JPH02298937A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To confine the processing time from developing to fixing, rinsing and/or stabilizing of the photosensitive material to within 45 seconds by incorporating two kinds of the compds. respectively contg. the compds. expressed by general formulas into one of silver halide photographic sensitive emulsion layers. CONSTITUTION:One kind of the compds. expressed by the general formula I and one kind of the compds. expressed by the general formula II are incorporated into at least one layer of the silver halide photographic sensitive material having at least one layer of the photosensitive silver halide emulsion layer on a base. At least one kind of anionic surfactants are incorporated into this silver halide photographic sensitive material and the processing time from the developing to the fixing, rinsing and/or liquid stabilizer of the silver halide photographic sensitive material is confined within 45sec. The generation of residual colors, etc., is decreased even when a high-speed processing is executed.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming an image on a silver halide photographic light-sensitive material, and more particularly to a method for forming an image on a printed light-sensitive material suitable for rapid processing.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of silver halide photographic materials to be processed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of processing within the same amount of time.

The above tendency can also be seen in printing plate making separators.

In other words, as the immediacy and number of times information is rapidly increasing, it has become necessary to perform printing plate-making work in a short delivery time and in larger quantities. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly.

However, shortening the processing time is not preferable because it causes deterioration of residual color and unevenness of residual color.

[Purpose of the invention]

In order to solve the above-mentioned problems, the purpose of the present invention is to provide good residual color even when performing ultra-quick processing in which processing time for development, fixing, washing, and/or stabilizing liquid is within 45 seconds. An object of the present invention is to provide a method for processing a silver halide photographic material without unevenness.

[Structure of the invention]

The above object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support. The silver halide photographic light-sensitive material contains at least one compound represented by the following general formula (Il) and at least one compound represented by the following general formula [II], and the silver halide photographic light-sensitive material is subjected to development, fixing, water washing and / Or achieved by a processing method characterized in that the processing time to the stabilizing solution is within 45 seconds.

General formula CI) (x+’) Peng.

[In the formula, Yl and Y2 are each a benzothiazole ring,
Represents a nonmetallic atomic group necessary to form a benzoselenazole ring, naphthothiazole ring, naphthoselenazole ring, or quinoline ring, and these heterocycles are lower alkyl groups, alkoxy groups, aryl groups, hydroxyl groups, alkoxy It may be substituted with a carbonyl group or a halogen atom.

Rt and Rx each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R1 represents a methyl group, an ethyl group, or a propyl group. xl represents an anion.

nn2 represents l or 2. m represents l or 0, and when it is an inner salt, m=o. ] General formula (It) [In the formula, R3-R3 represents a substituted or unsubstituted alkyl group.

A and ~A represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but may form a ring by adjoining each other. However, either one or both of A and A must be a phenyl group. ] The present invention will be explained in detail below.

The line speed in the process of the present invention is 1000+u+
+/■in or more, preferably 1500+s/in or more, preferably 1800+s/sin or more.

The processing time in the developing, fixing, washing and/or stabilizing solution of the present invention is 45 seconds or less, which means that the leading edge of the film enters the developing solution and then comes out of the fixing solution, washing solution and/or stabilizing solution. The time required for this is 45 seconds or less, which includes the time from the developer to the fixer and the time from the fixer to the washing solution.

In the present invention, it has been found that by increasing the processing line speed without shortening the length of the processing line, the object of the present invention can be achieved without causing the above-mentioned problems.

Next, general formula (1) will be explained.

In the above general formula CI), Y and Y are each a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring,
Represents a group of nonmetallic atoms necessary to form a naphthothiazole ring or a quinoline ring, and these heterocycles include lower alkyl groups (e.g., methyl group, ethyl group, etc.), alkoxy groups (
For example, methoxy group, ethoxy group, etc.), hydroxyl group,
Aryl groups (e.g. phenyl group), alkoxycarbonyl groups (e.g. tomexycarbonyl group), halogen atoms (
For example, chlorine atom, bromine atom, etc.) may be substituted. R,,R, are lower alkyl groups (e.g. methyl group,
ethyl group, propyl group, butyl group), alkyl group having a sulfo group (e.g. β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, sulfoalkoxyalkyl group (e.g. sulfoethoxyethyl group) , sulfopropoxyethyl group), and an alkyl group having a carboxyl group (for example, β-carboxylethyl group, γ-carboxypropyl group, γ-carboxybutyl group, δ-carboxybutyl group, etc.). R1 represents a methyl group, an ethyl group, or a propyl group. Xl represents an anion commonly used in cyanine dyes (eg, halogen ion, benzenesulfonate ion, p-toluenesulfonate ion, etc.). m represents 1 or O, and when it is an inner salt, m=o.

