JPS63177132A - Processing of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To simplify soln. preparing work by mixing a concd. soln. for a replenisher consisting of a part contg. a dialdehyde type hardener and an alkaline part contg. a specified 3-pyrazolidone type developing agent before replenishment and by replenishing the mixed soln. optionally together with water in accordance with the progress of processing of a sensitive material. CONSTITUTION:A concd. soln. for a replenisher consisting of a part contg. a dialdehyde type hardener and an alkaline part contg. a developing agent represented by formula I is mixed before replenishment. A sensitive material is processed by replenishing the mixed soln. optionally together with water in accordance with the progress of processing of the sensitive material. In the formula I, R is aryl group, each of R1-R4 may be the same or different and is H atom, alkyl, aryl or aralkyl group, and when R is unsubstd. phenyl group, R1-R4 are not simultaneously H atom. Thus, soln. preparing work can be further facilitated.

Description

[Detailed description of the invention] C) Industrial application field) The present invention relates to a method for processing silver halide photographic materials,
More specifically, the present invention relates to a simple processing method that does not require complicated preparation of a processing solution when developing a black and white photographic material using an automatic processor C (hereinafter referred to as an automatic processor).

(Prior art) In recent years, black and white photosensitive materials commonly used (for X-ray, plate making, micro, negative, etc.) can be processed using an automatic processor in about 7 minutes!
Developed in a short time of minutes. In particular, when an X-ray photographic material is processed in an automatic processor without sufficient pre-hardening in order to achieve high image density with a small amount of silver, the emulsion film of the material is developed during the development process. It is now common knowledge in the industry to add dialdehyde hardeners and indazoles, benzimidazoles, anthraquinone sulfonic acids, etc. as antifogging agents to the developer to strengthen the mechanical strength of the film. It becomes. These developing solutions consist of multiple components because they are required to have sufficient stability for long-term storage of up to 3 years from the time they are manufactured as a concentrated solution until they are used. Supplied as a concentrate. In the case of a developer containing a dialdehyde hardener, it is most often commercially available as a three-part concentrated solution. Specifically, alkaline parts containing developing agents such as hydroquinones and preservatives such as sulfites, parts containing auxiliary developing agents such as l-phenyl-3-pyrazolidone, and parts containing dialdehyde hardeners. It is made up of.

The above-mentioned antifoggant is contained in parts other than alkaline parts for long-term storage. /-Phenyl-3-pyrazolidone exhibits superadditive development activity in combination with hydroquinones, has high development activity, and is a cheap and very effective developing agent. However, the only drawback is that since it gradually hydrolyzes in alkaline, it is difficult to contain it in alkaline parts from the viewpoint of long-term storage. Therefore, it is necessary to add it to a separate note. Furthermore, since the dialdehyde hardener gradually polymerizes and deteriorates in alkali, it is necessary to add it to a separate part. In this case, F, A.

Photographic Processes by Mason
singChemistry (/ri7j londo
n, FocalPress l pages 13-43 and/!
J~/page 744. Father, it is possible to coexist the dialdehyde hardener tono-phenyl-3-pyrazolidone in the same concentrated solution! However, when they are made into a working solution, they produce insoluble precipitates, so they are not sufficient as a concentrate. The current Jllt-tsu exists under such constraints, albeit inconveniently.

On the other hand, when this development process is carried out using an automatic processing machine, the replenishers for each of the processing solutions, developer and fixer, are usually made by diluting and mixing processing agents each consisting of a plurality of lumps with water. The solution is prepared from K and stored in a replenisher stock tank, and a certain amount of developer and fixer are transferred from the replenisher stock tank to the developing tank and fixing tank of the automatic processing machine as the sensitive material is processed. Each will be replenished.

The automatic processor processing system mentioned above is a complete system that has been used for many years, but as electronic equipment has advanced and developed, there are now some changes to the basic system of wet processing silver halide sensitive materials. Shortcomings have also been highlighted.

That is, a major drawback is that the developer and fixer must be prepared by diluting and mixing them with water, respectively, and a stock tank must be provided for the processing liquid after the preparation. Although chemical mixers have become popular in recent years, they still have fundamental drawbacks, such as the need to prepare a solution using a processing agent made up of multiple parts, and the fact that the space for the chemical mixer is outside the actual production machine. It doesn't change.

