JP2001166417A - Silver halide photograph sensitive material and processing method for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity, less liable to a sensitivity change, ensuring improved black spot trouble, processing stain and defective fixation and processable under a diminished replenisher solution in rapid processing or long-term running processing and a processing method for the sensitive material. SOLUTION: The silver halide photographic sensitive material has a photosensitive silver halide emulsion layer on one side of the substrate, has <2.0 g/m2 total amount of gelatin one the emulsion layer side and contains a compound of the formula R-O-(CH2CH2O)m-(CH2)n-SO3-M+ [where R is alkyl; (m) is an integer of 1-15; (n) is an integer of 1-10; and M+ is a counter cation].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material and a method for developing the same.
The present invention relates to a silver halide photographic light-sensitive material having high sensitivity, high black spot resistance, improved processing stains and fixing defects, and reduced liquid replenishment, and a development processing method thereof.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material (hereinafter simply referred to as a light-sensitive material) obtains an image by performing development, fixing, washing or stabilizing treatment after exposure. The processing is usually performed by an automatic developing machine, and a method of replenishing a replenisher to keep the activity of the processing solution constant is generally widely used. The replenishment of the replenisher is intended for dilution of the eluate from the photosensitive material, correction of the amount of evaporation, replenishment of consumed components, and the like.

[0003] In recent years, with increasing interest in environmental issues, there has been a strong demand for reduction of photographic processing waste liquid. In order to reduce the photographic processing waste solution, there are known methods of reducing the replenishing amount of the processing solution or performing the washing step in a multi-stage counter-current system of two or more stages. As a result, sensitivity fluctuation, black spots increase, or processing stains are caused.

On the other hand, there has been a demand for shortening the development processing time for the purpose of efficiency and cost reduction. Conventionally, the entire processing until the photosensitive material is inserted into the automatic developing machine and emerges from the drying zone is required. Time (Dry to Dry) is 9
It generally took more than 0 seconds, but recently
A rapid process of less than 0 seconds is required. However, when such rapid processing is performed in combination with the above-described low replenishment, sensitivity fluctuations in the running processing, an increase in black spots, and processing stains become a serious problem. This is achieved by promoting the concentration of each processing solution or its replenisher in order to achieve low replenishment or rapid processing.
Decrease in processing solution replacement rate in processing tank or increase in carry-over of concentrated processing solution, resulting in increased effects of gelatin and organic compounds eluted from photosensitive material, resulting in sensitivity fluctuation, increase in black spots and processing stains Result.

As a result of intensive studies on the above-mentioned problems, the present inventor has found that a surfactant used in a light-sensitive material as a coating aid is eluted and accumulated in a processing solution and is added to a developing solution or a fixing solution. It was found that a complex was formed with the specific compounds contained therein, resulting in black spot failure, processing stains, or poor fixing. To solve these problems, JP-A-5-323523 and JP-A-6-323523
No. 130539 discloses a technique using a sulfoalkylpolyoxyethylene-based surfactant. These surfactants have an effect on the processing characteristics in a short period, but are not effective in a long-term running process. Was found to still cause processing stains and fixing defects.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and has as its object to provide high sensitivity with little sensitivity fluctuation in rapid processing or long-term running processing, black spot failure, processing dirt and the like. An object of the present invention is to provide a silver halide photographic light-sensitive material in which defective fixation is improved and a low replenishment liquid is used, and a development processing method thereof.

[0007]

The object of the present invention has been attained by the following constitutions.

[0008] 1. The support has at least one light-sensitive silver halide emulsion layer on one side thereof, the total amount of gelatin on the emulsion layer side is less than 2.0 g / m ² , and is represented by the general formula (1): Silver halide photographic light-sensitive material, characterized by containing a compound to be prepared.

[0009] Formula (1) R-O- (CH 2 CH 2 O) m - (CH 2) n -SO 3 - in M ⁺ wherein, R represents a substituted or unsubstituted alkyl group, m is 1
To 15 and n each represent an integer of 1 to 10. M ⁺ represents a counter cation.

[0010] 2. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of the support and containing the compound represented by the formula (1) is used as a developing time for 30 seconds. A method for developing a silver halide photographic light-sensitive material, wherein the method is processed as follows.

3. A replenishing amount of a developing solution is prepared by adding a silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and containing a compound represented by the above general formula (1) to a developer. A process for developing a silver halide photographic light-sensitive material, wherein the processing is performed at 250 ml / m ² or less.

4. A replenishing amount of a fixing solution containing a silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and containing a compound represented by the above general formula (1). A process for developing a silver halide photographic light-sensitive material, wherein the processing is performed at 250 ml / m ² or less.

5. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side of a support and containing a compound represented by formula (1) is washed with water or stabilized. 500 ml for replenishment of liquid
/ M ² or less, a method for developing a silver halide photographic material.

That is, as a result of the inventor's intensive studies on the above-mentioned problems, control of the influential substances eluted from the photosensitive material into the processing solution, specifically, the interface used in the photosensitive material as a coating aid or the like, It has been found that the object of the present invention can be achieved by selecting a specific compound as the activator, and further by setting the use amount of gelatin as a binder to less than 2.0 g / m ² . As a result, it was possible to shorten the development processing time or to reduce the replenishment of the developing solution, the fixing solution, the washing water or the stabilizing solution.

