JPS63148255A - Image forming method - Google Patents

Abstract

PURPOSE:To prevent uneven development by incorporating a specified polymer in the outermost layer of a silver halide photographic sensitive material on the emulsion layer side in a specified weight % of the binder of the outermost layer, and processing the photosensitive material in a developing time of >=15sec. CONSTITUTION:The outermost layer of the silver halide photographic sensitive material contains the polymer represented by the formula shown on the right in an amount of 4-300wt% of the binder in the outermost layer and the photosensitive material is processed in a developing time of <=15sec. In the formula, X is a unit derived from acrylamide monomer; Y is a unit derived from a monomer copolymerizable with said X; x is 70-100mol%; and y is 30-0mol%. Said polymer has an average molecular weight of 2,000-500,000, the monomer of X is embodied by acrylamide, methacrylamide, and the like, and that of Y is, preferably, vinyl alcohol, acrylic acid, methacrylic acid, and the like, thus permitting the processing time to be reduced, moreover, the operation for preparing the processing solution and its maintenance to be facilitated at the same time, and uneven development to be prevented.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention uses a silver halide photographic material for laser scanners (hereinafter referred to as photographic material) that is spectrally sensitized in the infrared region, which has high photographic sensitivity. The present invention relates to a method for forming an image, and particularly relates to an image forming method that does not cause uneven development even when development is performed in a short period of time (within 13 seconds).

(Prior art) One of the exposure methods for photographic light-sensitive materials is to scan an original image, and based on the image signal, expose the silver oxide photographic material to produce a negative or positive image corresponding to the image on the original image. 2. Description of the Related Art An image forming method using a single type of sub-scanner for forming an image is known. There are various recording apparatuses that utilize image forming methods using one-scanner type, and a semiconductor laser is used as one of the recording light sources of these one-scanner type recording apparatuses.

Semiconductor lasers are small, inexpensive, easy to modulate, and have a long life. Furthermore, since it emits light in the infrared region, a bright safelight can be used, which has the advantage of improving handling efficiency.

The sensitive material used in this semiconductor laser is a photographic X-sensitive material that is spectrally sensitized in the infrared region.This is a photosensitive material that is spectrally sensitized in the infrared region. It is obtained by spectral sensitization technology that extends to longer wavelengths. Is absorption of infrared light necessary for spectral sensitization in the infrared region? A sensitizing dye having the following properties is used.

(Problem to be solved by the invention) Recently, it has become desirable to be able to use images quickly even in one-type scanners using semiconductor lasers. (Conventional 2
0 seconds to 75 seconds or less).

For example, this point has become especially necessary in a system in which a laser scanner process and a development process are performed continuously. However, as the development time becomes shorter, edge image unevenness tends to occur, which is a serious problem.

The reason for this is that the developer remains unevenly on the surface of the photographic light-sensitive material during the crossover period from when it exits the developing bath to when it enters the fixing bath.

This is because the development with the developer remaining unevenly on the surface of the photosensitive material after the development squeeze increases the development speed of the photographic light-sensitive material in order to shorten the development time. This is because it remains as a.

In particular, when the development time is less than 75 seconds (herein, "development time" refers to the time from when the photographic light-sensitive material enters the developer until it enters the fixer), uneven development occurs significantly.

In order to solve this problem, it is known to use a specific ionic surfactant that is bath-dissolved even in a developer and has surface activity. This improves the wettability of the surface of the photosensitive material by utilizing the surface activity of the surfactant so that the developer remaining on the surface of the photosensitive material is spread uniformly.

It is true that this method improves development unevenness, but on the other hand, it is necessary to add a large amount of the ionic surfactant, which significantly deteriorates antistatic properties.

Therefore, a third object of the present invention is to form images by developing and fixing a photosensitive material for laser scanners that is spectrally sensitized in the infrared region and is antistatic so as to reduce power generation with respect to various materials. The goal is to provide a way to do so.

The second object of the present invention is to develop and fix a photographic material for a laser scanner, which is spectrally sensitized in the infrared region, to form an image without causing uneven development even when the development time is 75 seconds or less. It is about providing.

A third object of the present invention is to provide a method for forming an image by developing and fixing an a-photo material for a laser scanner that has good photographic sensitivity and can form an image in a short time.