(Problems to be Solved by the Invention) Therefore, the purpose of the present invention is, firstly, to simplify the liquid preparation work when processing silver halide photographic light-sensitive materials with an automatic processor; Eliminates the need for space for a replenisher stock tank; reduces the space of the entire automatic processing system; and thirdly, avoids direct contact with the liquid during liquid preparation, eliminating bad odors and improving the working environment. That's true.

Means for Solving Problem C) The above object of the present invention is to provide a silver halide photographic material comprising a support and a hydrophilic colloid layer comprising at least one silver halide emulsion layer. In the method of processing using an automatic processor, a replenisher consisting of a co-agent of parts containing a dialdehyde hardener and alkaline parts containing a 3-pyrazolidone-based image agent represented by the general formula below. This could be achieved by mixing the concentrate before replenishing and then replenishing the mixture and optionally water as the light-sensitive material is processed.

R represents an aryl group, R1, R2, 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, R1
, R2, R3 and R4 are never all hydrogen atoms at the same time. ) As a result of the investigation, the present inventor has determined that by composing the present liquid and the fixer concentrate into two parts, mixing the two parts of the concentrate immediately before use, and using the mixed liquid, This book devises a new system that takes up less space, simplifies liquid preparation work, and eliminates odors. Regarding the mixing method of concentrated liquid, see Japanese Patent Application Laid-Open No. 67-32.
As described in the RAT issue and JP-A-67-319-H7, a single container contains two Notes concentrates in a dispersed state, and there is a method for easily mixing them before use. Space I (There is a method in which the typesetting is contained in two containers, and when it is used, it is transferred to the other packaging material and mixed, or it is mixed in a separate mixing container.In either case, A container of mixed diameter can be used as a replenisher mixture tank, or it can be transferred to a concentrated liquid mixer tank installed in the automatic processing machine.The reserve tank can be used as a conventional diluted replenisher tank. Unlike a tank, the space is small.Alternatively, development processing may be carried out using a replenishment container and a reservoir tank as described in Japanese Patent Application No. 2149012 and No. 61-Cocotjtl. .

The compounds of the invention are described in British Patent No. 9μ3.9.2r, ibid.
, 093. Jri No., U.S. Patent No. J, 2j/.

Although it is included in the compounds described in No. 023, it does not specify any method for automatically developing the photographic light-sensitive material element of the present invention, and does not teach the structure and effects of the present invention as described above. do not have. The compound of the present invention can be processed easily and further technological value and progress can be discovered only by using the photosensitive material processing system of the present invention. The general formula will be further described.

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

Ro, R2, R3, and R4 are each 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.) represents.

Furthermore, 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 hydroxy 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 preferably a hydrogen atom, an alkyl group substituted with an amino group, or a hydroxyalkyl group. R
4 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 1 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.

■ /-phenyl-4AI≠-dihydroxymethyl-3
-pyrazolidone■ /-p-tolyl-+, g-dihydroxymethyl-3
-Pyrazolidone■ l-phenyl-cohydroxymethyl-≠-methyl-3-pyrazolidone■ /-phenyl-μ, ≠-dimethyl-3-pyrazolidone■ /-phenyl-cohydroxymeru≠.

≠-dimethyl-3-pyrazolidone■ l-phenyl-comorpholinomethylta, Hiro-
Dimethyl-3-pyrazolidone■ l-Phenyl-comonomorpholimethyl-≠-methyl-3-pyrazolidone■ /-phenyl-2-hydroxymethyl-μ-methyl-3-pyrazolidone■ l-phenyl-j,! -dimethyl-3-pyrazolidone [phase] l-phenyl-! -Methyl-3-pyrazolidone■ / -p-) +Fludermethyl-Hiroshi-Hydroxymethyl-3-pyrazolidone@/-p-hydroxyphenyl = France, Tadimethyl-3
-pyrazolidone@/-0-)lilugoomethyl-derhydroxymethyl-3-pyrazolidone0t-p-methoxyphenyl-μmmethyl-hiro-hydroxymethyl-3-pyrazolidone (V'4l-(J,!-
Dimethyl) phenyl-tei-methyl-μm hydroxymethyl-3-pyrazolidone The content of the developing agent represented by the above general formula in the alkaline part of the present invention is 0.3 per lt of the alkaline part.
N! Of% especially λ~2! It is preferable that it is f.

