JPH01124851A - Method for development processing of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the stability of a developing soln. which has stability to air oxidation, maintains the degree of concn. and does not assist silver staining by incorporating at least one kind of specific compds. into an alkaline developing soln. contg. hydroquinones as a developing agent. CONSTITUTION:A silver halide photosensitive material is processed with the developing soln. prepd. by incorporating at least one kind of the compds. expressed by formula I or II into the alkaline developing soln. contg. the hydroquinones as the developing agent. In formula I, R<1>, R<2> denote a hydrogen atom, alkyl group, etc.; there are a halogen atom, aryl group, etc., as a substituent. The carbon atoms of R<1> and R<2> are preferably 1-10. In formula II, A denotes a hydrogen atom, alkyl group, etc.; there are a halogen atom, aryl group, etc., as a substituent. More preferably A is a substd. or unsubstd. alkyl group, aryl group, etc. X is >C=0, >C=S, etc.; R<3> is a hydrogen atom, alkyl group or aryl group, etc.; Y is a hydrogen atom, etc. The stability to the air oxidation is improved and the degree of concn. is maintained and the stability to prevent promotion of the silver staining is enhanced by constituting the title material in such a manner.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for developing silver halide photographic materials, and particularly to a developer containing hydroquinones with improved stability.

(Prior Art) After exposure, silver halide photographic materials are generally processed through the steps of development, fixing, and washing. Among them, black and white developer is
It is generally an alkaline solution containing hydroquinones as a developing agent, aminophenols or 3-pyrazolidones as an auxiliary developing agent, and containing sulfites.

This sulfite is used in the form of an alkali metal sulfite or bisulfite, and is an essential component both for maintaining the development reaction activity of hydroquinone and for suppressing air oxidation of the developer. In addition, sulfite has the ability to dissolve silver halide appropriately, and is sometimes used in a method of improving graininess by actively utilizing so-called dissolution physical development action during the development reaction process.

On the other hand, higher stability of the developer is desired. If the developer is stable against air oxidation for a long period of time, a certain level of photographic performance can be obtained without the hassle of maintaining and managing the developer.

In particular, when maintaining and managing the liquid composition while replenishing a certain amount of replenisher in an automatic processor (hereinafter referred to as an automatic processor), reducing the amount of replenisher reduces the amount of waste liquid, that is, reduces the pollution load. This is also important from the perspective of reducing running costs. In order to reduce the amount of replenisher, the stability of the developer must be higher.A decrease in the amount of replenisher will further lengthen the residence time of the developer in the automatic processor and replenisher tank. This is because it increases the degree of air oxidation of the developer.

Air oxidation of the developer can be prevented by increasing the sulfite concentration in the developer, but there is a limit to increasing the sulfite concentration. One of the reasons is as follows. In other words, normally, a developer is prepared as a concentrated solution several times and diluted for use during actual development processing, but one of the biggest factors that controls the degree of concentration of this concentrated solution is sulfite. . If a large amount of sulfite is added to improve the stability of the developer, the concentration will decrease, and in extreme cases, the concentration will remain the same from the time the developer is first prepared to the time it is used in the field using an automatic processing machine. In other words, the same volume of developer is used each time, which is very disadvantageous in terms of transportation and space. Another reason is that a developer containing a large amount of sulfite causes more silver halide to dissolve and elute from the silver halide photosensitive material, resulting in more silver stains in the developer and promoting stains on the developing rack and rollers. This is because you will have to do so.

For these reasons, we added more sulfite to the developer, which is effective in improving the stability of the developer. The situation has been increasing in recent years.

(Object of the Invention) Therefore, the first object of the present invention is to improve the air oxidation stability of a developer containing hydroquinones as a developing agent.

The second purpose is to increase the stability of the developer while maintaining the :a degree of condensation of the developer concentrate.

The third objective is to increase the stability of the developer without promoting silver staining.

The fourth objective is to improve the stability of the developer, thereby reducing the amount of developer replenisher, reducing the pollution load, and increasing the economic efficiency of the development process.

(Structure of the Invention) The above object of the present invention is to provide an alkaline developer containing hydroquinones as a developing agent containing at least one compound represented by the following general formula (I) or (II). This was achieved by processing a silver halide photosensitive material with a special developer.