Hereinafter, the present invention will be described in detail. The photosensitive material according to the present invention is characterized by containing a compound represented by the following general formula (1).

[0016] Formula (1) R-O- (CH 2 CH 2 O) m - (CH 2) n -SO 3 - in M ⁺ wherein, R represents a substituted or unsubstituted alkyl group, preferably a carbon It is an alkyl group having several tens or more and 20 or less, particularly preferably a linear alkyl group having 10 or more and 20 or less carbon atoms. m represents an integer of 1 to 15, preferably 2 to 5
It is. n represents an integer of 1 to 10, preferably 2 to 5
It is. M ⁺ represents a counter cation, and examples thereof include group 5A onium compounds such as alkali metal cations, ammonium cations, and phosphonium cations, and group 6A onium compounds such as sulfonium and telluronium, and are preferably alkali metal cations.

Hereinafter, specific examples of the compound represented by the formula (1) will be shown, but the present invention is not limited to these compounds.

[0018]

Embedded image

The compound represented by the general formula (1) is
It can be synthesized by a usual method well known to those skilled in the art.

The amount of the compound represented by the general formula (1) is not uniform depending on the constitution of the light-sensitive material.
^{When +} is Na ⁺ , 1 mg / m ² or more and 100 mg
/ M ² or less, particularly preferably from 10 mg / m ^{2 to} 50 mg / m ² . Further, in a coating solution containing the compound, the static surface tension of the coating solution is 30 mN / m.
It is preferable to add the following amounts.

The position where the compound represented by the general formula (1) is added in the light-sensitive material is not particularly limited, but is preferably added to a layer forming a gas-liquid interface at the time of coating. It is preferable to add to the uppermost coating solution farthest from the body.

As the binder or protective colloid of the light-sensitive material according to the present invention, gelatin is preferably used. In the present invention, the total gelatin amount on the emulsion layer side is 2.0 g / m2.
It is preferably ² or less. Particularly preferably 1.8 g
/ M ² or less and 0.5 g / m ² or more.

As binders for forming the photosensitive material, in addition to gelatin, hydrophilic polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate and starch derivatives. Sugar derivative; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polyvinylimidazole and polyvinylpyrazole can be used.

As gelatin, besides lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Enzymatic degradation products of gelatin can also be used.

Next, the light-sensitive material according to the present invention will be described. As the silver halide photosensitive material according to the present invention,
A black-and-white silver halide photographic light-sensitive material is preferable, and examples thereof include a light-sensitive material for medical use, a light-sensitive material for printing plate making, a microfilm and a black-and-white light-sensitive material for general use, and more preferably a light-sensitive material for printing plate making. .

The light-sensitive material according to the present invention preferably employs a silver halide emulsion containing 60 mol% or more of silver chloride, specifically, a pure silver chloride emulsion and 60 mol% or more of silver chloride. It is preferable to use a silver chlorobromide emulsion, a silver chloroiodobromide emulsion containing 60 mol% or more of silver chloride, or the like.

The average grain size of the silver halide is 0.6
μm or less, especially 0.5 to 0.0
5 μm is preferred. The average particle size in the present invention is a term that is commonly used by experts in the field of photographic science and is easily understood. The particle diameter means a particle diameter when the particle is a spherical particle or a particle that can be approximated to a sphere. When the particle is a cubic, it is converted into a sphere, and the diameter of the sphere is defined as the particle diameter.
For details of the method for determining the average particle size, see Mies, James: The Theory of the Photographic Process (CE Mees & TH James:
The theory of the photogr
aphic process), 3rd edition, pp. 36-43 (1966 (published by Macmillan "Mcmilllan")).

The shape of the silver halide grains is not limited.
The shape may be flat, spherical, cubic, tetrahedral, octahedral, or any other shape. Further, it is preferable that the particle size distribution is narrower, and it is particularly preferable that the emulsion is a so-called monodisperse emulsion in which 90%, preferably 95% of the total number of particles fall within a particle size range of ± 40% of the average particle size.

Of the above tabular grains, tabular grains having a silver chloride content of 90 mol% or more and having a (100) plane as a main plane are preferably used, and these are described in US Pat.
4,337, 5,314,798, 5,32
No. 0,958, and the like, and intended tabular grains can be easily obtained.

The method of reacting the soluble silver salt with the soluble halide salt in the present invention may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Further, a method of forming particles under the condition of excess silver ions (so-called reverse mixing method) can also be used. Also,
As one type of the double jet method, a method of maintaining a constant pAg in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. Thus, a silver halide emulsion having a uniform grain size can be obtained.

The silver halide emulsion preferably contains at least one metal selected from the group VIII transition metals and rhenium. Examples of the group VIII transition metals include iridium, rhodium, ruthenium, osmium and the like. These metals can be added at any time between silver halide grain formation and coating, preferably during silver halide grain formation, during physical ripening and / or during chemical ripening. Further, it is preferably added during the formation of silver halide grains. As a method of addition, there are a method of adding uniformly in the particles, and a method of forming a core-shell structure and localizing a large amount in a core portion or a shell portion. These Group VIII transition metals are preferably added in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol, more preferably 1 × 10 ⁻⁶ mol to 1 × 10 ⁻³ mol per mol of silver halide. Range of moles.