In addition, the alkaline parts of the present invention may contain a dihydroxybenzene-based developing agent, a p-amine phenol-based developing agent, an alkaline agent, a preservative, a buffering agent, a chelating agent, an organic solvent, an antifoggant, etc. Can be done.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, co, j-
Dichlorohydroquinone, 3-dibromohydroquinone, ! -dimethylhydroquinone, etc., and hydroquinone is particularly preferred.

The p-amine phenol developing agents used in the present invention include N-methyl-p-amine phenol, p-7 minophenol, N-(β-hydroxyethyl)-p-amine phenol, and N-(μm hydroxyphenyl) glycine. ,
Among them, N-methyl-p-aminophenol is preferred among them, such as coatatill-p-aminophenol and p-benzylaminophenol.

In the present invention, it is preferable to use pyrazolidones represented by the general formula in combination with dihydroxybenzenes, especially hydroquinone.

The content of dihydroxybenzenes in the alkaline parts of the present invention is 0-2j09 per alkaline part/1.
．． In particular, it is preferably 10 to 1 zot.

Examples of the sulfite preservative used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, and potassium metabisulfite.

The alkaline agents or buffers used to set the pH include pH adjusting agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, and tribasic potassium phosphate.

Patent Application No. 1987/-21701 f borate), Japanese Patent Application No. 1983-
23μ33g For example, sucrose, acetoxime,
! -sulfosalicylic 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; I-phenyl-! -Mercaptotetrazole, Komerkabutobenzimidazole! -Mercazoto compounds such as sulfonic acid sodium salts,! - It may contain an anti-capri agent such as a penztriazole compound such as methylbenztriazole, and if necessary, a coloring agent, a surfactant, an antifoaming agent, a water softener, and JP-A-74
The amino compound described in No.-10424AiA may also be included.

The pH value of alkaline parts is 10-/J, especially i
o, z to ii, z are preferred.

Examples of dialdehyde hardeners used in the present invention include the following. Glutaraldehyde, alpha
-Methylglutaraldehyde,! -Methylglutaraldehyde, maleic dialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, α-
Dimethoxy succinic dialdehyde, β-isoprobyl succinic dialdehyde, α, α-diethyl succinic dialdehyde, butyl maleic dialdehyde, or bisulfite adducts thereof, and the like.

The amount of dialdehyde hardener in the part is
jO−≠00 per 1? , particularly preferably ioo to 3ooy. Parts containing the dialdehyde hardener of the present invention may also contain acids such as acetic acid,! - It is preferable to contain an indazole compound such as ditroindazoles.

The pH value is preferably A, j or less, particularly j, o or less.

In the present invention, developer solution C (working solution) can be prepared from the above-mentioned parts.

That is, the developer solution C (working solution) is prepared by mixing the solutions of the λ parts and water, and further adding a starter. As the starter, an aqueous solution containing an alkali halide such as potassium bromide or sodium bromide, or an acid such as acetic acid is used. The amount of developing agent in the developer solution (used solution) is 00OO! ~O0! Mol/l, the amount of geltaraldehyde hardener is /-! Of/l, especially 3-109
/l is preferred.

In addition, F, A are contained in the developer solution C (used solution).

MasoniFPhotographic Process
ssingChemistry (/ri7j Lond
on, FocalPress 1 pages 16-42 and R
e5earchDisclosure/lrj
7 (Dec, / 97ri) and Ko Ou O! (A
water softeners described in prill, /ri II),
The silver stain preventive agent described in JP-A Show Jt-Co≠3≠7, JP-A Show! Amine compounds such as alkanolamines described in No. t-104λ4t4 can be used.

In addition, Photograph by F. A. Mason
icProcessing Chemistry,F
224 N22 of ocalPress (/ri6)
Page Y, U.S. Patent No. 1, J, 0/! No., same, J-9
Those described in No. 2゜JG4L, Japanese Patent Application Laid-open No. Sho≠f-7μ933, etc. may be used.