Next, the configuration of the present invention will be explained in more detail.

First, specific examples of the compound represented by the above general formula [I] used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.

Examples of compounds represented by the above general formula [I].

-1, Below, bottom/margin ,・,1 (CH!)3SOs″′ CIN.

■ -15 E -20 ■ -22 ■ -23 (CHRI$SO,' ■ -25 ■ -26 ■ -27 ■ -28 ■ so, e ■ -29 ■ -32 (CH*)sCOOH(C)h )iCOO-■-33 ■-36 ■-37 General formula CI+) A1 to A6 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but adjacent ones may form a ring. However, either one or both of Al and A must be a phenyl group.

Specific examples of the compound represented by the general formula (II) are given below, but of course the compound is not limited thereto.

Compound Examples n-l ■-5 ■-8 The sensitizing dye of the present invention is preferably contained in the silver halide photographic emulsion in an amount of 1 mg to 2 g, more preferably 5 g to 1 g per mole of silver halide. be done.

The sensitizing dyes of the present invention can be directly dispersed into emulsions. Alternatively, they can be first dissolved in a suitable solvent, such as methyl alcohol, ethyl alcohol, methyl cellosolve, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. Furthermore, sensitizing dyes other than those of the present invention may be used in combination. When a sensitizing dye is used in combination, it is preferable that the total amount is the above content.

The sensitizing dye of the present invention can be easily synthesized with reference to US Pat.

Also, the present invention. The anionic surfactant used is not particularly limited as long as it has a hydrophobic part and a woody part in its molecule and exhibits a decrease in surface tension at least in its solution.

As the anionic surfactant particularly preferably used in the present invention, the following general formula (II[A), ([I B
), (mc) and (I[[D).

General formula (II[A) R, -OCO-CI2 R. -OCO-CI-R.

General formula (I[IB) R4-000-CH.

R, -OCO-C1 Enemy. -(6)-CI-R.

General formula (IIIC) General formula (II[D) In the above formula, R,,R,,R,,R6,R,,R,,R,
and R□. may be the same or different and each represents a halogen atom, such as chlorine or bromine, an alkyl group such as methyl, ethyl, butyl, isobutyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, octadecyl group, etc. It may be a chain or a branched chain, and preferably has 1 to 32 carbon atoms. These alkyl groups may be substituted with any substituent such as a halogen atom, such as a chlorine atom or a bromine atom, or an aryl group, such as a phenyl group or a naphthyl group. Also, R3 and R
7 represents an alkali metal salt of a carboxyl group, a sulfo group, and a phosphonic acid group. n□ and H2 represent integers of 1 to 3.

Specific compounds represented by the general formulas (I[IA) to (I[ID)] are illustrated below, but the compounds of the present invention are not limited thereto.

[Compound example]

C.I.

■ (lO) CsH+ 100cc82cH! CsH+ +0OCCHzCH-So, NaCHs(C
Hz)++ OOCC8! CH, (C)I*)
, , -00C-CH-3o , NaCIHIloo
CCH2 C+oHt+ OOCC)I 5O3NaCIls
(CI□)s OOCCHiCHs(CHz)x-0
0C-C1l-SOsNaCHx(CTo)s CH
(C2H6)CH200CCH2CHs(CHi)s
C)I(C2Hs)CHi OOCCHSOsNa
The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any used material can be used, but 50 mol% silver chloride
It is preferable that the particle size is 0.2 μm or more, and the particle size is 0.2 μm or more.
．． The thickness is preferably 5 μm or less.

In addition, the amount of gelatin on the emulsion layer side is 2.89/m” or less,
Preferably it is 2-5 g/m'' or less.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.

Any shape of the silver halide grains according to the present invention can be used. One preferred example is a cube having a (100) plane as a crystal surface.