In the present invention, a metal salt such as zinc, lead, thallium, rhenium, palladium, platinum or the like can be coexistent during physical ripening or chemical ripening. When incorporating a metal compound into the particles, the metal may be halogen,
Compounds such as carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl, and phenanthroline can be coordinated. The oxidation state of the metal can be arbitrarily selected from the highest oxidation level to the lowest oxidation level. Preferred ligands include JP-A-2-2082 and JP-A-2-20853,
Hexadentate ligands described in JP-A-2-20854, JP-A-2-20855 and the like, and common sodium salts, potassium salts, cesium salts or primary, secondary and tertiary amines as alkali complex salts There is salt. Also, a transition metal complex salt can be formed in the form of an aquo complex. Examples of these include K ₂ [RuCl ₆ ], (NH ₄ ) ₂ [RuCl ₆ ], K ₂
[Ru (NO) Cl ₄ (SCN)], K ₂ [RuCl
₅ (H ₂ O)]. Further, compounds represented by replacing Ru with Rh, Os, Re, Ir, Pd and Pt can also be used.

The silver halide emulsion is preferably subjected to chemical sensitization. As a method of chemical sensitization, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. Good. Known sulfur sensitizers can be used as the sulfur sensitizer. Preferred sulfur sensitizers include, in addition to the sulfur compound contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, and rhodanine. , Polysulfide compounds and the like can be used. As the selenium sensitizer, a known selenium sensitizer can be used. Also, these chemical sensitizers can be used in combination,
For example, there are a combination of a sulfur sensitizer and a noble metal sensitizer, a combination of a selenium sensitizer and a noble metal sensitizer, and a combination of a reduction sensitizer and a noble metal sensitizer. These chemical sensitizers can be added at any time during the preparation of a silver halide emulsion, but preferably at the time of chemical sensitization. The addition amount of these chemical sensitizers is preferably in the range of 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per mol of silver halide.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, amino Triazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole)
Mercaptopyrimidines, mercaptotriazines such as thioketo compounds such as oxazolinethione; azaindenes such as triazaindenes and tetrazaindenes (especially 4-hydroxy-substituted-1,3,3
a, 7-tetrazaindenes), pentazaindenes and the like; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as antifoggants or stabilizers, such as benzenesulfonamide, can be mentioned.

The light-sensitive material of the present invention may contain a dispersion of a water-insoluble or hardly-soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (eg, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or acrylic acid, Methacrylic acid, α, β-
A polymer having a monomer component of a combination of unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid, or the like can be used.

In the light-sensitive material of the present invention, an inorganic or organic hardener is added as a crosslinking agent for a hydrophilic colloid such as gelatin. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) Active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide]
Active halogen compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid and phenoxymucochloric acid), isoxazoles, dialdehyde starch, and 2-chloro-6- Hydroxytriazinated gelatin, carboxyl group-activated hardener and the like can be used alone or in combination.
These hardeners are described in Research Disclosure (hereinafter simply referred to as RD), Vol. 176, 17643 (published in December, 1978), page 26, paragraphs A to C.

Various other additives are used in the light-sensitive material used in the present invention. For example, a desensitizer, a plasticizer, a slipping agent, a development accelerator, an oil and the like can be mentioned.

The support used in the present invention may be either permeable or non-permeable, but for the purpose of the present invention, preferably a permeable plastic support. For the plastic support, a polyethylene compound (eg, polyethylene terephthalate, polyethylene naphthalate, etc.),
A support made of a triacetate compound (eg, triacetate cellulose or the like), a polystyrene compound (eg, syndiotactic polystyrene), or the like is used. The thickness of the support is preferably from 50 to 250 μm, particularly preferably from 70 to 200 μm.

In the present invention, the following compounds can be appropriately selected and contained in the constituent layers of the silver halide photographic material.

(1) Solid Dispersion Fine Particles of Dye JP-A-7-5629, page (3) [0017] to (1)
6) Compound described on page [0042] (2) Compound having acid group JP-A No. 62-237445 (8) Compound described on page 11, lower left column, line 11 to page (25) lower right column, line 3 ) Acidic polymer JP-A-6-186659, page (10) [0036]
(17) Compound (4) Sensitizing dye JP-A-5-224330, page (3) [0017]
(13) Compound described on page [0040] JP-A-6-194777 (11) page [0042]
Compounds described on page (22) to page [0094] JP-A-6-242533, page (2) on page [0015]
(8) Compound described on page [0034] JP-A-6-337492, page (3) [0012]-
(34) Compound described on page [0056] JP-A-6-337494, page (4) [0013]-
(14) Compound described on page [0039] (5) Supersensitizer JP-A-6-347938 (3) page [0011] to
(16) Compound described on page [0066] (6) Hydrazine derivative JP-A-7-114126, page (23) [0111]
To (32) [0157] Compound described in JP-A-9-90538, page (23) [0091] to
(42) Compound described on page [0163] (7) Nucleation promoter Japanese Unexamined Patent Publication (Kokai) No. 7-114126, page (32) [0158]
Compound described on page [36] [0169] JP-A-9-90538, page (36) [0164]
(52) Compound described in [0186] (8) Tetrazolium compound JP-A-6-208188, page (8), [0059] to
(10) Compound described on page [0067] (9) Pyridinium compound JP-A-7-110556, page (5) page [0028] to
(29) Compound described on page [0068] (10) Redox compound Compound described on pages (7) to (22) of JP-A-4-245243 (11) Syndiotactic polystyrene (SPS) support and undercoating No. 9-80664, page (3) [0022]-
(8) Compound described on page [0077] The above-mentioned additives and other known additives are described, for example, in RD No. 17643 (December 1978), N
o. No. 18716 (November 1979) and the same No. 30
8119 (December 1989). The types of compounds and the locations described in these three research disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 page classification page page classification Chemical sensitizer 23 III 648 upper right 996 III sensitizing dye 23 IV 648-649 996-8 IV desensitizing dye 23 IV 998 B dye 25 -26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right antifoggant / stabilizer 24 IV 649 Upper right 1006-7 VI Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-7 XI 650 right 1005-6 XI Antistatic agent 27 XII 650 right 1006-7 XIII Plasticizer 27 XII 650 right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Next, the developing process in the present invention will be described. To.

