing, it has conventionally been common to carry out a hardening reaction during the processing process.

Glutaraldehyde, which is commonly used in developing solutions, has a pungent odor and is not very safe when it comes into contact with the body. In addition, in the case of hardening films using aluminum salts, which are commonly used in fixers, the fixer is set to a pH range of 9U, where the hardening reactivity is highest, in order to reduce swelling in washing water and reduce drying load. It must be. That is, its pH range is from 42.2 to 4.6. However, in this pH range, a portion of thiosulfate, the main component of the fixer, decomposes and generates sulfur dioxide gas, as well as acetic acid gas, which is commonly used as a pH buffer, making the work environment difficult. Contamination with unpleasant odors remains a major problem. In addition, this sulfur dioxide gas can corrode not only the automatic processing machine but also surrounding equipment over a long period of time, which is now a bigger problem.

One of the roots of the problems associated with the development processing is the hardening reaction during processing, which is generally caused by glutaraldehyde in the developer and aluminum salt in the fixer. The reason lies in the fact that it is used. The former should not be applied at all, and even if the latter is applied, the pH of the fixer
It has been found that many of the above-mentioned problems can be solved by setting the value to 4.65 or more and applying it as a weak dura reaction.

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 a silver halide photosensitive material is sufficiently hardened in advance, for example, in photosensitive material systems that require high sensitivity and high density, such as medical mail photography, a large amount of coated silver is required, which is undesirable from the viewpoint of resource conservation and cost. .

Therefore, it is important to sacrifice photographic sensitivity to obtain density using as fine particles as possible, that is, the unit! It is common knowledge in the industry to increase the concentration (covering power) for ff1ffi.

On the other hand, with recent advances in the field of mechatronics, it has become increasingly important to speed up photo processing that is coupled with such hardware.

Under these circumstances, it is highly desirable to sufficiently increase the sensitivity and processing speed of a sensitive material processing system for an infrared laser scanner.

Generally, as the halide composition of a photosensitive material increases in chloride, the development speed increases, but the sensitivity decreases. Furthermore, silver chloride tends to be dissolved into the developer by sulfites in the developer, resulting in the problem of precipitation of silver sludge.

If a compound such as those described in JP-A-56-24347, US Pat. No. 3,173,789, and British Pat. The sensitivity of the material processing system is decreasing, and although development is fast and takes a short amount of time, and a certain gradation can be obtained, the sensitivity of the system is low.

On the other hand, as the amount of iodide increases, the sensitivity increases, but the development speed becomes slower (the gradation becomes lower), so there is a limit to the proportion of iodide.

Furthermore, in order to provide a photosensitive material with color sensitivity in the near-infrared light region, the (100) plane/(111) hemostasis of silver halide grains must be high. (100) plane/(111) There is a limit to the ratio of iodide in order to improve hemostasis. As described above, designing an emulsion of a sensitive material having high sensitivity to near-infrared light is extremely difficult and requires special techniques since the technology in this field is new.

Therefore, the purpose of the present invention is to provide a photosensitive material processing system for an infrared laser scanner: - Firstly, to obtain higher sensitivity from the photosensitive material and processing system, and secondly, to obtain images through rapid processing and to reduce the size of the automatic processor. Thirdly, to facilitate solution preparation work and maintenance of automatic processing machines.Fourthly, to reduce bad odors from the processing work environment. It also reduces the generation of harmful gases and eliminates corrosion of equipment.Fifth, it enables completely piping-free processing and there are no restrictions on the installation location.

(Means for Solving the Problems) The above object of the present invention is to provide an infrared laser scanner comprising a support and at least one silver halide emulsion layer and at least one hydrophilic colloid layer. In a method of processing a silver halide photographic light-sensitive material using an automatic processor, the silver halide emulsion layer has an iodine content of 0 to 2.
It contains silver chloroiodobromide grains with a mol% and chlorine content of 0 to 30 mol%, the swelling percentage of the hydrophilic colloid layer is 200% or less, and the following general developer is used in the developing process of an automatic processor. It has been found that this can be achieved by a method for processing silver halide photographic materials, which is characterized in that a developer consisting of one part containing a 3-pyrazolidone developing agent of formula (1) is used and replenished.

General formula (where R represents an aryl group. R,, R,, R3,
R4 may be the same or different and each represents a hydrogen atom, an alkyl group, an aralkyl group, or an aralkyl group. However, when R represents an unsubstituted phenyl group, R
+, Rz, Rz and R4 are never all hydrogen atoms at the same time. ) As a result of intensive studies, the present inventors have developed a silver halide photosensitive material for infrared laser scanners that has been identified by processing it with a highly active developer consisting of a one-part solution, resulting in high sensitivity, rapid processing, and easy processing. A new system was devised to enable liquid preparation work.

The compounds of the present invention are disclosed in British Patent Nos. 943928 and 109.
No. 3281 and U.S. Pat. No. 3,221,023, however, there is no specification of a method for automatically developing the specific photographic light-sensitive material element of the present invention. The composition and effects are not taught at all.

The compound of the present invention can be found to have further technical value and progress, such as high sensitivity and easy and rapid processing, only when it is used in a photosensitive material processing system such as the present invention.

General formula (1) will be further described.

Here R is an aryl group (e.g. phenyl, naphthyl group)
represents.

R1, R2, R3, and R4 each represent a hydrogen atom, an alkyl group (e.g., methyl, ethyl, propyl, isopropyl, higher alkyl group, etc.), an aryl group (e.g., phenyl, naphthyl group, etc.), an aralkyl group (e.g., benzyl group, etc.) represent.

Further, the aryl group of R and the alkyl group, aryl group, and aralkyl group of R1 to R4 described above may each have a substituent, and examples of each substituent include a hydroxyl group, an alkoxy group, a hydroxyalkyl group, an amino group, Examples include a nitro group, a sulfonic acid group, a carboxyl group, and a halogen atom.

In the above general formula, R1 is a hydrogen atom or an alkyl group substituted with an amine group, hydroxyalkyl/L/7. & is preferred. R4 is preferably a hydrogen atom.

More preferably, R2 is a hydroxyalkyl group,
R3 is a hydroxyalkyl group, an alkyl group, or a substituted alkyl group, and R is an aryl or substituted aryl group.

The number of carbon atoms in these alkyl groups is preferably 4 or less.