Also, U.S. Patent Nos. 4,183.756 and 4,225.6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr-3).
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used.

Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

In the present invention, monodisperse emulsions are preferred. As monodisperse silver halide grains in a monodisperse emulsion, the weight of silver halide contained within a grain size range of ±20% around the average grain size r is 60% or more of the weight of all silver halide grains. A certain amount is preferable, particularly preferably 70% or more, and still more preferably 80% or more.

Here, the average particle size 7 is the frequency ni of particles having particle size ri
The particle size r when the product n1Xri' of and ri8 is maximum
Define i.

(3 significant digits, round off the smallest digit.) The grain size here refers to the diameter in the case of spherical silver halide grains, and the projected image in the case of grains with shapes other than spherical. This is the diameter when the circumferential area is converted into a circular image.

The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the particle diameter or projected area on the print.

(The number of grains to be measured shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsions of the present invention have a degree of monodispersity of 20 or less, more preferably 15 or less. be.

Here, the average particle diameter and particle diameter standard deviation shall be determined from ri defined above. Monodisperse emulsion is disclosed in Japanese Patent Application Laid-Open No. 54-4852.
No. 1, No. 58-49938 and No. 60-122935
This information can be obtained by referring to the Publication No.

Although the photosensitive silver halide emulsion can be used as a so-called Pri+5ative emulsion without chemical sensitization, it is usually chemically sensitized.

For chemical sensitization, the Glafkides or Z
The book by Elikman et al., or the book by H. Fr.
Die
Grundlagen der Photogra
phischen Prozesse wit
Silberhalogeniden, Akade
micche Verlagsgesellscha
ft., 1968) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, and gold or other noble metal compounds can be used.

Further, there are no particular restrictions on the conditions such as I)H, I)Ag, temperature, etc. during chemical sensitization, but the pH value is preferably 4 to 9, particularly 5 to 8, and the 91g value is 5 to 11. In particular, it is preferable to keep it between 7 and 9. Also, the temperature is 40 to 9011Q1
Particularly preferred is 45 to 75°C.

In addition to the aforementioned sulfur sensitization and gold/sulfur sensitization, the photographic emulsion used in the present invention can also be subjected to reduction sensitization using a reducing substance, noble metal sensitization using a noble metal compound, or the like.

As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.

When carrying out the present invention, for example, 4-hydroxy-6-methyl-1,3,
Various stabilizers can also be used, including 3a,7-titrazaindene, 5-mercapto-l-phenyltetrazole, 2-mercaptobenzothiazole, and the like.

Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.

The silver halide grains used in the emulsion of the present invention are formed by cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts, etc. Alternatively, metal ions can be added using complex salts and included inside the particles and/or on the particle surfaces.

In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

In the silver halide photographic material according to the present invention, a sensitizing dye may be further added and used in combination.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxanol dyes, and the like.

The sensitizing dye used in the present invention is used at a concentration equivalent to that used for ordinary negative-working silver halide.

In particular, it is advantageous to use the dye at a concentration that does not substantially reduce the inherent sensitivity of the silver halide emulsion.

Approximately 1.0% of sensitizing dye per mole of silver halide. OX 10-
' to about 5 X 10-' moles of sensitizing dye are preferred, especially about 4 X 10-' to 2 X moles of sensitizing dye per mole of silver halide.
Preferably, a concentration of 10-' molar is used.

The sensitizing dyes of the present invention can be used alone or in combination of two or more. The sensitizing dyes may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for the purpose of supersensitization.

The silver halide photographic material according to the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation and halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. Among them, oxanol dyes: hemioxanol dyes and merocyanine dyes are useful.

In the silver halide photographic material according to the present invention, when dyes, ultraviolet absorbers, etc. are included in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like.

Various compounds can be added to the above photographic emulsion in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material.

Further, the silver halide photographic light-sensitive material of the present invention has U.S. Pat. No. 3,411,911 and U.S. Pat.
12, Japanese Patent Publication No. 45-5331, etc., may be included.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176 1 tea
17643 (December 1978) and volume 187■t
em18716 (November 1979), and the relevant parts are summarized in the table below.