After exposure, the silver halide photographic light-sensitive material of the present invention is developed by an automatic developing machine comprising at least four processes of developing, fixing, washing or stabilizing bath and drying.

As the developing solution used in the present invention, known developing agents can be used. Specifically, dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-)
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N
-Methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA iron) Salt, DTPA nickel salt, etc.) can be used alone or in combination. Among them,
It is preferable to use a developer containing ascorbic acid and its derivatives. Ascorbic acid and its derivatives
Known developing agents are described, for example, in US Pat.
88,548, 2,688,549, 3,02
2,168, 3,512,981, 4,97
Nos. 5,354, 5,326,816 and the like can be used.

In the present invention, a developing agent of ascorbic acid or a derivative thereof and a 3-pyrazolidone (for example, 1
-Phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-
3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o
-Aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol and the like and dihydroxybenzenes (for example, hydroquinone, hydroquinone monosulfonate, sodium salt of hydroquinone monosulfonic acid, potassium salt of 2,5-hydroquinone disulfonic acid and the like) It is more preferred to use the developing agents in combination. When used in combination, the developing agents such as 3-pyrazolidones, aminophenols and dihydroxybenzenes are usually used in an amount of 0.01 to 0.1 per liter of developer.
Preferably it is used in an amount of less than 2 mol. In particular, a combination of ascorbic acid and its derivative with 3-pyrazolidones, and a combination of ascorbic acid and its derivative with 3-pyrazolidones and dihydroxybenzene are preferably used.

In the present invention, in addition to a developing agent, an alkali agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffering agent (for example, carbonate, phosphate, borate,
Boric acid, acetic acid, citric acid, alkanolamine, etc.) are preferably added. As the pH buffering agent, carbonate is preferable, and the amount of addition is preferably 0.5 mol or more and 2.5 mol or less per liter of the developer, more preferably,
The range is from 0.75 mol to 1.5 mol. Also,
If necessary, dissolution aids (eg, polyethylene glycols and their esters, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, defoaming Agents, antifoggants (eg, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or Alkali metal salts, nitrilotriacetates, polyphosphates, biodegradable chelating agents, etc.), and development accelerators (for example, US Pat.
No. 4,025, compounds described in JP-B-47-45541, etc.), a hardener (for example, glutaraldehyde or a bisulfite adduct thereof) or an antifoaming agent can be appropriately added.

The pH of the developer is controlled by the alkaline agent.
It is preferably adjusted to 5 or more and less than 10.5. More preferably, the pH is 8.5 or more and 10.4 or less.

As the fixing solution, those having a commonly used composition can be used. The fixing solution usually has a pH range of 3 to 8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate; thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate; and organic sulfur that can form a soluble stable silver complex salt. Compounds known as fixing agents can be used.

The fixing solution contains a water-soluble aluminum salt which acts as a hardener, for example, aluminum chloride, aluminum sulfate, potassium alum, aldehyde compounds (for example, glutaraldehyde and a sulfurous acid adduct of glutaraldehyde).
Etc. can be added.

The fixing solution may contain, if desired, a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid or citric acid), a pH adjuster (eg, sulfuric acid), a chelating agent having a water softening ability. A compound such as an agent can be included.

The fixing solution contains salts such as acetic acid, citric acid, tartaric acid, malic acid and succinic acid, and optical isomers thereof. As salts of acetic acid, citric acid, tartaric acid, malic acid, succinic acid and the like, these lithium salts, potassium salts,
Lithium hydrogen tartaric acid, potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartaric acid, sodium potassium tartaric acid, and the like such as sodium salt and ammonium salt may be used.

The developing solution and / or the fixing solution can be used as a solution in which a solid processing agent such as a tablet or a granule is dissolved in a solvent such as water.