(Means for Solving the Problems) These objects of the present invention are directed to one ill Vc of the support.
In a method for forming an image by developing and fixing a silver halide photosensitive material #+ for laser scanners having at least seven silver halide emulsion layers that has been sensitized by infrared rays, the silver halide The outermost layer on the emulsion layer side of the photographic light-sensitive material contains a polymer represented by the following general formula (H) in an amount of 300% by weight based on the binder in the outermost layer, and is processed in a developing time of less than 1! seconds. This was achieved using an image forming method.

General formula [l) MoX+-1-Yshixy In the formula, X represents an acrylamide monomer residue, and Y represents a monomer other than X that can be copolymerized with X, and a mixture of λm or higher species may also be used. X is 70-100 molti, y is 30-
It represents 0 mol%. Moreover, the molecular weight is 0.2 to SO 1,000.

X of the polymer of the general formula (N) preferably used in the present invention is acrylamide, methacrylamide, and hyalkylacrylamide (alkyl includes methyl, ethyl, hydroxyethyl, etc.).

Examples of Y include N-alkylmethacrylate (alkyl is the same as above), and examples of preferred Y include vinyl alcohol, acrylic acid, and methacrylic acid.

Maleic acid, itaconic acid, m-hydric maleic acid, carboxystyrene, sulfostyrene, vinylsulfonic acid, -CO
NHC(CH3)2Cf-12SOaH and U salts thereof (e.g. alkali metal salts, ammonium salts, lower alkylamine salts, etc.), or vinylpyrrolidone, vinyloxazolidine, acrylic esters (e.g. H, methyl-,
ethyl-, hydroxyethyl-acrylate, etc.), methacrylic esters (e.g., methyl-, ethyl-, hydroxyethyl-methacrylate, etc.), itaconic esters (e.g., methyl, ethyl, hydroxyethyl-itacocate, etc.), styrene, maleic esters ( For example, monomethyl-, dimethyl-, monoethyl-7, diethyl, monohydroxyethyl, etc.), acrylonitrile,
Examples include methacrylate trile. Preferred examples among them are shown below.

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3, H3 UONH2 (1:0 cF (average molecular weight K, 10,000) (# 6,000) (# D, J, 10,000) (l 6,000,000) (# 2,000,000) Polymer of the present invention has a molecular weight of Q, CO to SO, preferably 0.2 to /j, particularly preferably 0.04c to 100,000.

The polymer represented by general formula (I) is preferably water-soluble and has a solubility in water of Q at 25°C, 1wt%.
The above is more preferable, and 1.0w1% or more is particularly preferable.

Further, the amount of the polymer of the present invention added is in the range of μ to 3oo*Wk with respect to the total binder present in the outermost layer on the emulsion layer side.
More preferably μ to 200 μm, particularly preferred! /′
i7.5~/rOM quantity chi. If the amount of the polymer of the present invention added is too small or too large, it will not be effective against uneven development or the binder will not be able to form a film.

By incorporating the polymer of the present invention in the outermost layer on the emulsion side, an image with high photographic sensitivity can be obtained without impairing the antistatic properties and without causing uneven development in processing within 16 seconds. was completed. In particular, the problem of developing solution '7' was solved by including the polymer compound of the present invention, which allowed the developer remaining on the surface of the photosensitive material to spread uniformly when it was transferred from the developing bath to the fixing bath. It is.

The polymer represented by the general formula [I] of the present invention is added to the outermost layer on the side of the silver halide emulsion layer of the photographic light-sensitive material.

In particular, in addition to the outermost layer on the emulsion layer side, the polymer of the present invention has an emulsion layer,
Even better performance can be obtained by adding it to the intermediate layer.

The silver halide photographic emulsion spectrally sensitized in the infrared region used in the present invention can be obtained by adding an enhancing dye having absorption in the infrared region to silver halide grains.

First, aggravating pigments that absorb infrared light will be described.

These are, for example, “The Theory” by Mees.
of thePhotographic Processes
s, 3rd edition" (published by MacMillan in 1966), pages 198 to 201. In this case, it is desirable that the spectral sensitivity, that is, the sensitivity to light in the infrared region, is high, and the emulsion It is desirable that the sensitivity change be small even during storage.For this purpose, many sensitizing dyes have been developed.These are described in US Pat.
No. 095.854, No. 2,095,856. No. 2,955.939, No. 3,482,978, No. 3,552,974, No. 3,573.921,
No. 3,582,344, e.g., U.S. Pat. No. 2,87
Triazine derivatives described in US Pat. No. 5,058 and US Pat.
Mercapto compounds described in U.S. Pat. No. 8, U.S. Pat.
．． 458.318, pyrimidine derivatives described in U.S. Pat. No. 3,615,632, and U.S. Pat.
, No. 083 describes the use of an azaindene compound to perform infrared sensitization using a desensitizing amount of an infrared enhancing dye.