Additive type RD 17643 RD 187
161, chemical sensitizer page 23 6
Page 48, right column 2, Sensitivity enhancer
Same as above 4゜brightener page 24 7, anti-stain agent page 25 right column page 650 left ~
Right column 8, dye image stabilizer page 25 9, hardener page 26 page 651 left column 10
, binder page 26 Same as above 1
1. Plasticizer/Lubricant Page 27 650
Right column 12, coating aids/surfactants pages 26-27
Same as above 13, static inhibitor page 27
In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials. Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose i[Il]ate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or a. Paper coated with or laminated with an olefin polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. Undercoat treatment is JP-A-52-1049
The treatments described in Japanese Patent No. 13, No. 59-18949, No. 59-19940, and No. 59-18949 are preferred.

The surface of the support may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

The development time in the present invention is within 20 seconds, preferably 15 seconds.
Describe the development, fixing, washing, and drying processes that take less than seconds.

The developing agent used in the black and white developer used in the present invention has dihydroxybenzene chains and l-
Most preferred is a combination of phenyl-3-pyrazolidones. Of course, a p-aminophenol type developing agent may also be included.

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

As the developing agent for l-phenyl-3-pyrazolidone or its derivative used in the present invention, l-7enyl-4,4-dimethyl-3-pyrazolidone, l-7enyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, Examples include l-phenyl-4,4-dihydroxymethyl-3-pyrazolidone.

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

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

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/a or more, particularly 0.4 mol/Q or more. Further, the upper limit is preferably 2.5 mol/Q.

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

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

JP-A-61-28708 (borates), JP-A-60-
Buffers such as No. 93439 (eg, 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, nitinol, 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, silver stain preventive agents such as the compounds described in JP-A-56-24347 can be used in the developer.

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

In addition to this, there are also works by F. A. Meson, “Photographic
"Processin Chemistry", published by Focal Press (
1966), 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.

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

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

Furthermore, "drying time" refers to a drying zone where the automatic processing machine is equipped with a drying zone where hot air is normally blown at 35°C to 100°C, preferably 40°C to 80°C. refers to time.

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

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 5.5.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, which contain thiosulfate ions and ammonium ions as essential components, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of the fixing agent used can be changed as appropriate, and is generally about 0.1 to about 6 mol/Q.

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

The fixing solution may include tartaric acid, citric acid, or conductors thereof, either alone or in combination.

Those containing 0.005 mol or more of these compounds per fixer 112 are effective, especially 0.005 mol or more per fixer 112. O1 mol/I2~0.0
3 mol/a is particularly effective.

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

The fixing solution may optionally contain a preservative (e.g. sulfite, bisulfite), a pH buffer (e.g. acetic acid, nitric acid),
It can contain a pH adjuster (for example, sulfuric acid), a chelating agent with water softening ability, and a compound described in Japanese Patent Application No. 60-213562.

Fixing temperature and time are approximately 20°C to approximately 50°C for 6 seconds to 1
The time is preferably 30' (!~40°C for 6 seconds to 30 seconds, and even more preferably 6 seconds to 15 seconds at 30°C to 40°C.

Where 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 comprised of an l-agent. is the same as for the developer.

Fixer agglomeration can stably exist as a l agent at pH 4,
5 or more, more preferably pH 4.65 or more. This is because if the pH is less than 4.5, the thiosulfate will decompose and eventually become sulfided, especially if the fixer is left for a long period of time before it is actually used.

Therefore, 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 pu is not so strict, but if it is fixed at too high a pH, the pH of the membrane will become high even after washing with water, and the swelling of the membrane will become large.Therefore, the drying load will become large, so the upper limit is around pH 7. Fixing solutions that use aluminum salts to harden films have a pH limit of 5.5 to prevent precipitation of aluminum salts.

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 from 50 m12 to 1500 mff per 1IIt of the photosensitive material.

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

Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using anti-mold water for washing water or stabilizing liquid, not only is it possible to save water by reducing the amount of replenishment to less than 3Q per 12 liters of photosensitive material, but it also eliminates the need for piping for installing an automatic processing machine. This makes 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-mildew water is used in combination with washing water or stabilizing liquid, the formation of lime scale can be effectively prevented.
! It is possible to perform water saving treatment of 0 to 3a, preferably 0 to la1 per unit.