General formula (I) R'-N-R''H In the formula, R1 and Rt are hydrogen atoms, alkyl groups (including those with substituents, methyl group, ethyl group, n-butyl group, t
-butyl group, n-octyl group, cyclohexyl group, etc.)
, alkenyl groups (including those with substituents, propylene group, cyclohexene group, etc.), aryl groups (including those with substituents, phenyl group, naphthyl group, etc.), or heterocyclic groups (including those with substituents) (including imidazole, triazole, tetrazole, lysine, pyrimidine, triazine, etc.), and R' and Rt are connected together with a nitrogen atom to form a hetero'f! J (morpholine ring, etc.) may be formed.

Substituents include halogen atoms (fluorine atoms, chlorine atoms,
bromine atom, etc.), aryl groups (phenyl group, p-chlorophenyl group, etc.), alkoxy groups (methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (
phenoxy group, etc.), sulfonyl group (methanesulfonyl group, p-)luenesulfonyl group, etc.), sulfonamide group (methanesulfonamide group, benzenesulfonamide group, etc.), sulfamoyl group (diethylsulfamoyl group, unsubstituted sulfamoyl group) ), carbamoyl group (
unsubstituted carbamoyl group, diethylcarbamoyl group, etc.)
, amide group (acetamide group, benzamide group, etc.),
Ureido group (methylureido group, phenylureido group, etc.), alkoxycarbonylamino group (methoxycarbonylamino group), allyloxycarbonylamino group (
phenoxycarbonylamino group, etc.), alkoxycarbonyl group (methoxycarbonyl group), aryloxycarbonyl group (phenoxycarbonyl group, etc.), cyano group, hydroxy group, carboxy group, sulfo group, nitro group, amino group, (unsubstituted) amino group, diethylamino group)
, an alkylthio group (such as a methylthio group), an arylthio group (such as a phenylthio group), and a heterocyclic group (such as a morpholino group and a pyridyl group). Here, R1 and R1 may be the same or different, and R1 and R1 may be the same or different.
The substituents of 8 may also be the same or different.

Further, the number of carbon atoms in R1 and Rz is preferably 1 to 10, particularly 1
~5 is preferred. The nitrogen-containing heterocycle formed by linking R1 and Hg includes a piperidyl group, a piperidyl group, a N
Examples include -alkylpiperazyl group, morpholyl group, indolinyl group, benztriazolyl group, and the like.

Preferred substituents for R1 and R8 are a hydroxy group, an alkoxy group, a sulfonyl group, an amide group, a carboxy group, a cyano group, a through group, a nitro group, and an amino group.

Specific examples of the compound represented by the general formula (I) used in the present invention are shown below, but the present invention is not limited to these compounds.

H CJs N-C11IaOCHs H CH3-N CtHaOC*Hs OH CHsOCtH4N-CxHaOCHsOf( CxHsOC*Ha N CJ40CtHsOH CtHsOC!)14 N CJs\-1-noOH Quantity CxHsSOxC zHa N C! HaSOtC
Js-Ol ＼---ノ1-G:D OHHoo-CH
l N CHl COOHl-01001( HOCHl CHt N-CHt CHt O
Hl-051 OH CH3CHz NCHt CHs -0O NH,O)1 1-(to) OH OH OHOH R In the formula, A is a hydrogen atom, an alkyl group, an aryl group, an amino group, a heterocyclic group, an alkoxy group, an aryloxy group, carbamoyl group, sulfamoyl group, acyl group, carboxy group, hydroxyamino group, or hydroxyaminocarbonyl group. group, aryloxy group, hydroxy group, sulfonyl group, sulfonamide group, sulfamoyl group, sulfo group, amide group, ureido group, cyano group, hydroxy group, aminocarbonyl group, carboxy group, nitro group,
Examples include amino groups, alkoxycarbonyl groups, aryloxycarbonyl groups, alkylthio groups, arylthio groups, and heterocyclic groups (pyridyl groups, morpholino groups, etc.).

Preferably, A is a substituted or unsubstituted alkyl group, aryl group, amino group, alkoxy group, or aryloxy group. Particularly preferred examples include substituted or unsubstituted amino groups, alkoxy groups, and aryloxy groups. The number of carbon atoms is preferably 1 to 10.