Alternatively, tricarbocyanine dyes and/or 4-quinoline nucleus-containing dicarbocyanine dyes described in JP-A-60-80841 are preferably used. Typical infrared exacerbating dyes are shown below, but of course the present invention is not limited thereto.

C, H, C rich Hs H% Shi-shi-shimu ■5 C2Hs I- CtHa I- CzHs I ■ C, H, I- (C11□), SO,- CtHs I- CtHs M Addition of these sensitizing dyes The amount ranges from 5X10-' mol to 5XlO-' mol per mole of silver halide, preferably 1X
10-' moles to 1×10 moles, particularly preferably 2×1
0- & mol to 5 x 10-' mol.

Next, the silver halide grains used in the present invention include silver chloride,
Any silver halide consisting of chlorine, bromine, or iodide, such as silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide, may be used, but especially silver bromide. , silver iodobromide, and silver chloroiodobromide are preferred. The silver iodide content in the halide eye is preferably 0 to 20 mol%, particularly preferably 0 to 10%. The content of silver chloride in the silver halide is preferably at most 20 mol %, more preferably at least 10 mol %, and particularly preferably at most 5 mol %.

The halogenated root particles particularly preferably used are (+00
) plane/(111) haemostasis is one or more silver halide grains, and 311 can be made by various methods. The most common method is to simultaneously add a silver nitrate aqueous solution and an alkali halide aqueous solution while keeping the p and Ag values at a constant value of 8.10 or less during particle formation (so-called controlled double jet method). , the Ag value is preferably 7.80 or less, and more preferably the pAg value is 7.60 or less.

When silver halide grain formation is divided into two types: nucleation and its growth, there is no restriction on the l'Ag value at the time of nucleation, and the PAg thereof is the same as described above.

These emulsions may have coarse grains, fine grains, or mixed grains thereof, but preferably have an average grain size of about 0.5 mm as measured by projected area method or number average method.
Preferably, the particles have a particle diameter of 0.4 to 1.0 microns. Also, the coefficient of variation for size distribution is within 20%, preferably 15%.
It is preferable to use a monodisperse emulsion within the following range.

The particle shape is preferably cubic, but irregular crystal shapes such as potato-shaped, spherical, plate-shaped, and plate-shaped with a particle diameter of 5 times or more that of particle I7 may be used as long as the above-mentioned preferable surface index conditions are satisfied. It may be something that you have.

The light-sensitive material used in the present invention does not have to have only one halogenated emulsion layer, but may have two or more layers, and two or more types of emulsions with different grain sizes, sensitivities, etc. may be mixed or used in separate layers. . Further, the emulsion layer is not limited to one side of the support, but may be provided on both sides.

These light-sensitive emulsions may be mixed with a substantially non-light-sensitive emulsion (for example, an internally fogged fine grain emulsion). Of course, it may be used by coating in separate layers.

Furthermore, even if the crystal structure of silver halide grains is uniform throughout the interior, there are also those with a layered structure with different interior and exterior 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.

Iridium ions are preferably used in the emulsion of the present invention, and the content of iridium ions is determined by adding a water-soluble iridium compound (for example, hexachloroiridium (Il)) during emulsion preparation.
l) acid salt, hexachloroiridate (IV) salt) in the form of an aqueous solution. It may be added in the same aqueous solution form as silver halide for grain formation, it may be added before grain formation, it may be added during grain formation, or it may be added after grain formation until chemical sensitization, but it is particularly preferred. is added during particle formation.

During the formation of silver halide grains, halogenated illumination agents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds, thione compounds, and amine compounds can be used to control grain growth.

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.

Various commonly used chemical sensitization methods such as gold sensitization, sulfur sensitization, reduction sensitization, and sensitization using 1,000-onythyl compounds can be applied to silver halide photographic emulsions.