After the fixing process, the film is washed and / or treated in a stabilizing bath. As a stabilizing bath, for the purpose of stabilizing an image, inorganic and organic acids and salts thereof, or alkali agents and salts thereof for adjusting the film pH (to adjust the film surface pH after treatment to 3 to 8) ( For example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid,
Polycarboxylic acid, citric acid, oxalic acid, malic acid, acetic acid, etc. used in combination, aldehydes (eg, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (eg, ethylenediaminetetraacetic acid or its alkali metal salt, nitrilotriacetic acid salt) , Polyphosphates, etc.), anti-binders (for example, phenol, 4-chlorophenol, cresol, O-phenylphenol, chlorophen, dichlorophen, formaldehyde, P-hydroxybenzoate, 2- (4-thiazoline) -benzo) Imidazole, benzoisothiazolin-3-one, dodecyl-benzyl-methylammonium-chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-
Trichloro-2'-hydroxydiphenyl ether, etc.), color tone adjuster and / or residual color improver (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent;
Specifically, sodium 2-mercapto-5-sulfonate-benzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole,
Mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine, etc.). Among them, it is preferable that the stabilizing bath contains an anti-binder. These may be replenished in liquid or solid form.

In view of the demand for reducing the amount of waste liquid, the replenishment amount is preferably as small as possible. However, it is an embodiment of the present invention that the replenishment amount of the developing solution and the fixing solution is 250 ml or less per 1 m ^{2 of} the photosensitive material. More preferably, it is 30 ml or more and 150 ml or less in the developing solution and the fixing solution. For washing water or stabilizing solution, the replenishment amount is 500 ml.
/ M ² or less is an embodiment of the present invention.

In the present invention, the replenishment amount for development, the replenishment amount for fixing and the replenishment amount for washing indicate the amount of processing solution replenished to the processing mother liquor along with the development processing of the photosensitive material. Specifically, when the same solution as the developing mother liquor and the fixing mother liquor is replenished, the replenishment amount of each solution is used.When the developing concentrated solution and the fixing concentrated solution are replenished with a solution diluted with water, The total amount of each concentrated solution and water, and when replenished with a solution obtained by dissolving a solid developing agent and a solid fixing agent in water, the total amount of each solid processing agent volume and water volume. In the case where the solid developing agent and the solid fixing agent and the water are separately replenished, it is the total amount of each solid processing agent volume and water volume. When replenished with a solid processing agent, it is preferable to express the total amount of the volume of the solid processing agent directly charged into the processing tank of the automatic developing machine and the volume of the replenishing water to be added separately. The developing replenisher, the fixing replenisher and the washing water or the stabilizing solution may be the same as the developing mother liquor and the fixing mother liquor in the tank of the automatic developing machine, or different liquids or solid processing agents, respectively.

The temperature of the developing, fixing, washing and / or stabilizing baths is preferably between 10 and 45 ° C., and each may be individually adjusted.

According to the present invention, the total processing time (Dry to Dry) from the insertion of the leading end of the film into the automatic developing machine until it comes out of the drying zone is reduced when processing is performed using the automatic developing machine due to the demand for shortening the developing time. It is preferably 60 seconds or less and 10 seconds or more. The term “total processing time” as used herein includes the total processing time required for processing the black-and-white photosensitive material, and specifically includes processing, such as development, fixing, bleaching, washing or stabilizing processing, and drying. Time including all process time,
That is, it is the time of Dry to Dry. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to
Dry) is 15 to 50 seconds. In order to stably process a large amount of photosensitive material of 100 m ² or more, in the present invention, it is a preferred embodiment that the development step time is 30 seconds or less, more preferably 18 seconds or less and 2 seconds or more. .

In order to remarkably exert the effects of the present invention, a heat transfer material of 60 ° C. or more, for example, 60 ° C.
To 130 ° C heat roller or 150 ° C or higher radiant object such as tungsten, carbon, nichrome, zirconium oxide / yttrium oxide / thorium oxide mixture, silicon carbide, etc. Those that transmit energy to a radiator such as copper, stainless steel, nickel, or various ceramics to generate heat or emit infrared rays and have a drying zone are preferably used.

Examples of the heat transfer material having a temperature of 60 ° C. or higher include:
A heat roller is mentioned as an example. In the heat roller, it is preferable that the outer periphery of the hollow roller made of aluminum is covered with silicon rubber, polyurethane, or Teflon. Both ends of the heat roller are preferably disposed inside the vicinity of the transport port of the drying unit by bearings made of a heat-resistant resin (for example, Lulon), and are rotatably supported on the side wall.

It is preferable that a gear is fixed to one end of the heat roller, and the heat roller is rotated in the transport direction by a drive unit and a drive transmission unit. A halogen heater is inserted in the roller of the heat roller, and the halogen heater is preferably connected to a temperature controller provided in the automatic developing machine.

The temperature controller is connected to a thermistor arranged in contact with the outer peripheral surface of the heat roller. The temperature controller detects the temperature from the thermistor at 60 ° C. to 150 ° C., preferably 70 ° C. to 130 ° C. Thus, it is preferable that the halogen heater be turned on and off.

Examples of the radiating object emitting a radiation temperature of 150 ° C. or higher, preferably 250 ° C. or higher include, for example, tungsten, carbon, tantalum, nichrome, zirconium oxide.
A method of controlling the radiant temperature by directly passing an electric current through a mixture of yttrium oxide / thorium oxide, silicon carbide, molybdenum disilicide, and lanthanum chromate to control the radiant temperature, or transferring thermal energy from a resistive heating element to the radiator to control the radiant element Examples of the radiator include copper, stainless steel, nickel, and various ceramics.

In the present invention, a heat transfer body of 60 ° C. or more and 150 ° C.
Radiating objects having the above reflection temperatures may be combined. or,
You may combine the conventional warm air of 60 degrees C or less.