S Representing -3O-, preferably X is -C-.

R3 represents a hydrogen atom, an alkyl group, or an aryl group. In this case, A and Rs may be linked to form a ring structure. These include those that are substituted, and the substituent is listed in A. Same as substituent. In particular, preferably R
s is a hydrogen atom.

Y represents a hydrogen atom or a group that can become a hydrogen atom through a hydrolysis reaction.

Specific examples where Y represents a group that can become a hydrogen atom through a hydrolysis reaction include the following.

1) A method of protection with an ester bond or a urethane bond, that is, Y represents -C-R4; examples of R4 include an alkyl group, an aryl group, and an amino group.

2) Method of protection with imidomethyl blocking group described in JP-A-57-158638, ie, Y represents a plurality of atoms necessary to complete a heterocycle having a membered ring or a 6-membered ring.

Specific examples of the compound represented by the general formula (If) are shown below, but the present invention is not limited thereto.

(II) - (2) CHs -C-NH-Of(' (n) - (3) Ca　He　OC-NHOH CH.

CH, -C-N-OH (II) - (6) Ht　NC-NH-OR (n)-(7) Hs ■ CHs　　C-N　OH (II)-(8) H-C-NHOH (II) - (9) (II)-0I HII CHs N CNHOH O3S (II)-0ri (If) -03i.

tC, Hq 0CNHOH HONI(CNHO)I (II) -〇6) (If) -01 (It) -0! ll CHs SO* N HOH (II) -@0 CHs CNH0CCHs (If) - (23) Other specific examples of the compound represented by the general formula (summer) and the synthesis of the compound of the general formula (■) are as follows. It can be synthesized by the known method shown below. U.S. Patent No. 3,661.996
No. 3,362,961, No. 3,293.034, Japanese Patent Publication No. 42-2゜794, U.S. Patent No. 3,491.
No. 151, No. 3.655.764, No. 3,467.7
No. 11, No. 3,455.961, No. 3,287.12
No. 5, No. 3,287.124, J, Am, Chew,
Soc, +73, 2981. J, Org, 27.
4054. Special Publication No. 49-10.692, and the general formula (
The compound represented by II) can be synthesized by the known method shown below.

Organic Fanctlonal Group
Preparations Tl5p, 406-43
2 (^ academic Press), Sy
ntheticOrganic Chemistry
, p, 419,565,569.576.577 (J
ohn Wllley & 5ons, Inc.).

These compounds may form salts with various acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, Shellic acid, and acetic acid.

The amount of the compound of the above general formula added is 1j of the developer! hit, preferably 0. 1 to 50 g, more preferably the developing agent used in the developer of the present invention is a combination of hydroquinones and 1-phenyl-3-pyrazolidones, or A combination of hydroquinones and p-aminophenols is good.

Hydroquinone-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2.3-dichlorohydroquinone, 2.5-dichlorohydroquinone, 2.3-dibromohydroquinone, and 2.5-dichlorohydroquinone. Examples include dimethylhydroquinone, and hydroquinone is particularly preferred.

The p-aminophenol developing agent used in the present invention includes N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl) Glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p-
Aminophenols are preferred.

The 3-pyrazolidone developing agent used in the present invention is 1
-Phenyl-3-pyrazolidone, 1-phenyl-4,4
-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, l-
Phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone,
1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-)yl-4,4-dimethyl-3-pyrazolidone, 1-p-)lylu-4-methyl-4-hydroxymethyl-3-pyrazolidone ,and so on.

Hydroquinone developing agents are usually 0.01 mol/2 to 1
．． 5 mol/Il, preferably 0.05 mol/l to 1.2
Mol/j! used in amounts of

In addition to this, p-aminophenol type developing agent or 3-pyrazolidone type developing agent is usually 0°0005 mol/
i~0.2 mol/Il, preferably 0.001 mol/l
It is used in an amount of ~0.1 mol/l.

Sulfites used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
etc., sulfite is 0°2 mol/j! The above is especially 0.
It is preferable to have 3 morphs of 2 or more, and the upper limit is preferably up to 2.5 mol/l in the developer concentrate.