Next, binders for the photographic layer of the light-sensitive material used in the present invention include proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose dextran; sugar fermentation conductors such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic It is also possible to use colloids such as polyvinyl alcohol, polyH-vinylpyrrolidone, polyacrylic acid copolymers, or derivatives and partial hydrolysates thereof.

Gelatin as used herein refers to so-called lime-processed gelatin, acid-processed gelatin, derivative gelatin, and enzyme-processed gelatin.

Surfactants may be added alone or in combination to the Yoshin component layer of the present invention.

These surfactants include saponin, dodecylbenzenesulfonic acid, di-2-ethylhexyl α-sulfosuccinic acid Na salt, p-octylphenoxyethoxyethoxyethoxyethoxyethoxyethoxyethoxylate Na salt, and dodecyl t4tI! 8: Na salt,
Anions such as triisopropylnaphthalenesulfonic acid Na salt, N-methyl-oleoyl taurine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N/, he/.

He'-Trimethylammoniodiaminoprono(bromide), cations such as dodecylpyridium dichloride, betaines such as N-dodecyl-N, N-dimethyl, carboxy7betaine, poly(average degree of polymerization (n=io) oxyethylenecetyl Ether, Bo1) (n=10) oxyethylene p-nonylphenyl ether, polyoxyethylene (n=/3) oleic acid monoester, bis(/
- polyoxyethylene ((1=/j)oxy-λ,
Nonions such as ≠-di-t-pentylphenyl)ethane are preferred.

In addition, fluorine-containing surfactants are particularly effective as antistatic agents, such as perfluorooctanesulfone%Na salt, N-propyl-N, e-fluorooctanesulfonylchrysine NatF, N-propyl-N-noξ-fluoro Octane sulfonylaminoethyl oxene polyoxyethylene (degree of polymerization n = 3) butane sulfone mNa salt, hehafluorooctane sulfonyl N', N', N'
-IJ methylammoniodiaminopropane chloride, heperfluorodecanoyl N/, N/-dimethyl-he'-carboxymethylammoniodiaminopropane are preferred. They are coating aids, antistatic agents, lubrication, antifoaming,
It is also applied for emulsification dispersion, sensitization, and other improvements in photographic properties.

In addition, in the present invention, lubricating compositions, such as U.S. Pat. 3rd ° Kota≠, j37
Modified silicones such as those shown in Japanese Patent Publication No. Shoj-2-/λ-ri No. 520 can be included in the photographic constituent layer.

The photographic light-sensitive material of the present invention has a photographic structure of 55.1 cm as described in US Patent No. 3. Hiroshi//, Ri No. 71, 3. Hiro //, Ri No. 72,
The polymer latex described in Japanese Patent Publication Akihiro J-JJJ/etc. may also be included.

Antifoggants, stabilizers, hardeners used in the silver halide emulsion layer, surface protective layer, etc. of the photographic material of the present invention,
There are no particular restrictions on plasticizers, lubricants, coating aids, matting agents, brighteners, dyes, etc.
You can refer to the description in vol. 76, pages 2-2 to 3 (where 7 is the year/month).

The photosensitive material used in the present invention is a photosensitive material that gives a silver image (for example, a medical photosensitive material, a photosensitive material for plate making, etc.)
Other examples include photosensitive materials that provide dye images (for example, color photographic paper, paper for color reversal, etc.).

Next, the development, fixing, water washing, and drying steps in the present invention, which are performed in a development time of 15 seconds or less, will be described.

The developing agents used in the black and white developer used in the present invention are dihydroxyhenzenes and 1-
Most preferred is a combination of phenyl-3-pyrazolidones. 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, 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

As the developing agent for 1-phenyl-3-pyrazolidone or its derivative used in the present invention, l-phenyl-4,4-dimethyl-3-birapritone, 1-phenyl-4-methyl-4-hydroquinemethyl-3-pyrazolidone , l-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, and the like.

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

The developing agent is usually 0. O1 mol/Il~1.2 mol/I!
It is preferable to use an amount of .

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/2 or more. Further, the upper limit is preferably up to 2.5 mol/P.

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 P such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.
Contains H regulator.

Patent application 1987-28708 (boric acid salt), 1986-
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; l-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, amine compounds such as alkanolamines described in JP-A-56-106244 can be used.

In addition, F. A. Messon, “Photographic Brothecine 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.

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 is t'l ' t
Say the time until R.

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

Furthermore, "drying time" is usually 35°C - 100"C5, preferably 40°C to 80°C, where a drying zone is installed in which hot air is blown. This refers to the time spent.