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

■1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone ■1-p-tolyl-4,4-dihydroxymer-3-pyrazolidone ■1-phenyl-4-hydroxymethyl-4-methyl-
3-pyrazolidone■1-phenyl-4,4-dimethyl-3-pyrazolidone■1-phenyl-2-hydroxymer-4,4-dimethyl-3-pyrazolidone■1-phenyl-2-morpholinomethyl-4゜4-dimethyl- 3-pyrazolidone■1-phenyl-2-morpholinomethyl-4-methyl-3-pyrazolidone■l-phenyl-2-hydroxymer-4-methyl-3
-Pyrazolidone ■ l-Phenyl-5,5-dimethyl-3-pyrazolidone [phase] 1-phenyl-5-methyl-3-pyrazolidone ■
1-p-tolyl-4-methyl-4-hydroxynor-3
-pyrazolidone 0l-p-hydroxyphenyl-4,4-dimethyl-3
-pyrazolidone@l-m-trilu-4-methyl-4-hydroxynor-
3-pyrazolidone @ 1- p-methoxyphenyl-4-methyl-4-hydroxynor-3-pyrazolidone ■ 1- (3,5-dimethyl)phenyl-4-methyl-
4-Hydroxymethyl-3-pyrazolidone The compound of the present invention is added to the developer solution 11 in an amount of 0.1 g to 30 g. More preferably, 0.5g to 20g is added. More preferably, 15g of Ig is added.

The swelling percentage referred to in the present invention is (a) when the photographic material is heated at 38°C.
Incubation treatment for 3 days at 50% relative humidity (
b)! measuring the thickness of the aqueous colloid layer; (C) immersing the photographic material in distilled water at 21° C. for 3 minutes; and (d) comparing it with the thickness of the hydrophilic colloid layer measured in step (b).
It can be determined by measuring the percentage change in layer thickness.

From the viewpoints of rapid processing (e.g. reduction of drying load) and simplification of processing (e.g. omission of the processing hardening film, reduction of the number of processing agent parts, etc.), the swelling percentage is set to 2 in the present invention.
It is necessary to keep it below 00%.

Such rapid processing and processing simplification (especially rapid processing)
Even better results are achieved by further reducing the swelling percentage.

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

The preferred swelling percentage is 180% or less and 30% or more,
Particularly preferred is 150% or less and 50% or more.

In the present invention, a person skilled in the art can easily control the swelling percentage to 200% or less by, for example, increasing the amount of hardening agent used in the photosensitive material.

aldehyde compounds, compounds having active halogens as described in U.S. Pat. No. 3,288,775, etc., compounds having reactive ethylenically unsaturated groups as described in U.S. Pat. No. 3,635.718, etc.; Organic compounds such as halogencarboxaldehydes such as mucochloric acid are known. Among these, vinyl sulfone hardeners are preferred. Polymeric hardeners can also be preferably used in the present invention.

The polymeric hardener used in the present invention is preferably a polymer having an active vinyl group or a group that is a precursor thereof. Among them, vinyl sulfonyl Particularly preferred are polymers in which an active vinyl group, or a precursor thereof, is attached to the polymer backbone.

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

In the present invention, it is preferable that the emulsion layer and/or other hydrophilic colloid layers contain organic substances that may flow out during the development process. When the substance to be washed away is gelatin, it is preferable to use a gelatin type that is not involved in the crosslinking reaction of gelatin by a hardening agent, such as acetylated gelatin or phthalated gelatin, and preferably has a small molecular weight. On the other hand, as polymeric substances other than gelatin, polyacrylamide as described in US Patent No. U33.271.158, or hydrophilic polymers such as polyvinyl alcohol and polyvinylpyrrolidone can be effectively used. Dextran, saccharose, pullulan, etc. 1! Types are also valid. Among these, polyacrylamide and dextran are preferred, and polyacrylamide is a particularly preferred substance. The average molecular weight of these substances is preferably 20,000 or less, more preferably 10,000 or less. Effectively, the flow rate during treatment is 10% or more and 50% or less, preferably 15% or more and 30% or less of the total weight of the coated organic substances other than silver halide grains.
% or less is preferable.

The layer containing the organic substance washed away in the process of the present invention may be an emulsion layer or a surface protective layer, but when the total amount of the organic substance coated is the same, the layer containing the organic substance is more likely to be contained in the surface protective layer than in the emulsion layer alone. It is preferable to contain it in the emulsion layer, and more preferably to contain it only in the surface protective layer. In a sensitive material having a multilayer emulsion layer structure, if the total amount of the organic substance coated is the same, it is preferable that the emulsion layer closer to the surface protective layer contains a larger amount.

The photosensitive silver halide used in the present invention includes, for example, silver bromide,
Silver halide consisting of chlorine, bromine and/or iodide, such as silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. 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, the quick and simple processing method using a one-part developer according to the present invention achieves the best balance of both high sensitivity and rapid processing, which were previously difficult to achieve. It turns out it can be done. Furthermore, the occurrence of silver stains can be effectively prevented to a level that poses no practical problem. In particular, by adopting the configuration of the present invention, the development time can be reduced to within 15 seconds as described later, and even more
o It is excellent in that it enables surprisingly ultra-quick processing with a dry processing time of less than 60 seconds.

Further, the ratio of (100) plane/(111) plane of the silver halide grains used in the present invention is preferably 3 or more, particularly preferably 4 or more, and still more preferably 5 or more. Further, the upper limit of the above ratio is 100% for the (100) plane. Here, if the (100)/(111) plane is less than 1, the photosensitivity in the near-infrared region will be significantly lost, and if it is less than 3, the photosensitivity is still insufficient in the present invention, which is not preferable. . On the other hand, it is preferable that the above ratio is 3 or more from the viewpoint that a high level of photosensitivity in the near-infrared region is ensured and high sensitivity can be obtained.

The silver halide grains of the present invention having a (100) plane/(111) plane ratio of 3 or more can be prepared by various methods.

The most common method is to keep the 96g value during particle formation at a constant value of 8.10 or less, and use a silver nitrate aqueous solution and an alkali halide aqueous solution faster than the particle dissolution rate, and without re-nucleation.
This is a method of simultaneous addition by selecting a high speed (so-called controlled double jet method). More preferably p
The Ag value is 7.80 or less, more preferably the p/Ig value is 7.
．． It is better to set it to 60 or less. When silver halide grain formation is divided into two processes, nucleation and growth, there is no limit to the pAg value during nucleation (the prIg value during growth is 8
．． It is good to set it to 10 or less, more preferably 7.80 or less, still more preferably 7.60 or less. The soluble root salt and the soluble halogen salt may be reacted by a one-sided mixing method, but a simultaneous mixing method is better in order to obtain good monodispersity.

The silver halide emulsion used in the present invention may contain 50 wt % or more of silver halide grains having a (100) plane/(111) plane ratio of 3 or more, preferably 4 or more, more preferably 5 or more. The content is preferably 60 wt% or more, more preferably 80 wt% or more.

These emulsions may have coarse grains, fine grains, or a mixture thereof, but preferably have an average grain diameter (as measured by the projected area method or number average method).
About 0.04μ to 1.0μ, more preferably 0.2μ to 0.0μ. Preferably, the emulsion consists of 7 micron emulsion grains. The particle shape is preferably cubic, but as long as it satisfies the surface index conditions of the present invention, it may be potato-shaped, spherical, plate-shaped, or plate-shaped with a particle diameter of 5 times or more the particle thickness (for details, see Research Disclosure +- (RESEARCHDISCLQSU
RE) Item No.