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

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

JP-A-62-186259 (Borate), JP-A-60
Buffers such as No.-93433 (eg, sucrose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

In the present invention, the developer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions.

Here, the chelate stability constants are L and G.

5illdn-A, E, Marte11, H''
5tabil 1tyConstants of M
etal-ion Complexes”, T
heChemical 5ociety, Lond
on (I964), S.

Written by Chaberek Liao A, E, Marte11,
”OrgantcSequesteringAge
nts' means a constant generally known by Wiley (I959) m, etc.

In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe''°).

In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include the following compounds, but are not limited thereto. Namely, ethylenediamine diorthohydroxyphenylacetic acid, triethylenetetraminehexaacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxy Ethyliminodiacetic acid, 1,3-diamino-2-propatoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine-N, N, N', N'
Tetrakis methylene phosphonic acid, nitrilo-N, N, N
-1rimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonethane-
2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-phosphonopropane-1,2,3-)licarboxylic acid, catechol-3,5-
Examples include disulfonic acid, sodium birophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate.

Further, dialdehyde-based hardeners or bisulfite adducts thereof are used in the developer, and specific examples thereof include gel tar aldehyde and bisulfite adducts thereof.

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 = mercapto such as 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, etc. R@aaarc
b Disclosure No. 176-1, NII
Development accelerators described in L17643, Section XXI (February issue, 1978) and, if necessary, toning agents, surfactants, antifoaming agents, water softeners, JP-A-56-10624
May contain the amino compound described in No. 4, etc.
- In the development process of the present invention, a silver stain preventive agent, such as the compound described in JP-A-56-24347, can be used in the developer.

The developer of the present invention includes European Patent Publication No. 136582
No. 958,678, U.S. Pat. No. 32,327
Amino compounds such as alkanolamines described in No. 61 and JP-A-56-106244 can be used for the purpose of accelerating development, increasing contrast, and other purposes.

In addition, "Photographic Processing Chemistry" by F. and A. Mason, published by Focal Press (
I966), pages 226-229, U.S. Patent No. 2,19
No. 3.015, No. 2,592゜364, Japanese Unexamined Patent Publication No. 1973-
64933 and the like may be used.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 7.0.

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

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 their derivatives can be used alone or in combination of two or more. These compounds are the fixer lj! per 0.
Those containing 0.005 mol or more are effective, especially those containing 0.005 mol or more. O1 mol/
It~0.03 mol/l is particularly effective.

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 water softening ability, and The compound described in No. 62-78551 can be included.

In the development processing method of the present invention, after the development and fixing steps,
Replenishment amount of 31 or less (0
It can also be treated with rinsing water or a stabilizing solution (including sump water rinsing). In other words, not only can water be saved, but also piping for installing an automatic processor can be eliminated.

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 is done.

For the above-mentioned water-saving treatment or piping-free treatment, it is preferable to apply anti-mold means to the washing water or the stabilizing liquid.

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, JP-A-62-
No. 115154, No. 62-153952, Patent Application No. 1983
The method using the antibacterial agent described in No. 63030 and No. 61-51396 can be used.

Furthermore, L, E, Glest, ``Water
QualityCriteria ″ Pho
to, Sci, & I! ng, Vol. 9
N [L6 (I965), M, W, Beach,
Microbiological Growths
in Motion-Picture Process
ing"SMPTI! Journal Vol.
85. (I976), R.

0, Deegan, Photo Processes
sing flash l1aterBiocides
J, 1maging Tech 1 G, Na
6 (I984) and Japanese Unexamined Patent Publication No. 57-8542, 57
-58143, 58-105145, 57-1
No. 32146, No. 5B-18631, No. 57-975
Antibacterial agents, antifungal agents, surfactants, etc. described in No. 30, No. 57-157244, etc. can also be used in combination.

Furthermore, R, T in the water washing bath or stabilizing bath.

Kreiman, J. Image,
Tech 1 0. (6) 2 4 2 pages (I98
The isothiazoline compound described in 4), Re5ea
rch I) isclosure volume 205, koji 205
26 (I981, May issue), isothiazoline compounds described in Volume 228, Na22845 (I9
Isothiazoline compounds described in 1983, April issue), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as antibacterial agents (?l1crobioclde).