The development temperature and time are about 25°C to about 50°C for 15 seconds or less, preferably 30°C to 40°C for 6 seconds to 15 seconds.
Seconds.

The fixing solution is an aqueous solution containing 1,000 sulfate, 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 periosulfate 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, ammonium sulfate, potassium alum, and the like.

Tartaric acid, citric acid, or conductors thereof can be used alone or in combination of two or more kinds in the fixer. It is effective to use these compounds in an amount of o, oos mol or more per 1N of the fixing solution, particularly 0.01 mol/1 to 0.03 mol/1.

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

The fixer may optionally contain preservatives (e.g. sulfites, bisulfites), pH buffers (e.g. acetic acid, boric acid), pHj
It can contain a Ji modifier (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-218562.

Fixing temperature and time are approximately 20°C to approximately 50°C for 6 seconds to 1
Minutes are preferred, but 6 seconds to 30 seconds at 30°C to 40°C are more preferred, and still more preferably 6 seconds to 15 seconds at 30°C to 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 solution can exist stably as a single agent at pH 4,
pH 5 or more, more preferably pH 4.

It is 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, when the pH is in the range of 4.5 or higher, less sulfur dioxide gas is generated, which improves the working environment. The upper limit of pH is not so strict, but if fixing is carried out at too high a pH, the pH of the membrane will become high even after subsequent washing with water, and membrane swelling will increase, resulting in a large drying load, so the upper limit is around pH 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 amount of each concentrate supplied to the processing tank liquid and the mixing ratio with dilution water can be varied depending on the composition of the concentrate, but generally the ratio of concentrate to dilution water is 1:0 to 8. The total amount of each of the developer and fixer is preferably 50 ml to 1500 ml per 1M of the photosensitive material.

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-mildew water as washing water or stabilizing liquid, 3I per photosensitive material! Not only is it possible to save water by replenishing the amount below, but it also eliminates the need for piping for installing an automatic processing machine, making it possible to further reduce the number of stock tanks. 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-mold water is used in combination with washing water or stabilizing liquid, water scale can be effectively prevented from forming, so a water-saving treatment of 0 to 31, preferably 0 to 12, per 1 photosensitive material is carried out. be able to.

Here, when the replenishment amount is O, there is no replenishment at all other than the amount that the washing water in the washing tank starts to reduce due to natural evaporation, etc., in other words, the so-called "reservoir water" is essentially not refilled. ” refers to the case where the processing method is carried out.

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 multistage countercurrent method is applied to the present invention, the photosensitive material after fixing will be processed in a progressively cleaner direction, that is, in sequential contact with the processing solution that is not contaminated with the fixer, resulting in even more efficient processing. Washing is done. According to this, unstable thiosulfates and the like are appropriately removed, the possibility of discoloration and fading is further reduced, and an even more significant stabilizing effect can be obtained. The amount of water used for washing is also much smaller compared to conventional methods.

When washing with a small amount of water, patent application 1729/1986
It is more preferable to provide a squeeze roller cleaning tank as described in No. 68.

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. 60-295894, No. 61-6
The method using the antibacterial agent described in No. 3030 and No. 61-51396 can be used.

Furthermore, L, E, West “Water Qual
ity Cr1teria” Photo Sci &
Eng, Vol, 9N (L 6 (1965), M
J, Be-ach “Microbiologica
l Growths in Motion-Pic-t
ure Processing” SMPTE Jou
rnal Vol, 85. (1975), RoQ,
Deegan, Photo Processing
Wash Water Biocides' J,
Imaging Tech, Vol 10. Nα6(1
984) and JP-A-57-8542, JP-A No. 57-581
No. 43, No. 5B-105145, No. 57-13214
No. 6, No. 5B-18631, No. 57-97530,
Antibacterial agents described in No. 57-157244, etc.
Anti-spill agents, surfactants, etc. can also be used in combination.

In addition, for the water washing bath, R, T, Reiman, J, Im
age.

RESEARCHD, an isothiazoline compound described in Tech to, (6) 242 (1984)
ISCLO5tlRE Volume 205, Item 205
26 (May 1981 issue), isothiazoline compounds described in Volume 228, Item 22845
(April issue, 1983), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides.