22534p, 20-p, 58 (January 1983)). These light-sensitive emulsions may be mixed with a substantially non-light-sensitive emulsion (for example, an internally fogged fine grain emulsion). Of course, emulsions with different grain sizes, halogen compositions, etc. may be coated and used in separate layers in order to expand the exposure latitude. The particle size is preferably 0.1 to 2 Opm.

Further, as for the particle size distribution, a narrow one, so-called "monodisperse", is preferably used.

More specifically, the monodispersed emulsion is preferably an emulsion in which 90% or more of all grains are contained within ±40% of the average grain size, preferably 90% or more of all grains are contained within 120% of the average grain size. It will be done.

Furthermore, even if the crystal structure of silver halide grains is internally uniform, there are also those with a layered structure with different internal and external structures, British Patent No. 635.841, and U.S. Patent No. 3,62.
It may also be of a so-called conversion type as described in No. 2,318. Further, either a type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the particle may be used.

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

Incorporation of iridium ions is achieved by adding a water-soluble iridium compound (for example, hexachloroiridate (III) salt or hexachloroiridate (IV) salt) in the form of an aqueous solution during the preparation of the silver halide emulsion. be done. It may be added in the same aqueous solution form as the halide for grain formation, or it may be added before grain formation, during grain formation, or between grain formation and chemical sensitization, but in particular Preferably, it is added during particle formation.

In the present invention, iridium ions are preferably used in an amount of 10-' to 10-5 mol per mol of silver halide, more preferably 5XIO-' to 5X10-' mol, particularly preferably 10-7 to to-b mol. be.

Here, if the amount of iridium ion is less than 10-" mol, it is undesirable in that it is impossible to further improve the high-light sensitivity. On the other hand, if it exceeds 10-5 mol, desensitization regarding photosensitivity in the infrared region occurs. It is undesirable because it has disadvantages such as:

In the present invention, water-soluble iodine compounds (e.g., potassium iodide, sodium iodide, ammonium iodide, etc.) are used during the middle and late stages of particle formation, immediately before chemical aggravation after desalination, and when infrared sensitizing dyes are added immediately after chemical sensitization. Any time may be used as long as it is before coating or immediately before coating after addition of an infrared sensitizing dye, but it is particularly preferred between the late stage of particle formation and before chemical aggravation. In addition, the water-soluble iodine compound is 5X10-' moles per 111 moles of halogenide.
l x 10-'' mol, preferably 2 x 10-' mol to 5 x
10-' mol, more preferably 5 X 10-' mol ~
3xto-' moles. If the water-soluble iodine compound is less than 5 x 10-' moles, the storage stability cannot be improved, which is undesirable.On the other hand, if it exceeds 5 x 10-' moles, capri will appear and the photographic properties will be soft, which is not preferred.

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).

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

During the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (for example, U.S. Pat. No. 3,271,157, U.S. Pat.
, No. 574,628, No. 3,704.130, No. 4. 297. No. 439, No. 4,276.374, etc.) Thione compounds (e.g., JP-A-53-144.3)
No. 19, No. 53-82, 408, No. 55-77.
No. 737, etc.), amine compounds (e.g., JP-A-54-1
No. 00717, etc.) can be used. In addition to silver halide solvents, compounds that control crystal habit by adsorbing onto the grain surfaces, such as cyanine sensitizing dyes, tetrazaindene compounds, and mercapto compounds, can be used during grain formation.

The (100) plane/(111) plane ratio of the particles can be determined by Kubelkamunk's dye adsorption method (hereinafter referred to as "Kuberkamunk method"). This method preferentially adsorbs to either the (100) or (111) plane, and
A dye is selected in which the association state of the dye on the 100) plane and the association state of the dye on the (111) plane are spectrally different. The (100) plane/(L l 1) plane ratio can be determined by adding such a dye to an emulsion and examining the spectra in detail with respect to the amount of the dye added.

The detailed ratio of (l OO) planes on the surface of silver halide grains can be found in Tadaaki Tani, “Identification of crystal phase of silver halide fine grains in photographic emulsions using dye adsorption phenomenon,” Journal of the Chemical Society of Japan, 94.
2-946 (1984).

Silver halide photographic emulsions can be prepared using commonly used chemical sensitization methods, such as gold sensitization (U.S. Pat. No. 2,540.085,
No. 2.3.99.083, etc.), aggravation due to group II metal ions (US Pat. No. 2,448.060, No. 2.
No. 598,079), sulfur sensitization (U.S. Pat. Nos. 1 and 5),
No. 74,944, No. 2,278,947, No. 3,
No. 021.215, No. 3,635.717, etc.),
Reduction sensitization (U.S. Patent No. 2,518,698, Research Disc?
losure) Vol.

176 (1978, 12) RD-17643, No.
), exacerbation by thioether compounds (e.g., U.S. Pat. Nos. 2,521,926 and 3.021,21)
No. 5, No. 3,046,133, No. 3,165.5
No. 52, No. 3.625゜697, No. 3.635.
No. 717, No. 4°198.240, etc.), or various sensitization methods combined therewith are applicable.

More specific chemical sensitizers include sodium thiosulfate and allyl thio-carbamide.
Sulfur sensitizers such as rbamide), thiourea, thiosulfate, thioether and cystine;

and reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.

In the present invention, as an infrared sensitizing dye,
It is preferable to use at least one of tricarbocyanine dyes and/or 4-quinoline nucleus-containing dicarbocyanine dyes as described in No. 235,515.

The above-mentioned infrared sensitizing dye used in the present invention is contained in a silver halide photographic emulsion in a proportion of 5X10-' mol-5X 10-'' mol, preferably 1X10-'mol-1X10-' mol per mol of silver halide. Contained in

The infrared sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, lysine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

Although the dye is usually added after chemical sensitization, it may be added during grain formation or before chemical sensitization. Ultrasonic waves can also be used for dissolution.

U.S. Pat. No. 2,912,343, U.S. Pat. No. 3,342,605, U.S. Pat.
The method described in Patent No. 3.429.835 and the like can also be used. Furthermore, the above infrared sensitizing dye may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but as mentioned above, in any step of dispersion in the silver halide emulsion, can also be dispersed.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3,703,3
No. 77, No. 2,688,545, No. 3,397,
No. 060, No. 3,615.

No. 635, No. 3,628,964, British Patent No. 1,
No. 242,588, No. 1,293,862, Japanese Patent Publication No. 43-4936, No. 44-14030, No. 43-10773, U.S. Patent No. 3.

416,927, Japanese Patent Publication No. 43-4930, U.S. Pat. No. 3,615,613, and U.S. Patent No. 3,615.

No. 632, No. 3,617,295, No. 3.