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, Hakuhodo (1988) may also be included.

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. 163217/1982.
It is also preferable to adopt a water washing step configuration as in No. 290619.

Furthermore, 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 according to the treatment according to the method of the present invention, is used in Japanese Patent Application Laid-Open No. 1986-1999. As described in Japanese Patent Application No. 235133, it can also be used in a processing liquid having a fixing ability, which is a processing step before that.

In the present invention, "developing process time" or "developing time" refers to the time from when the leading edge of 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, ``r fixing time.'' The period from immersion in the fixing tank liquid until immersion in the next washing tank liquid (stabilizing liquid) ``Washing time'' refers to the time during which the film is immersed in the washing tank liquid.

In addition, "drying time" is usually 35℃ to 10℃ for automatic processors.
A drying zone is installed in which hot air of 0°C, preferably 40°C to 80°C is blown, and refers to the time spent in the drying zone.

In the development process of the present invention, the development time is 5 seconds to 3 minutes, preferably 10 seconds to 2 minutes, and the development temperature is preferably 25C to 50C, more preferably 25'C' to 40C.

The fixing temperature and time are preferably about 0° C. to about 50° C. and 5 seconds to 3 minutes, and more preferably 25° C. to 40° C. and 10 seconds to 2 minutes.

Water washing or stabilization bath temperature and time are 0 to 50℃ for 5 seconds to 3
minutes is preferred, and 10 seconds to 2 minutes at 15°C to 40°C is more preferred.

According to the method of the invention, the developed, fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is approximately 0℃~
The drying time is carried out at about 100°C, and although the drying time can be appropriately changed depending on the surrounding conditions, it is usually about 5 seconds to 2 minutes, and particularly preferably about 5 seconds to 1 minute at 40°C to 80°C.

The photographic material used in the developing method of the photosensitive material of the present invention is not particularly limited, and general black and white photosensitive materials are mainly used, as well as color photosensitive materials that undergo reversal processing, such as black and white development of color reversal film or paper. It can also be used in liquids.

In particular, photographic materials for laser printers for medical images, scanner materials for printing, medical direct photography X-ray materials, medical indirect trauma X-ray materials, CR7 image recording materials, and microphotosensitive materials. , general black and white negative film, black and white photographic paper, etc.

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

Of course, a back layer, an antihalation layer, an intermediate layer, a top layer (for example, a protective layer), etc. can be included if necessary. A silver halide emulsion is one in which silver halides such as silver chloride, silver iodide, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide are dispersed in a hydrophilic colloid. 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, followed by physical ripening and chemical ripening such as gold sensitization and/or sulfur sensitization. The emulsion thus obtained has cubic, octahedral, spherical, and other shapes.
(January 1983), high aspect ratio tabular silver halide grains can be used, and internal latent image type silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2068 can be used. It can also be used in combination with silver halide grains.

During the manufacturing process or just before coating, the silver halide emulsion is
Spectral sensitizers (e.g. cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (e.g. 4-hydroxy-
6-methyl-1,3,3a.

7-titrazaindene), sensitizers (e.g., compounds described in U.S. Pat. No. 3,619.198), anti-capri agents (e.g., benzotriazole, 5-nitrobenzimidazole, polyethylene oxide, hardeners, Coating aids (eg, saponin, sodium lauryl alphaate, 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 a cellulose acetate film or a polyethylene terephthalate film by a dip method, an air knife method, a bead method, an extrusion doctor method, a double-sided coating method, or the like.

Next, the method of the present invention will be explained with examples, but the present invention is not limited thereto.

Example 1 1.1 Tonzari 30 g of gelatin 1 6 g of potassium bromide was added to 60 g of water
A silver nitrate aqueous solution (5 g as silver nitrate) and a potassium bromide aqueous solution containing 0.15 g of potassium iodide were added by a double jet method over a period of 1 minute into a container maintained at .degree. C. with stirring. Furthermore, silver nitrate aqueous solution (145 g as silver nitrate) and potassium iodide 4.
An aqueous solution of potassium bromide containing 2 g was added by double jet method. At this time, the addition flow rate was accelerated so that the flow rate at the end of addition was five times that at the start of addition. After the addition was completed, the reconsideration salts were removed at 35°C by the sedimentation method, the temperature was raised to 40°C, 75 g of gelatin was continuously added, and the pH was adjusted to 6.
．． Adjusted to 7. The resulting emulsion has a projected area diameter of 0.9
The tabular grains were 8 gm, average thickness 0.138 pm, and the silver iodide content was 3 mole %. This emulsion was chemically sensitized using gold and sulfur sensitization.