Furthermore, specific examples of anti-piping agents include phenol, 4-chlorophenol, pentachlorophenol, cresol,
0-phenylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-thiazoline)-hencyimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4.4'-trichloro-2'-hydroxydiphenyl ether and so on.

It is preferable that the water treated with anti-mold measures and stored in a water stock tank be used both as dilution water for the undiluted solution of processing solutions such as the developer-fixer and as washing water, since it takes up less space. The dilution water treated with mold treatment and the washing 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.

Specific examples of chelating agents include ethylenediaminetetraacetic acid (IogK = 16.1, the same applies hereinafter), cyclohexanediaminetetraacetic acid (17,6), diaminopropanoltetraacetic acid (13,8), diethylenetriaminepentaacetic acid (
18,4), triethylenetetraminehexaacetic acid (19,7
), and their sodium salts, potassium salts, and ammonium salts, and the amount added is preferably 0.01 to 10
g/l.

More preferably 0. 1~5g/j! It is.

Furthermore, various surfactants can be added to the washing water for the purpose of preventing water droplets from becoming uneven, in addition to silver-image protection and stabilizing agents. 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, to adjust the membrane pH (for example, 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 formalin (used in combination with acids, etc.) and formalin. In addition, chelating agents, fungicides (thiazole,
Various additives such as isothiazole type, halogenated phenol, sulfanilamide, henzotriadurr, etc.), surfactants, optical brighteners, hardeners, etc. may be used.
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, ammonium thiosulfate, etc. as a membrane pH1WA adjuster for the processor to improve image storage stability.

Water washing or stabilization bath temperature and time by the above method is 0°
6 seconds to 1 minute at C to 50°C is preferable, but 15"0 to 40
6 seconds to 30 seconds at °C, more preferably 15 °C
6 to 15 seconds at ~40°C is preferred.

According to the method of the present invention, the developed, fixed and washed photographic material is dried by squeezing out the washing water, that is, by using a squeeze roller method. Drying is carried out at about 40°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 more preferably 4 minutes.
It is about 5 seconds to 30 seconds at 0°C 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 from development, fixing, washing and drying is 3
The processing time is within minutes and 15 seconds, preferably within 100 seconds, and most preferably 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, 'dry 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. To tell.

(Example) The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example 1 (1) After adding an appropriate amount of ammonia to a container heated to 5j0c containing yA-cleaved gelatin, potassium bromide, and water as a monodisperse silver halide emulsion, the pAg value in the reaction container was reduced to 7.
．． The average particle size was determined by adding silver nitrate water bath solution and potassium bromide water bath solution to which iridium chloroiridate (Ill) salt was added to the silver nitrate water bath solution to give a molar ratio of iridium to silver of 60% by double jet method. is 0.6! Monodispersed bromide buttonhole 41 particles of μ were prepared.

In this emulsion grain, g% of the total number of grains existed within Shihiro Q% of the average grain size. After this emulsion desalination treatment,
After adjusting the pH to 6.2 and the pAg to 2, gold/sulfur sensitization was performed using potassium thiosulfate and chloroauric acid to obtain the desired photographic properties of 7.

The (100) plane/(///) fixation ratio of this emulsion was measured by the Kubelkamunk method and was found to be /2. This emulsion was named A.

Next, a monodisperse emulsion B having an average powder size of 0.3 jμ was prepared by changing A only by reducing the amount of ammonia added before grain formation.

(2) Preparation of emulsion coating solution Add 2 to emulsion 〇, jtK; l and emulsion Bθ, 5 to 4LO0C
After heating to an emulsion, a methanol solution of an infrared sensitizing dye, structure A (R x io M/l) was prepared at 70%
CC2 supersensitized shaving g/-bis[Hiro, 6-di(naphthyl-2-oxy)pyrimidin-2-ylabano] stilbene-λ,2'-disulfonic acid catrium salt (Hiro, Hiro x 10 M/ l) Aqueous solution (≠, ≠×lo M/
l) OCQ, methanol@liquid of structural formula B (2,l!×
10 M/1) 3jCC1μ-hydroquine-6-methyl-/, 3, j3, 7-titracindene water bath solution, coating aid dodecylbenzenesulfonate water bath solution, thickener polybotacium p-vinylbenzenesulfonate Compound polyacrylamide (molecular weight 0.♂ million, Q
, 297 m2) and an aqueous solution of dextran (molecules ff30,000)! This was added to prepare an emulsion coating solution.