635, 721, etc. can be used in combination.

In the present invention, together with the above-mentioned sensitizing dye,
The compound described in No. 35515 is used for the purpose of further enhancing the supersensitizing effect and/or for the purpose of further enhancing the preservability.
can be used.

In the present invention, together with the above-mentioned sensitizing dye,
In combination with a storage improver for sensitive materials as described in No. 235515, approximately 0 per mole of halogenated i in the emulsion
．． Amounts of 0.1 to 5 grams can be used.

The ratio (weight ratio) of the above-mentioned infrared sensitizing dye to the above-mentioned photosensitive material storage improver is preferably in the range of 1/1 to 1/300, particularly preferably in the range of 1/2 to 1150. used for.

The supersensitizer or photosensitive material storage improver used in the present invention can be directly dispersed in the emulsion, or can be dispersed in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol, propatool, methyl cellosolve). , acetone, etc.) or a mixed solvent using two or more of these solvents, and then added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid in accordance with the method for adding aggravating dyes.

The infrared sensitizing dye and the photosensitive material storage improver may be added to the emulsion prior to the addition of the infrared sensitizing dye, or
It may be added later. Further, these and the infrared aggravating dye may be dissolved separately and added separately to the emulsion at the same time, or they may be mixed and then added to the emulsion.

Antihalation dyes and/or antihalation dyes used in the present invention
Alternatively, as the anti-irradiation dye, a dye having substantial absorption at long wavelengths of 750 nm or more is used.

Here, the antihalation dye is used for the intermediate layer, undercoat layer, antihalation layer, back layer, emulsion layer, etc., and the antiirradiation dye is used for the intermediate layer, etc. in addition to the emulsion layer. Moreover, these dyes are preferably used in an amount of 10-3 to 1 g.
/m", more preferably 10-'10.5 g/m"
It is used in the amount added. For example, U.S. Patent No. 2,895
No. 955, No. 3,177.078, No. 4,581.
No. 325, the dyes described in JP-A-50-1.00, 116, and the dyes described in JP-A-61-162987 and JP-A-61-23.
Dyes such as those described in No. 5515 are preferably used.

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

Further, other dyes may be used in place of the above dyes or in combination with these dyes. Dyes that may be used instead or in combination include, for example, U.S. Pat.
pyrazolone oxonol dyes described in US Pat. No. 782, diarylazo dyes described in US Pat. No. 2,956,879, US Pat.
styryl dyes and butadienyl dyes described in US Pat. No. 487, merocyanine dyes described in US Pat. No. 2,527,583, US Pat.
, No. 284, No. 3. 718. Merocyanine dyes and oxonol dyes described in US Pat. No. 472, US Pat. No. 3,9
Examples include enaminohemioxonol dyes described in No. 76.661.

Various compounds can be added to the photographic light-sensitive material of the present invention in order to prevent a decrease in sensitivity and generation of capri during the manufacturing process, storage or processing of the light-sensitive material.

These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-thitraazaindene, 1-phenyl-5-mercaptotetrazole, and many other heterocyclic compounds. A large number of compounds such as mercury compounds, mercapto compounds, and metal salts have been known for a long time. Examples of compounds that can be used are C, E, K, Mees
Author: “The Theory of the Photo”
“Graphic Process” (3rd edition,
(1966) on pages 344 to 349, citing the original literature. For example, thiazolium salts described in U.S. Pat. No. 2,131.038 and U.S. Pat. No. 2.694,716;
．． Azaindenes as described in US Pat. No. 3,287,135; sulfocatechols as described in US Pat. No. 3,236,652; British Patent No. 6
Oximes described in US Pat. No. 23.448, etc.; US Pat. No. 2,403.927, US Pat.
mercaptotetrazoles, nitrones, and nitroindazoles described in U.S. Pat. No. 2,839,405, etc.;
U.S. Patent No. 3゜220.83
Thiuronium salts (thiur
onium 5 alts) ; U.S. Patent No. 2゜56
Examples include salts of palladium, platinum, and gold, which are described in No. 6.263 and No. 2.597,915.

In the present invention, as a matting agent, US Pat. No. 2.992.
No. 101, No. 2,701,245, No. 4.142.8
Homopolymers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid as described in No. 94 and No. 4,396,706, organic compounds such as starch, silica, titanium dioxide, sulfuric acid, strontium,
Fine particles of an inorganic compound such as barium can be used.

The particle size is 1.0 to 10 μm, especially 2 to 5 μm.
It is preferable that

The surface layer of the photographic light-sensitive material of the present invention contains a slipping agent as described in US Pat. No. 3,489,576 and US Pat. In addition to the silicone compounds described in Japanese Patent Publication No. 047.958 and the colloidal silica described in Japanese Patent Publication No. 56-23139, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpropane, bentanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention.

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

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

There may be two or more silver halide emulsion layers, and the two or more silver halide emulsion layers may have different sensitivities, gradations, etc.

Further, one or more silver halide emulsion layers or non-photosensitive layers may be provided on both sides of the support.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

As an antistatic agent, in particular, U.S. Pat.
Fluorine-containing surfactants or polymers described in JP-A No. 60-80849, JP-A No. 59-74554, and Japanese Patent Application No. 60-249021 and JP-A No. 61-32462;
No. 0-76742, No. 60-80846, No. 60-8
No. 0848, No. 60-80839, No. 60-7674
No. 1, No. 58-208743, Patent Application No. 1339-1983
No. 8, No. 61-16056, No. 61-32462,
Nonionic surfactants described in JP-A No. 57-204540, Japanese Patent Application No. 61-324, etc.
Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in No. 62 can be preferably used. In addition, as an inorganic antistatic agent, JP-A-57
Composite oxides prepared by doping conductive tin oxide, zinc oxide, or these metal oxides with antimony or the like, as described in Japanese Patent No. 118242, etc., can be preferably used.

In addition to gelatin, acylated gelatin such as phthalated gelatin and malonated gelatin is used as a protective colloid in the silver halide photographic emulsion layer and intermediate layer used in the present invention.
Cellulose compounds such as hydroxyethyl cellulose and carboxymethyl cellulose; soluble starches such as dextrin; hydrophilic polymers such as polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide and polystyrene sulfonic acid can be added.

Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

Also, U.S. Patent Nos. 3,411,911 and 3.411
．． No. 912, No. 3,142,568, No. 3,32
No. 5,286, same No. 3. 547. 650, Japanese Patent Publication No. 45-5331, etc., a polymer latex consisting of a homopolymer or copolymer of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc. is used to improve the dimensional stability of photographic materials and to improve the film properties. It can be included for purposes such as improving the

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention can contain a plasticizer, a fluorescent brightener, an air fog inhibitor, a toning agent, and the like.