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

As a method of reducing the amount of replenishment, a multistage countercurrent system (for example, two stages, three stages, etc.) has been known for a long time. If this multi-stage countercurrent method is applied to the present invention, the photosensitive material in the fixer 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. 6O-2FT3939, the method using a magnetic field described in JP-A No. 60-263940, and the method using ion exchange resin described in JP-A No. 61-131632. How to make pure water, patent application 1986
-253807, 60-295894, 61-
The method using the antibacterial agent described in No. 63030 and No. 61-51396 can be used.

Furthermore, L, E, West Water Quali
ty Cr1teria” Photo Sci & E
ng, Vol, 9No. 6 (1965), M.W.
, Be-ach″Microbiological G
rowths in Motion-Pic-ture
Processing”SMPTE Journal
Vol, 85. (1976).

R. O. Deegan, “Photo Proce
ssing Wash Water Biocides”
J, IIQaging Tech, Vol 10. N
o, 6 (1984) and JP-A-57-8542, 5
No. 7-58143, No. 58-105145, No. 57-
No. 132146, No. 58-18631, No. 57-97
Antibacterial agents, anti-inflammatory agents, surfactants, etc. described in No. 530, No. 57-157244, etc. can also be used in combination.

Furthermore, for the washing bath, R.T. Kreiman J.Ima
RESEARCH, an inthiazoline compound described in GE, Techlo, (6) 242 (1984)
DISCLO5URE Volume 205, Item 20526
(1981, May issue), Volume 228, Item 22845 (1
Inthiazoline compounds described in Japanese Patent Application No. 1983-51396 (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,
O-7 Dynylphenol, chlorophene, dichlorophene, formaldehyde, geltaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-
(4-Thiazoline)-benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-dimethylammonium-chloride, N-(fluorodichloromethylthio)-7talimide, 2.4.4'-1-dichloro-2'- Hydroxydiphenyl ether and the like.

The water that has been treated with anti-mold measures and stored in the water stock tank is diluted with water for diluting the undiluted solution of the processing solution such as the developer/fixer, and the amount thereof added is preferably 0. Old ~10g/Q, more preferably 0.1~
It is 5g/ff.

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

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

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate in order 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 ~50°C is preferred, but 6 seconds to 1 minute at 15°C to 40°C
The heating time is more preferably from seconds to 30 seconds, and even more preferably from 6 seconds to 15 seconds at 15°C to 40°C.

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 0°C to about 100°C, and the drying time can be changed as appropriate depending on the surrounding conditions, but usually it is about 5 seconds to 1 minute, but preferably at 40°C.
~80°C for about 5 seconds to 30 seconds.

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 1
Within 00 seconds, preferably within 60 seconds, more preferably within 50 seconds
It should be processed within seconds.

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 section of the automatic processor to the moment the leading edge emerges from the processor after being processed.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 In a container heated to 40°C containing gelatin, sodium chloride, and water, an aqueous silver nitrate solution, 2 x 10-' mol of potassium hexachloroiridate per mol of silver chloride, and 4810 ml of potassium hexachloroiridate were added. Silver chlorobromide particles containing 35 mol% silver bromide (breadth of distribution 12%, cubic crystal 9 grain size 0.33 μm) was adjusted while maintaining the pH at 3,0 pAg at 7.7, and after returning to pH 5,9, it was desalted in a conventional manner.

This emulsion was gold-sensitized and sulfur-sensitized and used as a sensitizing dye in Table-1.
2 of the general formula CI) per 1 mole of silver halide.
40mg5 of 200+ag of the compound represented by general formula (II) was added, and further l-phenyl-5- per mole of silver halide was added.
After adding 70 mg of mercaptotetrazole and 1-2 g of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene and 5 gelatin to stop the ripening, add 4 ml of hydroquinone per mole of silver halide.
g, 3 g of potassium bromide, 5 g of saponin, 2 g of styrene-maleic acid polymer, 3 g of ethyl acrylate polymer latex, and l-
After adding hydroxy-3,5 dichlorotriazine sodium salt and formalin, a protective film was applied onto the undercoated polyethylene terephthalate support so that the amount of silver was 3.5 g/2 gelatin as shown in Table 1. Add potassium bromide leg, l to an aqueous solution of 500 g of gelatin as
-decyl-2-(3-inpentyl)succinate-2
- Add 4g of sodium sulfonate, add and disperse 100g of silica having an average particle size of 5μ°, and coat the emulsion layer and protective layer at the same time so that the amount of gelatin is as shown in Table 1.