In the present invention, an automatic developing machine is used, and each time a photosensitive material is developed, a mixed solution of the two parts and a necessary amount of water are added depending on the stiffness.
Water is added to K as a replenisher.

Conventional treatment agents typically consist of a plurality of parts. When it is composed 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 the solution is used. This is to avoid it. Processing agents that are made up of multiple parts usually dissolve and mix the base parts one after another in pre-prepared water, and then the final volume is made up to a certain volume with water before it is used as processing solution C. .

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

The developer concentrate mixture is normally replenished with water to dilute it as the photographic material is processed in the automatic processing machine according to the method of the present invention. 2. It is most preferable to have an R-piece configuration from the viewpoint of machine simplicity and replenishment accuracy.

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 fixer solution, and the time from when it is immersed in the fixer tank solution until it is immersed in the next washing tank solution (C stabilizing solution). say the time

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

Furthermore, "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 30°C to 10°C (preferably 40°C) is blown. say.

Developing temperature and time are approximately 4 seconds at 0C to 4 seconds at 0C.
2 minutes is preferable, but t seconds to 0 seconds at 3o 0C-4to'C is more preferable, and still more preferably 30'C-uoo
It is to develop in 100 to t0 seconds at c.

The fixing solution is an aqueous solution containing thiosulfate and has a pH of 3.r or higher, preferably 2.0 to 2.0.

More preferably p　Hμ, - yo, O.

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. /~about 6 lulu/l
be.

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

Like the developer, which is made up of one part concentrate, the fixer is also mixed immediately before being supplemented with light. M7゛hi, pH≠, 6
In the above, it is also possible to dilute and replenish only water.

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 o, oo per fixer It.
Those containing z mol or more are effective, especially 0.07 mol/l ~
0.03 mol/l is particularly effective.

Specifically, 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 a preservative (e.g. sulfite, monosulfite), a pH buffer agent (e.g. acetic acid, boric acid), a pH adjuster (e.g. sulfuric acid), a chelating agent with water softening ability, or a patent application. Showa 40-2/r! It can contain the compounds described in No.

The fixing temperature and time are the same as for development, about 2o0
c ~ approx! Preferably t seconds to λ minutes at 0°C, but 306C-≠
It is more preferable that the fixing time is from t seconds to 0 seconds at 0°C, and even more preferably from 3 seconds to 0 seconds at 0°C.

The amount of supply to the mixing tank solution and the mixing ratio with dilution water can be varied depending on the composition of the mixture concentration, but in general, the mixing ratio of liquid to dilution water/water The total amount of each of these viewing liquids, retaining liquid, and fixing liquid is from zOml/zoo to light-sensitive material/m2 at a ratio of o - r.
Preferably it is rsl.

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 water washing treatment, and the water washing treatment in the present invention includes not only conventional water washing treatment but also so-called water saving treatment and stabilization treatment. Also,
Water containing various additives known in the art can also be used as the wash water or stabilizing liquid. By using anti-mold water as the washing water or stabilizing liquid, it is possible not only to save water by replenishing the amount of 3 L or less per m2 of photosensitive material, but also to eliminate the need for piping for installing an automatic processor.

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.

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 No. 6 of the Japanese Patent Publication No. 72-72.

Further, part or all of the overflow liquid from the washing or stabilizing bath, which is generated by replenishing the water treated with mold-proofing means depending on the treatment, is disclosed in Japanese Patent Application Laid-Open No. 60-23
As described in No. 1133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that. By doing so, the above-mentioned stock water can be saved, and waste liquid is also reduced, which is preferable.

The anti-mildew methods include the ultraviolet irradiation method described in %Kaisho Otsu θ--Δ3ri No. 3, the method using a magnetic field described in To-Kot3ri≠0, and the same &/-/J1632. A method of purifying water using an ion exchange resin as described in the patent application No. 1983-
No. 213107, 40-29! r91fi issue, same j/
-6 JOJO issue, same t/-! The method using the antibacterial agent described in No./J Riwo can be used.