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

The surface of the support is preferably subjected to corona discharge treatment, glow discharge treatment, or ultraviolet irradiation treatment in order to improve adhesion to the hydrophilic colloid layer. Alternatively, an undercoat layer made of styrene-butadiene latex, vinylidene chloride latex, etc. may be provided.
A gelatin layer may be further provided on top of the gelatin layer.

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

These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

Exposure to obtain photographic images can be performed using tungsten electric lamps, cathode ray tube flying spots, light emitting diodes, laser light (
For example, gas laser, YAG laser, dye laser,
Any of various known light sources including infrared light such as a semiconductor laser (semiconductor laser, etc.) can be used. Exposure time is 1/1
0' to 1/10" second. The spectral composition of the light used for exposure can be adjusted with a color filter if necessary. The photosensitive material of the present invention is particularly suitable for use in scanners using semiconductor lasers. There is.

As the developing agent used in the black and white developer used in the present invention, a combination of dihydroxybenzenes and the 1-phenyl-3-pyrazolidones of the present invention is most preferable because it is easy to obtain good performance. Of course, a p-aminophenol type developing agent may also be included.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. ,
Examples include 2-methyl-p-aminephenol and p-benzylaminophenol, among which N-methyl-p-aminophenol is preferred.

The developing agent is usually 0.01 mol/I! Preferably it is used in an amount of ~1.2 mol/l.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The amount of sulfite is preferably 0.2 mol/1 or more, particularly 0.4 mol/1 or more. Further, the upper limit is preferably 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 range is from 10 to 12.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H1P4 moderator.

Japanese Patent Application No. 1987-28708 (Borate), Japanese Patent Application No. 1988-
Delays such as No. 93433 (e.g., sucrose, acetoxime, 5-sulfosalcylic acid), phosphates, carbonates, etc. may also be used.

Additives used in addition to the above components include 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, methanol; 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain antifoggants such as mercapto compounds, indazole compounds such as 5-nitroindazole, and benztriazole compounds such as 5-methylbenztriazole, and may further contain color toning agents, surfactants, and antifoaming agents as necessary. , hard water softener, JP-A-1987-
It may also contain the amino compounds described in No. 106244.

In the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

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

In addition, F. A. Meson, “Photograph Ink Brosesin Chemistry”, published by Focal Press (1
966), pages 226-229, U.S. Patent No. 2,193.
, No. 015, No. 2,592゜364, Japanese Unexamined Patent Publication No. 48-6
Those described in No. 4933 may also be used.

Conventional treatment agents typically consist of multiple parts. When it is made up of one part, it prevents the components from deteriorating or changing due to interactions between the processing agent components contained in the processing agent after it is manufactured and before it is used. This is to avoid it. Processing agents that are made up of multiple parts are usually dissolved and mixed in sequence in pre-prepared water, and the final volume is made up to a certain volume with water before being used as a processing solution (working solution). .

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

As the photosensitive material is processed in the automatic processing machine in accordance with the method of the present invention, the developer concentrate is normally replenished with water to dilute it; in this case, as in the present invention, the developer concentrate is
It is most preferable to consist of parts in terms of machine simplicity and replenishment accuracy. Due to its composition, it is possible to make it into two parts and dilute it with water, but in the case of two parts, it is necessary to increase the number of pumps and replenish it, or to devise packaging materials to separate the two parts until just before use. Therefore, there are problems in that the work becomes complicated and the automatic processor becomes complicated.

In the present invention, "development time" and "fixing time" respectively mean
The time from when the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution, and the time from when it is immersed in the fixing tank solution until it is immersed in the next washing tank solution (stabilizing solution). say the time

Further, "washing time" refers to the time during which the product is immersed in the washing tank liquid.

In addition, "drying time" refers to the time the machine is in the drying zone, which is usually equipped with a drying zone where hot air of 35°C to 100"C, preferably 40°C to 80"C, is blown. means.

The developing temperature and time are preferably from about 5°C to about 50'C for 6 seconds to 2 minutes, more preferably from 30°C to 40'C for 6 seconds to 30 seconds, even more preferably from 30''C to 40°C. 6 seconds~
It should be developed in 15 seconds.

The fixing solution is an aqueous solution containing thiosulfate, and has a pH of 3.8.
Above, preferably 4.2 to 5.5. More preferably the pH is 4.65 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0. 1 to about 6 mol/l
It is.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid, or conductors thereof can be used alone or in combination of two or more. These compounds are the fixer 17! 0.0 per
Those containing 0.05 mol or more are effective, especially 0.01 mol/1
~0.03 mol/l is particularly effective.

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

The fixing solution may optionally contain preservatives (e.g., sulfites, bisulfites), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), chelating agents with hard water softening ability, and patent applications. The compound described in No. 60-218562 may be included.

The fixing temperature and time are the same as for development, approximately 0°C.
It is preferably 6 seconds to 2 minutes at ~50°C, more preferably 6 seconds to 30 seconds at 30°C to 40°C, even more preferably 30°C~
It should be fixed in 6 to 15 seconds at 40°C.

When the fixer concentrate is replenished into the automatic processor in the method of the invention with water to dilute it as the light-sensitive material is processed, it is most preferred that the fixer concentrate is composed of one part. is the same as for the developer.

The fixer stock solution can exist stably as a single agent at pH 4,
5 or more, more preferably pH 4.65 or more. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used. Therefore pH 4,5
Within the above range, sulfur dioxide gas is generated less and the working environment is also improved. The upper limit of pH is not so strict, but if it is too high
If the film is fixed with H, even if it is washed with water thereafter, the membrane pH will become high and the membrane will swell to a large extent, resulting in a large drying load, so the pH is limited to about 7. In fixing solutions that use aluminum salts to harden films, the pH limit for preventing precipitation of aluminum salts is 5.5.

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

The mixing ratio of each concentrate to the processing tank solution and dilution water can be varied depending on the composition of the concentrate, but the ratio of concentrate to dilution water is 1: θ to 8 The total amount of each of these developer and fixer is equal to the photosensitive material lrr? It is preferable that the area is from 50 m1 to 1500 m6.

In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed.

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water as washing water or stabilizing liquid, it is not only possible to save water by reducing the amount of replenishment to less than 31 ml per 1 - of photosensitive material, but also eliminates the need for piping for installing an automatic processing machine. Furthermore, the number of stock tanks can be reduced. That is, the solution dilution water and washing water or stabilizing solution for the developer and fixer can be supplied from a common single layer stock tank, making it possible to further downsize the automatic developing machine.

If anti-mildew water is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
It is possible to save 0 to 31 liters of water, preferably 0 to 1 liter, per '.

Here, when the replenishment amount is 0, no replenishment is performed at all except for appropriately replenishing the amount of washing water in the washing tank that has decreased due to natural evaporation, etc. In other words, the so-called "reservation water" is essentially not refilled. Refers to cases in which a processing method is used.

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in the direction of the processing solution that is not contaminated with the fixer. Good washing with water is performed. According to this, unstable thiosulfates, etc. are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect is obtained. The washing water is also less than conventional. , a very small amount is required.