In addition to gelatin, as a surface protective layer made by Yom Co., Ltd., an average molecular weight of 8000 is used.
Polyacrylamide, polystyrene sulfonate soda, polymethyl methacrylate fine particles (average particle size 3)
．． An aqueous gelatin solution containing 0 gm), polyethylene oxide, and a hardening agent was used.

Anhydro-5,5'-dichloro-9-ethyl-3,31-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt was added to the above emulsion as a sensitizing dye at a ratio of 500 μ/1 mol Ag; 20 potassium iodide
It was added at a ratio of 0/1 mole Ag. Furthermore, as a stabilizer, 4-hydroxy-6-methyl-1,3,3a,? -Tetrazaindene and 2.6bis(hydroxyamino)-4
- Diethylamino-1,3,5-triazine and nitrone, trimethylolpropane as a drying antifoggant, a coating aid, and a hardening agent are added to form a coating solution, and a surface protective layer is simultaneously applied to both sides of the polyethylene terephthalate support. A photographic material was created by coating and drying. The amount of silver coated on this photographic material is 2 g/nf per side.

This photosensitive material was subjected to stepwise exposure with an optical wedge using a sensitometer, and developed using the following formulations of developer, fixer, and washing solution.

2. Potassium hydroxide 17g Sodium sulfite 31g Potassium sulfite 39g Diethylenetriaminepentaacetic acid 1g Boric acid
9g 8 Baydroquinone
25g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.7g diethylene glycol 10g 5-methylbenzotriazole 0.65g KBr
3g of water equals 1j! (P H1
Exemplary compound 1-0 of the present invention is added to the above developer (adjusted to 0.35). J.

1-07), I-(26), II-(2), II-Q
3 g of L If -(22) was added per developer i. The pH was then adjusted to 10.35. As a comparative example, a sample was prepared in which 20 g of sodium sulfite was added per 11 developing solutions (pH was adjusted to 10.35).

500mj of each of the above developers! Put it in a 500m1 beaker, cover the beaker with Saran wrap,
A hole with a diameter of 0.5 cm was made in the cover and left at 30°C for 12 days, and then the remaining amount of hydroquinone was analyzed and quantified.

On the other hand, 3 g/j of potassium bromide was added as a starter to each developer solution that had been aged at 30°C for 12 days. , glacial acetic acid 4 m
j! / It-added material was used to perform the following development process using a roller conveyance type automatic developing machine.

Processing process Temperature Time Development 35℃ 25 seconds fixing
35℃ 20 seconds water washing 20℃
25 seconds.Fuji F (manufactured by Fuji Photo Film Co., Ltd.) was used for fixing.

Table 1 shows the temperature of the working solution added with the exemplary compound of the present invention at 30°C.
The results of the residual amount of hydroquinone and photographic properties after 12 days are shown.

In addition, in photography, fog represents the value obtained by subtracting the base density from the optical density of the unexposed area, and G is the capri value (
It was determined from the intersection of the characteristic curve and the concentration obtained by adding 0.25 to the base concentration (including the base concentration), and the intersection of the characteristic curve and the concentration obtained by adding 1.75 to that concentration.

The relative sensitivity was determined using the fog value (including base density) + 1°0 as a reference point, and was expressed as a relative value, with the sensitivity when developing with a new developer being 100.

Dm represents the maximum concentration.

Table 1 The following is clear from the results in Table 1.

In the developer Ha-1 that does not use the compound of the present invention,
This shows that the deterioration of hydroquinone is large and the photographic properties are greatly reduced. Sodium sulfite 20 g/j
! Although the residual rate of hydroquinone in the continuous addition image solution 2-2 is considerably higher than that in N[L-1, the photographic properties are still insufficient.