Furthermore, L, E, West @Water Qua
lityCriteria' Photo Sci &
Eng, Vol, 21it (/9 j j),
M, W, Beach"'Microbiology
cal Growths inMotion-Pi
ture Processing'SMPTE J
our own Vol, rj (lri761゜R,O
, Deegan, “Photo Processin.
gWash Water Biocides''' J
, ImagingTech, Vol 10. &A
(/rire) and JP-A-37-j No. 1, 77-!
I/≠3 issue, same jr-iozi4Ar issue, same! 7-/J
Co/4A4 issue, 5r-irtJ1 issue, same! 7-971
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 30, J-7-/J-7-μμ, and the like can also be used in combination.

In addition, for the washing bath, R.T. Kreiman, J.Im.
age, Tech/0. (5) Kosan-(/ri♂≠)
Inthiazoline compounds described in K, RESEARC
HDISCLO8URE Volume 203, Item 20
! 26 (1/year, ! month issue), inthiazoline compounds described in the same volume, Item 2r4fi
! Isothiazoline compounds described in (/ri 23, Sangetsu issue), patent application 1987-! Compounds such as those described in No. 73 Ribu can also be used together as microbiocides.

In addition, "Chemistry of antibacterial and antifungal" by Hiroshi Horiguchi, Sankyo Publishing (Showa 3)
7), "Anti-bacterial and anti-mold technology... book", Japanese Society of Anti-bacterial and Anti-mold, Hakuhodo (1987) may also be included.

Washing or stabilization bath temperature and time are o'C-t.

Preferably t seconds to minutes at 0C, but 6 at ir0cm≠00C
More preferably seconds to seconds, and even more preferably /! 0C~4Ao0
It is preferable to process at c for t seconds to 2j seconds.

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 ≠00C to about too0C, 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 about 10 seconds at ao 0C to to'c. ~Hiroo seconds.

The time from the moment the leading edge of the photosensitive material to be processed by the method of the present invention enters the film insertion section of the processor to the moment the leading edge emerges from the processor after being processed @Dr
Rapid processing can be achieved in which the y to Dry' time is within 1 minute, preferably within 1 minute, and more preferably within 700 seconds.

In the processing of the present invention, there are no particular limitations on the photographic light-sensitive material, and general black-and-white light-sensitive materials are mainly used.

Preferably X-ray film for direct photography, X for indirect photography
- Ray film, CRT film, etc. Examples include medical or industrial X-ray photographic materials, X-ray duplex photographic materials, and medical CRT image photographic materials. Alternatively, it can also be used as a general black and white negative film.

A silver halide photographic material applicable to the method of the present invention comprises a support and at least four silver halide emulsion layers coated thereon. Further, the halogenated emulsion layer can be coated not only on one side of the support but also on both sides.

Of course, a pack layer, an antihalation layer, an intermediate layer, an uppermost layer (eg, a protective layer), etc. can be included as necessary.

Silver halide emulsions contain hydrophilic colloids such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, such as gelatin, modified gelatin, and colloidal colloids. albumin, casein, carboxymethyl cellulose,
hydroxyethylcellulose, soda alginate, polyvinyl alcohol, polyvinylpyrrolidone, or a mixture thereof). Silver halide emulsions are usually prepared by combining a water-soluble silver salt (for example, silver nitrate) and a water-soluble halide salt by a method well known in the art (for example, a single jet method, a double jet method, a controlled jet method, etc.). It is produced by mixing in the presence of a hydrophilic colloid and undergoing physical ripening and chemical ripening such as metal sensitization and/or sulfur sensitization. The emulsion obtained in this way has cubic, r-hedral, spherical shapes, as well as Re5earch Di
sclosure2, zz3<<(January
/ri, r3) can be achieved by using tabular silver halide grains with a high cross-sectional ratio.
It can also be used in combination with the internal latent image type silver halide grains and the surface latent f2 type silver halide grains described in the /-λOtt publication.

During the manufacturing process or just before coating, silver halide emulsions contain spectral sensitizers (e.g., cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g., μm hydroxy-t-methyl-i, 3,3a), .