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 as described in Japanese Patent Application No. 172968/1983.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the washing or stabilizing bath with anti-mold water depending on the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in Japanese Patent Application No. 5133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. This is more preferable because the stock water can be saved and the amount of waste liquid can be reduced.

Anti-mildew methods include the ultraviolet irradiation method described in JP-A No. 60-263939, the method using a magnetic field described in JP-A No. 60-263940, and the use of ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986-
No. 253807, No. 60-2'15B94, No. 61-
The method using the antibacterial agent described in No. 63030 and No. 61-51396 can be used.

Furthermore, L, E, West “Water Qualt
Ly Cr1teria" Photo Sci & E
ng, Vol, 9 No. 6 (1965), M
, W, Be-ach' Microbiologica
l Growths in Motton-Pic-t
ure Processing” SMPTE Jou
rnal Vol, 85+ (1976), R,0
, Deegan, “Photo Processing
Wash WaterB ioc 1des”J,
Imaging Tech, Vol 10. No,
6 (1984) and Japanese Unexamined Patent Publication No. 57-8542, 57
-58143, 58 105145, 57-1
No. 32146, No. 58-18631, No. 57-975
30, No. 57-157244, etc., antibacterial agents, anti-inflammatory agents, surfactants, etc. can also be used in combination.

Furthermore, for the washing bath, R9T, J by Kreiman,
Image.

TechlO, (6) 242 (1984).
LO5URE Volume 205, Item 20526 (1
Isothiazoline compounds described in Vol. 228, Item 22845 (1983, May issue)
It is also possible to use isothiazoline compounds described in Japanese Patent Application No. 61-51396 (Japanese Patent Application No. 1982-51396) as antibacterial agents (Microbiocides).

Furthermore, specific examples of anti-fungal agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
O-phenylphenol, chlorophene, dichlorophene, pol-11 aldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2
-(4-thiazolyl)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4,4'-trichloro-2'-hydroxy Examples include diphenyl ether.

In addition, "Chemistry of anti-bacterial and anti-mildew" by Hiroshi Horiguchi, Sankyo Publishing (Showa 5)
7), ``Handbook of Antibacterial and Antifungal Technology'', Japanese Society of Antibacterial and Antifungal Research, Gihodo (1988).

It is preferable that the water treated with anti-mildew means and stored in the water stock tank be used both as dilution water for the undiluted solution of the processing solution such as the developer-fixer and as washing water, since it requires less space. However, the anti-mildew solution dilution water and the rinsing water (or stabilizing solution) can be stored separately in separate tanks, or only one of them can be taken directly from the tap.

When stored in separate tanks, the washing water (or stabilizing bath) can contain various additives in addition to applying anti-mildew measures as in the present invention.

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

A specific example of the chelating agent is ethylenediaminetetraacetic acid C1ogK=16.1. (same below), cyclohexanediaminetetraacetic acid (17,6), diaminopropanoltetraacetic acid (13,8), diethylenetriaminepentaacetic acid (18,
4), triethylenetetraminehexaacetic acid (19,7), etc., and their sodium salts, potassium salts, and ammonium salts, and the amount added is preferably 0.01-10g, #
! , more preferably 0. It is 1 to 5 g/l.

Also, JP-A No. 58-434542, No. 58-11403
Silver image stabilizers such as those described in No. 5 and No. 61-83534 can also be included in the washing water.

Furthermore, various surfactants can be added to the washing water of the present invention for the purpose of preventing uneven water droplets. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include compounds described in "Surfactant Handbook" published by Kogaku Tosho Co., Ltd.

Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting the membrane pH (e.g. pH 3
~8) various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) Typical examples include aldehydes such as (used in combination) and formalin. In addition, various additives such as chelating agents, bactericidal agents (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, fluorescent brighteners, and hardening agents are used. Good too,
Two or more of the same or different desired compounds may be used in combination.

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 membrane pIl adjusting agent after treatment in order to improve image storage stability.

Water washing or stabilization bath temperature and time by the above method is 0℃
Preferably 6 seconds to 2 minutes at ~50°C, but 6 seconds to 2 minutes at 15°C to 40°C
It is more preferable that the treatment be carried out for 2 to 30 seconds, and more preferably for 6 to 15 seconds at 15° C. to 40° C.

According to the method of the invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is carried out at about 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 1 minute, but it is particularly preferably 4
(Approximately 5 seconds to 30 seconds at 1 to 80"C.

In the present invention, an even more excellent effect is exhibited in that the lower the swelling percentage of the photosensitive material, the shorter the drying time thereof.

According to the method of the present invention, the so-called dry-to-dry processing time for development, fixing, washing, and drying is within 3 minutes and 30 seconds, preferably within 100 seconds, and most preferably within 60 seconds. Is Rukoto. As for the treatment of the infrared laser scanner window material of the present invention, it is particularly preferable that the development time be within 15 seconds and the dry-to-dry treatment time be within 60 seconds. In addition to such a reduction in processing time, the replenisher, which is a one-part component of the developer and fixer, simultaneously simplifies the liquid preparation work and simplifies maintenance.

Here, "to dry" refers to the time from the moment the leading edge of the photosensitive material to be processed enters the film insertion area of the processor to the moment the leading edge emerges from the processor after being processed. say.

The photographic light-sensitive material of the present invention is not particularly limited, and is mainly used as a general black-and-white light-sensitive material. Preferably X for direct photography
- Ray film, X-ray film for indirect photography, CRT
It is used in a system that irradiates an object such as a human body with X-rays, etc., and converts the X-rays that have passed through the object into visible light and exposes the object to visible light. Examples include medical or industrial X-ray photographic materials, X-ray duplex photographic materials, medical CR'I'' image photographic materials, and the like.

(Example) Next, a specific example of the present invention will be 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 After putting an appropriate amount of ammonia into a container heated to 55°C containing gelatin, potassium bromide, and water, the pAg in the reaction container was While maintaining the value at 7.60, a silver nitrate aqueous solution and a potassium bromide aqueous solution to which hexachloroiridate(1) salt had been added so that the molar ratio of iridium to silver was 1O-7 mol were added by the double jet method, and the average Particle size is 0
．． Monodisperse silver bromide emulsion grains of 55μ were prepared. This emulsion grain has 9 of the total grains within ±40% of the average grain size.
8% were present. Also, I X l O-'' moles of potassium iodide per mole of silver were added late in grain formation.

After desalting this emulsion, the pH was 6.2 and the pAg was 8.
6, gold/sulfur sensitization was performed using sodium thiosulfate and chloroauric acid to obtain desired photographic properties. The (l OO) plane/(111) hemostasis rate of this emulsion was measured by the Kubelkamunk method and was 93/7. This emulsion is made into an emulsion.