On the other hand, the developer using the exemplified compound of the present invention is
It can be seen that although the amount of addition of Ha-8 is as small as 3 g/It, the residual rate of hydroquinone is higher than that of Ha-2 (and the photographic performance is close to that of the new solution).

By using the compound of the present invention in this way, the stability over time of the developer can be dramatically improved.

Example 2 A developer replenisher A as shown below was prepared.

Developer replenisher A Potassium hydroxide 29g Potassium sulfite 44.2 g Potassium metabisulfite 12.6g Diethylenetriaminepentaacetic acid 1g Boric acid
3g diethylene glycol 20m15
-Methylbenzotriazole 0.06 g5-Nitroindazole 0.2g Hydroquinone
30g 1-phenyl-3-pyrazolidone 1.5g glacial acetic acid
Add 7.5g water and 1f
Exemplary compound of the present invention per developer replenisher Alff adjusted to fipH 10,30! −(
26) and II-(22) were added in an amount of 3 g each. As a comparative example, per developer replenisher A and developer replenisher Alff,
30g of sodium sulfite was added. The composition of each developer is shown in Table 2. Each developer replenisher was adjusted to p) 110°30, and as a starter, potassium bromide 3g/l and glacial acetic acid 4mj! Table 2 shows the composition of the developer solution (mother solution).

The above-mentioned developer (mother liquor) was put into a roller conveyance type automatic processor, and the X-ray photographic material used in Example 1 was exposed and then subjected to a heat treatment.

Development 35℃ 24 seconds 61 tank fixing
35℃ 25 seconds 6j! To replenish the tank developer, use the developer replenisher mentioned above at 50 mj per 4-cut size sheet! The amount was replenished. The fixer was 44% of the Fuji F used in Example 1.
60ml was replenished per cut size sheet.

In addition, the automatic processing machine is operated 6 days a week, and 10
The apparatus was kept on standby for hours, and 15 half-exposed 4-cut sheets (10 inches x 12 inches) were processed per day.

The running experiment as described above was conducted for a total of 42 days. Table 3 shows changes in photographic properties during this period, the amount of hydroquinone remaining in the developing tank, and the condition of the silver sludge.

Table 2 From the results in Table 3, the following can be said. 0 The photographic properties of developer-1, which did not use the compound of the present invention, began to decline over time compared to the starting point, and after 24 days, it became practically useless. At the same time, the deterioration of hydroquinone increases.

Therefore, under the present processing conditions, the aged liquid HIl-1 requires liquid replacement in the developing tank after less than one month has passed, which is very disadvantageous in terms of handling.

On the other hand, developer No. 2 using a large amount of sodium sulfite and developer No. 11L3 and No. 4 using the compound of the present invention were
The photographic properties after 2 days remained at a level close to that of the new solution.

At the same time, the residual rate of hydroquinone also shows a high value.

However, since developer NCL-2 uses a large amount of sodium sulfite, it dissolves more silver halide in the film, producing a large amount of silver sludge that contaminates the developing rack, rollers, etc. do. Therefore, it is very disadvantageous in terms of maintenance of the automatic processing machine.

(Effect of the invention) According to the present invention, by using the compound of the present invention,
The stability of the developer can be significantly improved. Furthermore, compared to increasing the amount of sodium sulfite, it is possible to provide a more stable developer concentrate without drawbacks such as a decrease in concentration rate and the generation of silver sludge.

Therefore, effects such as a reduction in the amount of developer replenishment, a reduction in the pollution load, an increase in the economic efficiency of the development process, and ease of maintenance of the automatic processing machine can be achieved.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Scope of Claim] A method of developing a silver halide photographic light-sensitive material using a developer containing hydroquinones, wherein the developer contains at least one compound represented by the following general formula (I) or (II). A method for developing a silver halide photographic material, characterized by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1 and R^2 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group, and R^
1 and R^2 may be linked together with a nitrogen atom to form a heterocycle. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A is a hydrogen atom, an alkyl group, an aryl group, an amino group, a heterocyclic group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group, or an acyl group. group, carboxy group, hydroxyamino group or hydroxyaminocarbabonyl group, and X is -C-, -C-, -SO_2
- or -SO-, R^3 represents a hydrogen atom, an alkyl group or an aryl group, and Y represents a hydrogen atom or a group that can become a hydrogen atom by hydrolysis.