(CH2)3O3- Structural formula B (3) Preparation of coating solution for the outermost layer of the sensitive material layer A 10 wt% gelatin aqueous solution heated with 0'CK, a thickener polyethylene sulfonic acid sorter, and a matting agent polyester were added. Methyl methacrylate fine particles (average particle size 7.7 μrn), hardener/jbis-(vinylsulfonyl)-furopanol-2° coating aid t-octylphenoxy7ethoxyethanesulfonate sodium water bath solution and p-nonylphenoxybutane Sodium sulfonate salt and polyethylene surfactant water bath solution as antistatic agent (
Polyoxyethylene cetyl ether), a water bath solution of a fluorine-containing compound having the following structure, and the polymer of the present invention were added as shown in Table 7 to prepare a coating solution.

C3F17SO3K CsF 17SO2N (C3H7) (cH2cH,
, -o+15H and C3F17502N (C3[(7
)(CH2CH20su4 (CH2+4SO3N a(
4) Preparation of back coating solution: 10 wt% aqueous gelatin solution heated to 0'C/
KPK thickener polyethylene sodium sulfonate aqueous solution, dye aqueous solution of structural formula C (jXlo-2 mol/1) JO
CA, hardener N, N'-ethylene bis-(vinylsulfonylacetamide) water bath solution.

Coating aid t-octylphenoxyethoxyethanesulfur 7
A coating solution was prepared by adding an aqueous sodium ionate solution.

Structural formula C (5) Preparation of coating solution for the outermost layer of the back layer A 10 wt % gelatin aqueous solution heated to 00C, a thickener polyethylene sulfone powder water bath solution, a matting agent polymethyl methacrylate fine particles (average particle size, 2 μm), coating aid sodium t-octylphenoxyethoxyethoxyethanesulfonate solution, antistatic agent polyethylene surfactant aqueous solution (polyoxyethylene lenonylphenyl ether), and a water bath solution of a fluorine-containing compound having the following structure. and? It was added to prepare a coating solution.

csF't 7SO3K and C6F17SO2N (C3H7) (CH2CH20+
+CH2CH2+4SO 36) Preparation of coating sample The above-mentioned back coating solution was coated together with the outermost layer coating solution of the back layer on one side of a polyethylene terephthalate support so that the gelatin coating property was ell/m 2 . Subsequently, on the opposite side of the support, apply the emulsion coating solution containing the infrared sensitizing dye described in (2) and the outermost WI coating solution for this so that the amount of lead to be coated is J, 697 m2. did.

The resulting sample films were tested for unevenness in development, re-sensitivity, and static markings for urethane rollers used in a portion of a laser scanner and an automatic processor, respectively, using the methods described below.

(7) Evaluation of static marks After conditioning the humidity of an unexposed sample with Cos'C110%RH for 2 hours, the sample was placed in a dark room under the same air training conditions, and the static mark was After rubbing with a urethane rubber roller and a nylon roller, it was developed using the method described below.

The degree of occurrence of static marks was evaluated in the following μ stages.

A: No static marks are observed. B:
Slightly recognized C:
Considerable D: V was observed all over the surface.The compositions of the developer and fixer are as follows.

<Developer> Potassium hydroxide 17g Sodium sulfite bog diethylenetriaminepentaacetic acid 2g Potassium carbonate
jg boric acid
3g hydroquinone
λsg diethylene glycol
/2/1≠-hydroquinemethyl-≠-methyl-/-phenyl-3-pyrazolidone (compound of the present invention) i, bzgj-methylbenzo I-IJ azo-/l/ 0.6 g acetic acid /, r9 bromide Potassium 2g/l with water (pH
10, /j).

<Fixer> Ammonium thiosulfate / 1LOfl Sodium sulfite /j9 Ethylenediaminetetraacetic acid/Nicatorium/Dihydrate 2-Yoda hydroxide thorium 6g/L with water (Adjust pH≠, ysvc with acetic acid).

The developing process is as described above.

Processing temperature, time development 3z'c×i/, s seconds constant H3r0cx/2. s Sand water washing 200C x 7.3 seconds drying 6o0C Dry to Dry processing time 60 seconds (8) Development unevenness evaluation method Sample film jjcm Development unevenness was evaluated.

A: There is no unevenness in the image at all. B; Slightly acceptable C: Quite acceptable. D: It is observed almost all over the surface.