7-chitrazaindene), sensitizer C, e.g., U.S. Pat.
J, 4/2, No. 192), antifoggants C such as benzotriazole,! - Nitrobenzimidazole, polyethylene oxide, hardening agents (e.g. formalin, glyoxal, mucochloric acid, -
monohydroxy≠,6-dichloro-5-)riazine),
Coating aids (for example, saponin, sodium lauryl alphate, dodecylphenol polyethylene oxide ether, hexadecyltrimethylammonium bromide), etc. can be added. The silver halide emulsion thus produced is coated and dried on a support such as cellulose acetate film or polyethylene terephthalate film by a dip method, an air knife method, a pea method, an extrusion doctor method, a double-sided coating method, or the like.

C Example) The present invention will be illustrated below with examples, but the present invention is not limited thereto.

Example 1 Processing ■ Development concentrate formulation) AR for Jr.
tA artB artC Starter developer preparation method> Approximately! Water λot was put into the replenisher stock tank of the OL, and then Part A, Part B, and Part C were sequentially added and dissolved while stirring, and finally the solution was made up to 311 with water to obtain a developer replenisher tpHlo, 30).

Add 20 m of the above starter to this developer replenisher/l.
After the developer added at a ratio of 1 pH 10, J) was first added to the developing tank of an automatic processor, the developer replenisher was added each time the photosensitive material was processed. rd/four cut 1
Sheets were supplemented (/O1nch X/21ncN.

<Fixer concentrate formulation> Part A Pa for Jr.
rtB Fixer Preparation Method> Put a water cot into a replenisher stock tank with approximately 1000 O2, then add and dissolve the above Part A% Part Bs sequentially while stirring, and finally set with water to replenish the fixer. It was made into a liquid.

The same fixer replenisher was first poured into the fixing tank of the automatic developer (pii≠, stiff.

From then on, every time the photosensitive material is processed, add the above fixer replenisher to JO.
m/17! J-cut/sheet 110inchX/ko1nch)
Replenished.

The development process is as follows.

Also, the dry-to-dry processing time is 4 seconds.

Processing■ Kugen gI! Preparation of Concentrated Solution> Developing Solution Preparation Method for 3et> The concentrated solution of Part B was added into the container of Part A with moderate stirring. This mixed solution //.

At was used as a developer replenishment mixture, and the mixing container was used as a developer replenishment mixture stock tank.

2.33L of water was added to the developer replenishment mixture//, and 20ml of the starter used in the processing process.
1 was added to the developing tank of the automatic developer used in Process I.

(pH 10, /!t) After that, each time the photosensitive material is processed, the above developer replenishment mixture /J, J111 and water 31.1WLl are added.
/ 7 pieces cut into quarters (#) inch x 7 pieces 1 inch) was replenished.

<Fixing concentration prescription> Part A Jr. ar
tB Fixer Preparation Method> The concentrated solution of Part B was added to a Part B solution vessel while stirring moderately. This mixed solution/J.

St was used as a fixing replenishment mixed liquid, and the mixing container was used as a fixing replenishment mixed liquid stock tank.

Water was added to this fixing replenishment mixture/1 to fill the fixing processing tank of the automatic processor used in the process fiI (pH 4t, stiffness).

Thereafter, each time the photosensitive material is processed, the fixing replenishment mixture 2 is applied.
/lnl and water J P1R1/1 piece cut into quarters (10inch
L coir! ch) supplemented.

The development process is exactly the same as the processing process.

Treatment■ Treatment■ is ≠-hydroxymethyl-p-methyl-/-722-3-pyrazolidone l/
μ? rCompound of the present invention (2) was replaced with /-p-tolyl-Hiro-methyl-der-hydroxymethyl-3-pyrazolidone 749 (Compound of the present invention ◎Exactly the same as treatment ◎ except for NC.

For processing steps to (1), 7di

The treatment was carried out for 6 days a week for 7 days, and continued for 3 weeks. During this time, when the replenishment mixture in the replenishment tank decreased and became insufficient, the groove was filled with a new replenishment mixture prepared by the adjustment method shown above.

Next, the results of treatments I to ① were summarized in light weight.

Sensitivity was determined as a relative value of the reciprocal of the exposure amount required to obtain a blackening degree of Capri value +/-0. Fog values were measured as the net density increase corrected for the base density. The gradation is KazuQ+7. It appeared as the slope of the straight line connecting the density of Jj and the density point of fog+1.0.