In addition, dyes (a) and (b) are applied to the opposite side of the above-coated surface.
) with a gelatin amount of 3.
3 g/m", dye (a) at 180 mg/ta", and dye (b) at 50 mg/Tsuru 8.

Dye (a) Dye (b) The sample obtained in this way was processed under the following conditions in a normal roller type automatic developing machine using the following developer and fixer, and the residual color was evaluated. did.

Note that residual color is evaluated in 10 levels, with IO being the best, 1 to 4 being unusable, and 5 or higher being usable. The results are shown in Table 1.

From Table 1, it can be seen that the products of the present invention have good residual color.

When changing the developing, fixing, and washing times at the same line speed, the depth of the tank and the number of rollers were adjusted.

Processing conditions (process) (temperature) (time)
Image 35℃ 12
Second fixation 34℃
12 Excerpt washed at room temperature
Dry for 12 seconds 50
°CtO second developer formulation (composition A) Pure water (ion exchange water) 150ml 12-functional ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50g Potassium sulfite (55% v/v aqueous solution) 100mQ Potassium carbonate 50g Hydroquinone
15g 5-methylbenzotriazole 200mg 1-phenyl-5-mercaptotetrazole 0mg Potassium hydroxide, amount to bring the pH after use to 1014 Potassium bromide 4.5g (composition) Pure water (ion exchange water) 3mff diethylene glycol 50g ethylenediaminetetraacetic acid Disodium salt 5mg Acetic acid (90% aqueous solution) 0.3+Q5
-Nitroindazole llO+5g1-
When using 700 mg of phenyl-3-pyrazolidone developer, it was dissolved in 500 m<2 of water in the order of composition 1 above and finished to 1 for use.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 40
m12 Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g Sodium citrate dihydrate
2g acetic acid (90% v/v aqueous solution)
13.6mff1 (composition) Pure water (ion exchange water) L7@Q sulfuric acid (
50%W aqueous solution) 4.7g aluminum sulfate (AI220.Aqueous solution with a converted content of 8.1% w/v) 2
6.5g When using a fixer, the above composition A1 was dissolved in water 500@Q in the order of composition, finished to 1Q, and used. which fixer p
H was about 4.3.

Table 1 Example 2 An emulsion was prepared in the same manner as in Example 1. However, the silver chlorobromide particles had a distribution width of 15% and a cubic grain size of 0.36 μm. In addition, the compounds shown in Table 1 were added as anionic surfactants to the emulsion layer so that the surface tension was 36 dyne/am, and l-decyl-2-(3-inpentyl) was added to the protective film layer.
Instead of sodium succinate-2-sulfonate, 4 g of the compound shown in Table 1 was added as an anionic surfactant. All other conditions were the same as in Example 1. The results are shown in Table 2.

From Table 2, it can be seen that the products of the present invention have good residual color.

i evening insert “,) Table 2 The surfactants used for comparison are shown below.

r0 [Effects of the Invention] According to the present invention, it was possible to provide a processing method in which residual color and the like are less likely to occur even when ultra-rapid processing is performed.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support,
At least one layer of the silver halide photographic light-sensitive material contains at least one compound represented by the following general formula [I];
A silver halide photographic light-sensitive material containing at least one compound represented by the following general formula [II] is processed within 45 seconds from development to fixing, washing with water and/or stabilizing solution. A processing method characterized by: (2) The processing method according to claim 1, wherein the silver halide photographic material according to claim 1 contains at least one anionic surfactant. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. These heterocycles may be substituted with a lower alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an alkoxycarbonyl group, or a halogen atom. R_1 and R_2 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R_3 represents a methyl group, an ethyl group, or a propyl group. X_1 represents an anion. n_1 and n_2 represent 1 or 2. m represents 1 or 0, and when it is an inner salt, m=0. ] General formula [I
I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 to R_2 represent substituted or unsubstituted alkyl groups. A_1 to A_6 represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, or a phenyl group, but may form a ring by adjoining each other. However, either 1 of A_2 or A_5
one or both must be phenyl groups. ]