(9) Evaluation of photographic sensitivity 7 film samples! Optical wedge exposure was performed using a semiconductor laser scanner having a wavelength of 7 rOnm. After exposure, the strips were developed and fixed in the manner described above, and further washed with water to obtain strips with a black and white image. The density was measured using a P-type densitometer manufactured by Fuji Shagu Film Co., Ltd., and the sensitivity and resolution were obtained. The reference point for optical rust that determined the sensitivity was [Kaburi-4-0]
, 3''. Treatment was performed as described above.

Comparative polymer (al) As is clear from Table 1, the sample (1-/-I-7) containing the polymer of the present invention showed almost no static marks and no development unevenness. Sensitivity was also high (gives an excellent image. In contrast, processing unevenness occurred significantly in the control, and samples 1-r to ■-2 used for comparison did not have sufficient effect due to the small content of the present invention. This results in uneven development.

Comparative samples) -/ 0~) -/ / are cases where comparative surfactants were used, and although treatment unevenness was certainly improved, static marks were significantly generated. Comparative samples 1-/Col 1-/3 are cases where comparative polymers were used, and there was no improvement in development unevenness, and furthermore, the photographic sensitivity was greatly reduced.As described above, the polymers of the present invention It is clear that photographic materials using this method can produce excellent images in total thickness even if they are developed in a short period of time.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Date 2/7/2017 Director General of the Patent Office Tono Guki 1, Indication of Case Patent Application No.
t No. 2, Title of the invention Image forming method 3, Relationship with the case of the person making the amendment Patent applicant Location 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment Column 5 of "Detailed Description of the Invention" of the specification The description in the "Detailed Description of the Invention" section of the Description of Contents of the Amendment is amended as follows.

2) My page io row "Area method," "Area method" and correct it.

3) λth page Hiroki "Dextran" Delete.

4) Page 22! row After "derivative" "Dextran" Insert.

5) Correct the first item to read "Bromhydroquinone" on page // line as [Bromhydroquinone, 2.3-Sif'romhydroquinone].

6) Page 27, line 7 "Glysine" "glycine" and correct it.

7) 2nd page ioth line "Buffer" "Buffer" and correct it.

8) 1st page, 1st row "Meson" "Mason" and correct it.

9) Line 13 of page λ "Pro-Shichishin" "Processing" and correct it.

1o) No. 30 ¥L! row “　ノ　oo　0csJ　 "lOooC" and correct it.

11) Page 31! 4th line from "or their conductors" Correct as “, gluconic acid or their derivatives”・ 12) 2nd line from page 32 t "It's the same thing as with developer." Delete.

1g) Page 31, line 14c “Do this” "do this" and correct it.

14) Page 37, line 3 after "compound" "," Insert.

1B) 3rd page, line After "stability" "constant" Insert.

16) No. 0 page/line "Lola" "roller" and correct it.

17) No. 1/page/line 1 “It is what is done.” "It can be done." and correct it.

18) jth line from the bottom of the third page "Ethylene" "styrene" and correct it.

lo) 1st line from the bottom of page φμ K after “Phenoxy” "Ethoxy" Insert.

2G) Da! page lth row "Ethylene" "styrene" and correct it.

21) 1st page, 1st line After "Phenoxy" "Ethoxy" Insert.

22) No. 4!L/th line from the bottom of page 6 "Ethylene" "styrene" and correct it.

23) Page 7, line 12 K after “mark” "test" Insert.

24) 4th ct page, line 15F "(Compound ■ of the present invention)" Delete.

2G) No. ≠ 3rd line on page 2 “io, tsJ (-10, J!J and correct it.

26) Page 13, line 2 "Processing" "developing" and correct it.

Claims (1)

[Claims] A method for forming an image by developing and fixing a silver halide photographic material for laser scanners having at least one infrared spectral sensitized silver halide emulsion layer on one side of a support. , the outermost layer on the emulsion layer side of the silver halide photographic light-sensitive material contains 4 to 300% by weight of a polymer represented by the following general formula [I] based on the binder in the outermost layer, and the developing time is within 15 seconds. An image forming method characterized by processing. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X is the acrylamide monomer residue, Y is
represents a monomer other than X that can be copolymerized with X, and may be a mixture of two or more types. x is 70 to 100 mol%, y is 30
~0 mol%. Moreover, the molecular weight is 0.2 to 500,000. )