It is clear from Table I that the simple treatments ① and ② of the present invention make the liquid preparation work easier than the treatment process, reduce the amount of swiss, and reduce bad odors from the working environment during liquid preparation. objectives have been achieved.

Furthermore, the results of photographic properties indicate that the treatments (1) and (2) of the present invention make it possible to maintain preferable photographic performance for a longer period of time, similar to the conventionally used treatments.

The stability of the 3-pyrazolidones in the developing concentrate formulation Part A of Example 1 in the alkaline solution was evaluated at 50° using a polypin medium-tight stopper.
The results of the investigation after aging in C for λ weeks are as follows.

Therefore, it can be seen that the purpose of the present invention cannot be achieved unless the specific 3-pyrazolidones of the present invention are used in the simple treatment system of the present invention using the present liquid as a co-agent.

(Effects of the Invention) According to the present invention, it is possible to convert the current solution into 2 notes, and the replenisher can be prepared by simply mixing concentrated solutions of 2 notes each of the current solution and the fixer. Overall, the liquid preparation work can be made easier, and the space of the replenisher stock tank can be eliminated, making it possible to reduce the space of the entire automatic processing system. Furthermore, since the fixer replenisher can be easily prepared, bad odors can be reduced from the working environment during liquid preparation.

In addition, it is possible to easily prepare liquids using an automatic developing machine, which enables complete piping-free processing, eliminates restrictions on installation location, and makes maintenance easier than usual. be done.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment Date February 1, 1939, Case Indication Long-awaited application No. 1 in 1939! No. 3 No. 2, Name of the invention Processing method for silver halide photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment 1 of ``Detailed Description''& Contents of Amendment The description in the ``Detailed Description of the Invention'' section of the specification is amended as follows.

l) the page jth line “Make it unnecessary;” “Make it unnecessary.” and correct it.

2) Page 7, line 1 "Dispersion" "Separation" and correct it.

3) 1st page, row 0 "Wrapping material" "container" and correct it.

4) Page r/row "Automatic development" "Automatic processor" and correct it.

s) 1st page, line 10 "From Hydroquinone" "Bromhydroquinone" and correct it.

6) Line 13 of page 1 "Jibrom" "Jibrom" and correct it.

7) Page 1, line 12 [After about 6 mol/l JO "(Used liquid)" Insert.

8) Page 0, row 0 after "those" "Invitation" Insert.

9) Page 3, line 3 After “Fixer” "(Used liquid)" Insert.

10) Page 27, line λ "genus" "increase" and correct it.

11) Page 27! row “DlsJ [DisJ and correct it.

12) No./page 6th line After “full amount” "(Replenishment amount)" Insert.

ls) Page 22 is the line "Hi" "Yes" and correct it.

14) Whistle page 30! row [10,zJ "10./!" and correct it.

15) Page 30, line 10 "but" Delete.

16) Page 33 l! rth row "Automatic developer" "Automatic processor" and correct it.

17) Page 31, line 72 "Automatic developing machine" "Automatic processor" and correct it.

18) Page 3.2, line 20 "Hi" color "Yes" and correct it.

19) Page 33, line 1 r　CpHto, tz) after J "." Insert.

20) No. 34! page λth line After "shrink" "liquid" Insert.

21) Page 33, line 3 "Automatic developing machine" "Automatic processor" and correct it.

22) Page 31, line 13 After a "long period" "Across," Insert.

23) Page 30, line λ "Automatic developing machine" "Automatic processor" and correct it.

Claims (1)

[Scope of Claims] A method for processing a silver halide photographic material comprising a support and a hydrophilic colloid layer including at least one silver halide emulsion layer using an automatic processor, A concentrated replenisher solution consisting of two parts, a part containing a hardening agent and an alkaline part containing a developing agent represented by the following general formula, is mixed before replenishment, and then a part containing a hardening agent and an alkaline part containing a developing agent represented by the following general formula are mixed together, and then a concentrated solution is added as the photosensitive material is processed. , a development processing method in which development processing is performed by replenishing the mixed solution and water if necessary. General formula ▲ 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. )