Next, in a container heated to 70°C containing gelatin, sodium chloride, and water, a very small amount of 1,000 onythyl was added, followed by a silver nitrate aqueous solution and equimolar amounts of potassium bromide and sodium chloride (potassium bromide and The molar ratio of sodium chloride is 80/
Monodisperse silver chlorobromide emulsion grains having an average grain size of 0°52 μm were prepared by simultaneously adding the aqueous solution of mixture 20) by a double jet method.

In this case as well, 101 moles of iridium ions (trivalent) were added in a molar ratio to silver in the aqueous solution of added halide, and 10@-3 moles of potassium iodide per mole of silver was added in the latter stage of grain formation.

(100)/(111) The hemostasis rate was 9515. These emulsion grains were subjected to desalting and optimum chemical sensitization in the same manner as A to obtain emulsion B. Furthermore, potassium bromide and water are added.
After putting an appropriate amount of ammonia into a container heated to 0°C, while maintaining the pAg value in the reaction container at 7.60, add hexachloroiridium to the aqueous silver nitrate solution so that the molar ratio of iridium to silver is 101 mol. (III) Acid salt was added. The molar ratio of potassium bromide and potassium iodide is 98/
An aqueous solution of 2 was added by the double jet method, and potassium iodide with a molar ratio of 10-3 mol to silver was added in the latter stage of grain formation to form a monodisperse solution with an average grain size of 0.5μ (
100)/(111) An optimally chemically sensitized silver iodobromide emulsion C having a hemostasis rate of 91/9 was obtained.

In the preparation method of emulsion A, grain formation was carried out at a pAg value of 8.10, and the average grain size was 0°53μ (100) /
An emulsion with a (111) ratio of 70/30 was prepared and named emulsion.

(2) Preparation of silver halide emulsion for comparison In the preparation method of emulsion B, the molar ratio of potassium bromide and potassium chloride was 30/70, and the average grain size was 0.54.
An emulsion with a (100)/(111) hemostasis rate of 97/3 was prepared and named emulsion E.

(3) Preparation of emulsion coating solution Weigh out 1 kg of each of these emulsions A to E in a container, heat them to 40°C to dissolve the emulsions, and then add a methanol solution (9x 10-', 17 mol/1) in 70 cc.

Aqueous solution of the following supersensitizer (4,4×10-” μmol/
1) 90cc, methanol solution of the following photosensitive material storage improver (2,8 x 10-''μmol/1) 35cc, 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene aqueous solution, coating aid An aqueous solution of dodecylhenzenesulfonate and an aqueous solution of a thickener polybotacium p-vinylbenzenesulfonate compound were added to prepare an emulsion coating solution.

(Infrared sensitizing dye) (Super sensitizer) 4.4'-bis[4,6-di(naphthyl-2-oxy)
Pyrimidin-2-ylaminocostilbene-2,2'-
Disulfonic acid disodium salt (sensitive material storage improver) G Hz CH= CHz (4) Preparation of coating solution for surface protective layer of window material layer Add a thickener to a 19 wt % aqueous gelatin solution heated to 40°C. Polyethylene sodium sulfonate aqueous solution, cloak agent polymethyl methacrylate i particles (average particle size 3.0 μm), hard 111 agent N, N'-ethylene bis(vinylsulfonylacetamide), coating aid t-octylphenoxyethoxyethanesulfonic acid A coating solution was prepared by adding an aqueous solution of Sl-IJ, an aqueous polyethylene surfactant solution as an antistatic agent, and an aqueous solution of a fluorine-containing compound having the following structure.

C,F, ,SO□N(C3H7)C112COO and CeF l? 502N (C3H?) (C
H2C11□-○+mouth! 1 (5) Preparation of back coating solution 1 kg of lQwt% gelatin aqueous solution heated to 40°C, thickener polyethylene sodium sulfonate aqueous solution, and 50 cc of the following back dye aqueous solution (5 x 10-''mol/#)
, Hardener N.

A coating solution was prepared by adding an aqueous solution of N'-ethylenebis-(vinylsulfonylacetamide) and an aqueous solution of sodium t-ocdylphenoxyethoxyethanesulfonate as a coating aid.

(Back dye) (6) Preparation of coating solution for surface protective layer of bank layer Add 10 wt% aqueous gelatin solution heated to 40°C, add thickener polyethylene sodium sulfonate aqueous solution, matte agent polymethyl methacrylate fine particles (average particle size 3.0μm), coating aid t-octylphenoxyethoxyethanesulfonate aqueous solution, and antistatic agent polyethylene surfactant water? 8 liquid and an aqueous solution of a fluorine-containing compound having the following structure were added to prepare a coating liquid.

C, F,, So□N (Cillt) CIl□COO
to and CaF l? 5OZN (C3117)
(Creating a coating sample of CH2C11□-O-hsH (7) Apply the aforementioned bank layer coating solution to the surface protective layer of the back layer
At the same time, gelatin was coated on one side of the polyethylene terephthalate support at a coating amount of 4 g/rr.Subsequently, gelatin containing near-infrared sensitizing dye as described in (3) was coated on the opposite side of the support. The emulsion coating solution and the surface protection layer coating solution were mixed so that the coating silver amount was 3.5 g/%, and the hardening film in the surface protection layer coating was prepared to prepare samples with different swelling percentages of the coating film. Coating was carried out by adjusting the amount of the agent in various ways.The name of each sample prepared, the name of the emulsion used and the swelling percentage employed are as shown in Table 1 below.

Table 1 (8) Swelling rate measurement method a) Incubate the coated sample at 38°C and 50% relative humidity, b) Measure the thickness of N, C) Immerse in distilled water at 21°C for 3 minutes, and d) measuring the percentage change in layer thickness compared to the layer thickness measured in step b).

(9) Normal sensitometry (7) Seven types of samples were measured at room temperature on the 7th day after application while keeping the temperature and humidity at 25°C and 65% RH.
Scanning exposure for lo-7 seconds was performed using a semiconductor laser with a wavelength of nm. After exposure, the following processing steps (1)
and (II).

<Processing (■)><Developer prescription (formulation for 381)> Pa for 381
rt A Potassium hydroxide 1107g Potassium sulfite 1680g Sodium hydrogen carbonate 285g Boric acid
38g diethylene glycol
456g ethylenediaminetetraacetic acid 6
3.5g 5-methylbenzotriazole 2.28g
Hydroquinone 1140 with water
Up to 9.507! part
B Glacial acetic acid 416.5g Diethylene glycol 644.5g 5-nitroindazole 9.5g 1-phenyl-3-pyrazolidone-! part C Geltar aldehyde 187.3g Sodium metabisulfite 478.8 in water
up to 950mg starter acetic acid 270 potassium bromide 300 water
Up to 1.51 Developer solution preparation method) Add water 201 to the replenisher stock tank of about 501, then add the above Part A, Part B, Part
Add and dissolve C sequentially with stirring, and finally add 38% with water.
1! This was used as a developer replenisher (pH 10,30>).