In the present invention, an automatic developing machine having the following method and mechanism can be preferably used.

(1) Deodorizing device: JP-A-64-37560
No. (2) upper left column to (3) upper left column (2) Washing water regenerating purifying agent and apparatus: JP-A-6-2503
No. 52, page 3 (0011) to (8), page 0058 (3) Waste liquid treatment method: JP-A-2-64638, lower left column of page (2) to lower left column of page (5) (4) developing bath and fixing Rinse bath during bath: JP-A-4-31
No. 3749, page 18 [0054] to page (21) [00]
65 "(5) Water replenishment method: JP-A-1-281446, page (2), lower left column to lower right column (6) Method of detecting outside air temperature and humidity to control drying air of automatic developing machine: JP-A-1-315745 No. (2) Bottom right column
(7) Lower right column of page and JP-A-2-108051 (2) Lower left column of page to (3) Lower left column of (3) Silver recovery method of fixing waste liquid: JP-A-6-27623, page (4), "0012" ”To (7)“ 0071 ”

[0065]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of Silver Halide Emulsion A >> Simultaneous mixing of an aqueous silver nitrate solution B and a water-soluble halide solution C comprising sodium chloride and potassium bromide in mother liquor A at pH 3.0, 40 ° C. and a constant flow rate. Over 30 minutes to obtain cubic grains of silver chlorobromide (AgCl / AgBr = 70/30 mol%) of 0.18 μm. At this time, the silver potential (EAg) was 160 mV at the start of mixing, and was 100 mV at the end of mixing. Subsequently, after removing unnecessary salts by ultrafiltration, 15 g of gelatin per mol of silver was added, and p was added.
H was adjusted to 5.7 and dispersed at 55 ° C. for 30 minutes. After dispersion
Chloramine T was added in an amount of 4.times.10.sup.- ⁴ mol per mol of silver. The silver potential of the silver halide emulsion A prepared as described above was 190 mV (40 ° C.).

(Mother liquor A) Ossein gelatin 25 g Nitric acid (5%) 6.5 ml Deionized water 700 ml Na [RhCl_Five(H_TwoO)] 0.02 mg (silver nitrate aqueous solution B) silver nitrate 170 g nitric acid (5%) 4.5 ml ion-exchanged water 200 ml (halide solution C) sodium chloride 47.5 g potassium bromide 51.3 g ossein gelatin 6 g Na_Three[IrCl₆0.15 mg of ion-exchanged water 200 ml of the obtained silver halide emulsion A
(ST-1) is 1.5 × 10^-3Mole, potassium bromide
8.5 × 10^-FourPH 5.6, EAg12
Adjusted to 3 mV. Sulfur flower dispersed in fine particles
2 × 10 as a child ^-Five1.5 × 10 mol and chloroauric acid^-Five
After molar addition and chemical ripening at 50 ° C for 60 minutes,
ST-1 at 5 × 10 per mole of silver^-3Mole, fog control
3 × 10 agent (AF-1)^-FourMolar and potassium iodide
5 × 10^-3The moles were each added. Temperature dropped to 40 ° C
Thereafter, the sensitizing dyes (S-1 and S-2) were each added with 1 mol of silver.
2 × 10 per^-FourMolar addition for chemical and spectral sensitization
A silver halide emulsion A was prepared.

ST-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene AF-1: 1-phenyl-5-mercaptotetrazole

[0069]

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<< Preparation of Subbed Support >> A subbed support was prepared according to the method described below.

[Coating of Undercoat Layer on Emulsion Layer Coating Side] Thickness 100
After a corona discharge of 30 W / m ² · min onto a biaxially stretched polyethylene terephthalate support of μm,
The undercoat layer described in Example 1 of JP-A-9-19941 was applied, and dried at 100 ° C. for 1 minute.

[Application of Subbing Layer on Back Side of Backing Layer] A 30 W / m ² coating was applied to the opposite side of the support subjected to the above-mentioned subbing process.
After performing min corona discharge, the undercoat layer U
C-1 and then 10 W /
After applying a corona discharge of m ² · min, the following undercoat layer UC
-2 was applied at a speed of 70 m / min using a roll-fit coating pan and an air knife, dried at 90 ° C. for 2 minutes, and heat-treated at 140 ° C. for 90 seconds. The numerical values were expressed as the amount with per 1 m ^2.

(Undercoat layer UC-1) 2-hydroxyethyl methacrylate / butyl acrylate / t-butyl acrylate / styrene copolymer (25/30/25/20 mass% ratio) 0.5 g Surfactant A 6 mg hexamethylene-1,6-bis (ethylene urea) 10 mg (undercoat layer UC-2) Water-soluble conductive polymer B 0.6 g Hydrophobic polymer particle C 0.4 g Polyethylene oxide compound (Mw = 600) 0.1 g Hardener E 0.1g

[0074]

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<< Preparation of Photosensitive Material >> The following first layer, second layer and third layer (protective layer) are arranged in this order from the support surface side on the subbing layer on the emulsion layer coating side of the subbed support prepared above. At the same time, and cooled and set. Then, on the undercoat layer UC-2 on the back surface of the support, the following backing layer was coated at a coating speed of 200 m /
The photosensitive material sample 101 was prepared by coating at -1 min, cooling and setting at -1 ° C., and simultaneously drying both surfaces. still,
The numerical values are shown in the weight per 1 m ² .

(First layer) Gelatin 1.22 g Silver halide emulsion A 3.3 g as silver amount 5-nitroindazole 0.01 g 2-mercaptohypoxanthine 0.02 g Suspension of colloidal silica / vinyl acetate / vinyl pivalate Suspended polymer (75 / 12.5 / 12.5 mass% ratio) 1.4 g Dextran (average molecular weight 70,000) 0.1 g 4-mercapto-3,5,6-fluorophthalic acid 0.05 g Sodium polystyrene sulfonate (Average molecular weight: 500,000) 0.015 g The coating solution had a pH of 5.8 and an EAg of 125 mV.

(Second layer) Gelatin 0.4 g Nucleation promoter Na 0.016 g Dextran (average molecular weight 70,000) 0.1 g Latex polymer L1 0.5 g Disinfectant Z 0.005 g Hardener (H-1) 0.07 g Polymethyl methacrylate latex (particle size 3 μm) 0.01 g (third layer): protective layer gelatin 0.4 g Colloidal silica / vinyl acetate / vinyl pivalinate suspension polymer (75 / 12.5 / 12 0.18 g Fungicide Z 0.005 g Surfactant: Comparative 1 (sodium dihexylsulfosuccinate) 0.010 g Hardener (H-1) 0.120 g Polymethyl methacrylate latex (particle size 3 μm) 0.01 g (backing layer) Gelatin 2.6 g Dye F-1 0.11 g Dye F-2 0.02 g Colloidal silica / Suspension polymer of vinyl acid / vinyl pivalinate (75 / 12.5 / 12.5 mass% ratio) 0.7 g Sodium polystyrene sulfonate 0.010 g Matting agent (monodisperse polymethyl methacrylate having an average particle size of 3 μm) Dodecylbenzenesulfonic acid 0.005 g Hardener (H-1) 0.05 g Hardener (H-2) 0.07 g

[0078]

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[0079]

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Next, the first layer in the sample 101,
Samples 102 to 108 were prepared in the same manner as Sample 101, except that the amounts of gelatin in the second and third layers and the type of surfactant in the third layer (protective layer) were changed as shown in Table 1 below. . In Table 1, Comparative Example 2 of the surfactant used in the third layer is shown below.

Comparative 2: nC ₁₂ H ₂₅ —O— (CH ₂ CH
About ₂ O) ₃ -SO ₃ Na sample prepared as "development processing and evaluation of the photosensitive material" or 101 to 108, the exposure shown below was developed and various evaluations.

(Exposure and development processing)
Through the interference filter and the wedge, so as to have a blackening ratio of 8%, and then developed using a plate making automatic developing machine LMD1060 manufactured by Dainippon Screen Co., Ltd. under the following developing treatment prescription and conditions.

[0083] Each treatment liquid formulation is as follows.

<Developer> Diethylenetriaminepentaacetic acid / sodium pentasodium 1 g Sodium sulfite 30 g Potassium carbonate 53 g Potassium hydrogen carbonate 17 g 1-Phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone 1.5 g Sodium erythorbate monohydrate 55 g 1-phenyl-5-mercaptotetrazole 0.025 g potassium bromide 4 g 5-methylbenzotriazole 0.21 g sodium hydroquinone monosulfonate 5 g 8-mercaptoadenine 0.07 g potassium hydroxide was added to adjust the pH to 10.2. Finished to 1L.

<Fixing solution> (Starting solution: per 1 L of working solution) Sodium thiosulfate 200 g Sodium sulfite 22 g Sodium gluconate 5 g Trisodium citrate dihydrate 12 g Citric acid 12 g The pH of the working solution is 5.4 with sulfuric acid. And finished to 1L.

<Washing Water> 1 L of tap water to which 8.8 ml of the following purifying agent was added was used as washing water.

A purifying agent was prepared according to the following formulation. Hydrogen peroxide solution 35% by mass 85.8 g Salicylic acid 0.1 g 5-Chloro-2-methyl-4-isothiazoline-3one 15.0 g Polypropylene glycol 3.1 g Diethylenetriaminepentaacetic acid / 5 sodium 12.0 g pH using sulfuric acid Was adjusted to 3.1, and finished to 1 L using pure water.

<Amount of replenishment of processing solution> A developing solution, a fixing solution, a purifying agent for rinsing water and tap water for dilution of the above formulation were used as respective replenishing solutions, and were directly replenished to a developing tank, a fixing tank and a rinsing tank under the following conditions. did.

[0089] (Measurement of sensitivity) Each developed sample obtained above was
Density measurement was performed using an optical densitometer PDA-65 (manufactured by Konica Corporation), and a characteristic curve composed of vertical axis density D and horizontal axis exposure amount LogE was prepared. In the characteristic curve, the reciprocal of the exposure amount giving an optical density of 3.0 was defined as sensitivity, and the sample 10
The relative sensitivity was expressed by setting the sensitivity at 1 to 100.

(Evaluation of Black Pot) The unexposed portion of the developed sample prepared above was visually observed with a 100-power loupe, and was observed for 2 mm.
² , the number of black pots having a diameter of 5 μm or more was measured.