20 ml of the above starter for this developer replenisher 11
After first filling the developing tank of an automatic processor with a developer added at a ratio of
(25.7 cm x 36.4 cm) was replenished.

Fixer formulation (for 38jl!) part A Ammonium thiosulfate 70wt/volχ 7.61 Ethylenediaminetetraacetic acid disodium trihydrate 0.76g Sodium sulfite 570g Boric acid -380
g Sodium hydroxide 254.6g acetic acid
with 570g water
9.51part B Aluminum sulfate 380g sulfuric acid
148.2g with water
1.9′! <Fixer Preparation Method> Water 201 was put in a replenisher stock tank of about 5 ON, and then Part A, Part B were sequentially added and dissolved while stirring, and finally the fixer was adjusted to 381 with water to obtain a fixer replenisher.

The fixing tank of an automatic processor was first filled with the same fixer replenisher (pH 4, 25).

Thereafter, add 60ml of the above fixer replenisher each time the window material is processed.
/Replenished one B4 size sheet.

Each treatment step was performed as follows (Dryt.

Dry for 96 seconds).

Processing ■〉 The compositions of the developer and fixer concentrates 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 present invention) 5.5g5
-Methylbenzotriazole 2g water 11
(Adjust the pH to 10.30).

Replenisher kit size 51 Fixer concentrate Ammonium thiosulfate 560g Sodium sulfite 60g Ethylenediaminetetraacetic acid disodium trihydrate
0.10g sodium hydroxide
Adjust to 11 with 24g water (pH 5, IO with acetic acid)
).

Replenisher kit size 51 (water stock tank liquid) Ethylenediaminetetraacetic acid disodium salt/trihydrate salt
0.5g/l automatic developing machine
Dry to Dry 60 seconds processing developing tank (
1) 6. ! M 35 °C x 11.5 seconds Fixing tank (2) 6.51 35 °C
12.5 seconds flush tank (3) 6. 57
! 20℃×7. 5 seconds squeeze roller cleaning tank (7) 200ml host stock tank (4) 25 & dry 60℃
However, although a heater was used to maintain the temperature of both the developer and the fixing tank, cooling water was not used.

When starting the development process, each tank was filled with the following processing solution.

Developing tank: 333 ml of the above developer concentrate, 667 ml of water
1, an aqueous solution I containing 2 g of potassium bromide and 1.8 g of acetic acid Qmj? was added to adjust the pH to 10.15.

Fixing tank: 250ml of the above fixer concentrate and 750ml of water
ml Water washing tank and washing tank: Same composition as the above water stock tank liquid Above photosensitive material B4 size (25.7 cm x 36° 4 cm
) Every time one sheet is processed, 20ml of developer concentrate and stock tank water are placed in the developing tank.10ml of fixer concentrate and stock tank water are placed in the 40ml fixing tank.
Stock tank water from 30mj2 squeeze roller cleaning tank to washing tank
60m! ! was replenished and the running process continued in the opposite direction to the film direction. During this time, developer, fixer, and sailor (if necessary, new replenishers were added as well.

These results are shown in Table 2.

1) G has an optical density of 0.0 on the characteristic curve. It is shown by the convergence between two points: the logarithm of the exposure amount that gives a density of 8, and the logarithm of the exposure amount that gives a density of 2.0.

2) Sensitivity is the exposure amount E - 1o at a density of fog + 0.3
The gE value was determined by the treatment using sample 9-1 according to the present invention ([
The value in method 1) is set as 1.0, and the relative value is shown.

3) Silver stains were removed at 20% per day during the above running treatment experiment.
Immediately after continuous processing of 0 sheets, developer 11 was collected from the developing tank of the automatic processor, and the amount of silver precipitated at the bottom of the beaker after being left for 2 days was observed and ranked.

4) Drying property was evaluated during the above continuous treatment.

In button 4), the ○ mark indicates the level with no practical problems.
The mark indicates the impractical level.

As shown in Table 2, the processing system of the present invention speeds up processing without adversely affecting photographic performance, simplifies liquid preparation, reduces the space required for automatic processors and replenishment tanks, and eliminates odors, especially odors generated from fixing solutions. All reductions have been achieved.

Regarding sensitivity, as the proportion of silver chloride decreases, and as silver iodide is included, sensitivity increases.

However, if the proportion of silver iodide is too high, the sensitivity will increase, but the gradation will become lower, so there is a certain limit.

Regarding silver stains, it would be better if the proportion of silver chloride was lowered as in the present invention, but there is also a limit to the proportion of silver iodide in relation to the development speed.

From the viewpoints of sensitivity and gradation silver stain development speed, the silver halide composition is defined as that of the present invention. Furthermore, in rapid processing, drying is one of the major factors governing the processing time, and it depends on the swelling percentage.

If the swelling percentage is 200% or less as in the present invention, rapid processing can be achieved without treatment hardening, that is, without disadvantages such as bad odor.

Example 2 The developer concentrate composition of processing (If) was 50
The stability of 3-pyrazolidones in an alkaline solution was investigated after aging at ℃ for 2 weeks, and the results are shown in Table 3 below.

Table 3 *) Conventional compounds (3-pyrazolidones cannot coexist with alkalis) Therefore, in order to use a single developer as a simple processing system as in the present invention, 3-pyrazolidones can be used in combination with the formula of the present invention. (
It can be seen that the object of the present invention cannot be achieved unless the compound 1) is specified.

(Effects of the Invention) According to the present invention, in processing a silver halide photographic material for an infrared laser scanner using an automatic processor,
It can be seen that images with high sensitivity can be obtained by rapid development processing.

Furthermore, since rapid processing is possible by shortening development time, drying time, etc., the automatic processor can be made smaller.

In addition, in the present invention, even if the developer is a one-part developer containing a specific 3-pyrazolidone-based developing agent, sufficiently high photographic performance can be maintained, and furthermore, the developer can be In addition to making maintenance easier, it also makes it possible to simplify and downsize the automatic processing machine.

Furthermore, it is possible to reduce bad odors from the development processing work environment, reduce the generation of harmful gases, and suppress corrosion of equipment.

procedural amendment gate January 9, 1986

Claims (1)

[Claims] (1) A method of processing a silver halide photographic light-sensitive material for infrared laser scanners, which comprises a support and at least one hydrophilic colloid layer including at least one silver halide emulsion layer, using an automatic processor. wherein 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 photographic light-sensitive material characterized in that the developer used in the development step of an automatic processor is supplemented with a one-part developer containing a 3-pyrazolidone developing agent represented by the following general formula (I). processing method. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, R represents an aryl group. R_1, R_2, R
_3 and R_4 may be the same or different and each represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl 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) (100) plane/(1
11) A method for processing a silver halide photographic material according to claim (1), wherein the number of surfaces is three or more.