(Evaluation of processing stain) The automatic developing machine LMD
Using 1060, 100 m ² of each sample was continuously treated and then left for 24 hours with the power on. Thereafter, three 610 × 508 mm size check samples were processed, and the processing stains of the samples were visually observed. In addition, evaluation was performed according to the rank shown below, and it was judged that there was no practical problem if it was in the range of ranks 3-5.

Rank 5: No dirt adhered to the first sheet. Rank 4: Small dirt adhered slightly to the first sheet, but no dirt adhered to the second sheet. Rank 3: First sheet And the second sheet has no stain. Rank 2: The first and second sheets have stains, but the third sheet has no stains. Rank 1: Table 1 shows the evaluation results of the respective samples obtained as described above.

[0093]

[Table 1]

As is evident from Table 1, the sample according to the present invention was able to obtain high sensitivity, to suppress the occurrence of black spots, and to obtain excellent results with no processing stain.

Example 2 Developing treatments 1 to 6 were performed in the same manner as in Example 1 except that the developing time was changed to the contents shown in Table 2 using the samples 104 and 106 produced in Example 1. Evaluation of the processing stain was performed in the same manner as in Example 1. Table 2 shows the obtained results.

[0096]

[Table 2]

As is evident from Table 2, the use of the photosensitive material according to the present invention and the development time of 30 seconds or less proved that the processing stain resistance was superior to that of the comparative example.

Example 3 Developing treatments 7 to 12 were performed in the same manner as in Example 1 except that the replenishing amount of the developing solution was changed to the contents shown in Table 3, using the samples 104 and 106 produced in Example 1. Immediately after the start of the continuous treatment and after the treatment of 100 m ^{2 of the} sample, the same sensitivity, black spots, and stains as in Example 1 were evaluated.
Shown in

[0099]

[Table 3]

As is clear from Table 3, the use of the light-sensitive material according to the present invention and the replenishing amount of the developing solution of 250 ml / m ² or less suppressed the occurrence of black spots as compared with the comparative example. It was also found that the sensitivity fluctuation was small and the processing stain resistance was improved even after continuous processing.

Example 4 Developing treatments 13 to 18 were performed in the same manner as in Example 1 except that the replenishing amount of the fixing solution was changed to the contents shown in Table 4 using the samples 104 and 106 produced in Example 1. The processing stain after continuous processing as in Example 1 and the odor of the fixing solution shown below were evaluated. The results obtained are shown in Table 4.

(Evaluation of odor of fixer) ○: Slight odor not △: Smell, but not sensible if used. ×: Strong odor, not easy to use.

[0103]

[Table 4]

As is clear from Table 4, by using the photosensitive material according to the present invention and setting the replenishing amount of the fixing solution to 250 ml / m ² or less, the processing stain after the continuous processing was improved as compared with the comparative example. In addition, good results were obtained with respect to the odor of the fixing solution and poor fixing. In addition, in the evaluation of the processing stains in the processing numbers 13 and 14, spot-shaped fixing spot defects occurred in the evaluation samples.

Example 5 Using the samples 104 and 106 produced in Example 1, the washing tank of the automatic developing machine LDM1060 was modified to a two-stage countercurrent washing method, and the replenishing amount of washing water was as shown in Table 5. Developing processes 19 to 23 were performed in the same manner as in Example 1 except that
Processing stains after the continuous treatment were evaluated in the same manner as in Example 1, and the obtained results are shown in Table 5.

[0106]

[Table 5]

As is clear from Table 5, the photosensitive material according to the present invention was used, and the replenishing amount of washing water was 500 ml / m ^2.
By performing the following, it was confirmed that the treatment stain resistance after the continuous treatment was improved with respect to the comparative example.

[0108]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and little sensitivity fluctuation, improved black spot failure, processing stains and defective fixing, and realized low replenishment liquid in rapid processing or long-term running processing. A material and a method for developing the same can be provided.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03C 5/31 G03C 5/31

Claims (5)

[Claims] 1. A support having at least one light-sensitive silver halide emulsion layer on one side thereof, wherein the total amount of gelatin on the emulsion layer side is less than 2.0 g / m ² , and (1)
A silver halide photographic material comprising a compound represented by the formula: Formula (1) R-O- (CH 2 CH 2 O) m - (CH 2) n -SO 3 - M + wherein, R represents a substituted or unsubstituted alkyl group, m is 1 to 15 , N represents an integer of 1 to 10, respectively. M ⁺ represents a counter cation. ] 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side of a support and containing a compound represented by the above general formula (1). A method for developing a silver halide photographic light-sensitive material, wherein the processing is performed with a development time of 30 seconds or less. 3. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on one side of a support and containing a compound represented by the above general formula (1). A method for developing a silver halide photographic material, wherein the processing is performed at a replenishment rate of a developer of 250 ml / m ² or less. 4. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on one side of a support and containing a compound represented by formula (1). A method for developing a silver halide photographic material, wherein the processing is performed at a replenishment rate of a fixing solution of 250 ml / m ² or less. 5. A silver halide photographic material having at least one photosensitive silver halide emulsion layer on one side of a support and containing a compound represented by the formula (1). 500 ml for replenishment of washing water or stabilizing solution
/ M ² or less, a method for developing a silver halide photographic material.