JPH04281447A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To offer a backing layer in which dyes can be easily decolored and cracking is hardly caused. CONSTITUTION:The backing layer of the silver halide photographic sensitive material contains a compd. expressed by formula 1. Formula 1: M2SO4.nH2O (M: alkali metal, n: integer of 0-3) This photosensitive material has a conductive layer containing a water-soluble conductive polymer, hydrophobic polymer and hardening agent, or one of metal oxides, or both of these.

Description

Detailed Description of the Invention [0001] The present invention relates to a silver halide photographic light-sensitive material, and more specifically, the present invention relates to a silver halide photographic light-sensitive material, and more specifically, the dye added to the backing layer is easily decolorized and This invention relates to a silver halide photographic material whose backing layer is less likely to crack. BACKGROUND OF THE INVENTION In recent years, the amount of information has increased as part of the information industry, and with this, there has been a demand for faster processing. In response to this, demands for rapid processing of silver halide photographic light-sensitive materials, especially printed light-sensitive materials, are becoming extremely strict in the printing industry. On the other hand, in order to improve workability and stability, rabbit access development is used, which is an improved version of so-called lith development, which has been commonly used in the development of printed photosensitive materials, to improve its shortcomings in retention. It's starting to look like this. In addition, by incorporating a high contrast agent such as a hydrazine compound into the silver halide emulsion even with an ordinary developer, it is possible to achieve high contrast equivalent to that of lithographic development, and
"to Dry" development in about 90 seconds became possible. However, in recent years, there has been a growing demand for even shorter development times, such as ultra-quick "Dry to Dry" development of 60 seconds or less, and as a matter of course, deterioration in image quality cannot be tolerated. By performing such ultra-quick processing and shortening the processing time, the backing dye becomes difficult to decolor, and furthermore, "Dry to Dry"
In order to shorten the drying time, it is necessary to raise the drying temperature, but raising the drying temperature in this way has caused a problem in that the backing layer may crack after treatment. [0005] As a result of various studies on these problems, the inventors of the present invention discovered that the initial objective could be achieved by adding a certain type of sulfate to the backing layer, and thus completed the present invention. It's arrived. OBJECTS OF THE INVENTION Accordingly, it is an object of the present invention to provide a silver halide photographic material in which the dye added to the backing layer is easily decolorized and the backing layer is not easily cracked. DESCRIPTION OF THE INVENTION The above object of the present invention is to provide (1) a silver halide film having at least one photosensitive silver halide emulsion layer on a support and at least one backing layer on the opposite side of the emulsion layer; 1. A method for producing a silver halide photographic material, which comprises adding a compound represented by the following formula 1 to at least one layer on the backing layer side. Formula 1 M2 SO4 .nH2 O [In the formula, M represents an alkali metal, and n is an integer from 0 to 3. (2) The method for producing a silver halide photographic material according to claim 1, which comprises at least one conductive layer containing a water-soluble conductive polymer, a hydrophobic polymer, and a hardening agent. (3) This is achieved by the method for producing a silver halide photographic material according to claim 1 or 2, which comprises at least one conductive layer containing a metal oxide. The present invention will be explained in more detail below. "Dry t" used in the present invention
"Dry" refers to the total time from when the leading edge of the photosensitive material is inserted into the automatic developing machine until it comes out of the automatic developing machine after undergoing development, fixing, washing, and drying. In other words, the total length (m) of the processing line including the transition portion of each layer is expressed as the line conveyance speed (m
It is the quotient (sec) divided by /sec). Specific examples of the compound represented by formula 1 used in the present invention are K2 SO4 , Na2 SO4 .10
H2 O, LiSO4 ・H2 O, Rb2 SO4
etc. The silver halide photographic material used in the present invention is produced by a conventional method, and when coating the backing layer, the compound represented by Formula 1 is added to the backing coating solution. The silver halide photographic material thus obtained is rapidly processed after exposure. This rapid processing method will be explained below. This rapid processing includes the steps of development, fixing, washing, and/or stabilization, and is preferably used for processing using an automatic processor. An automatic developing machine has a developing tank, fixing tank, washing tank, and/or
Alternatively, each stabilization treatment tank is provided, and a transition portion is provided between each tank. In the present invention, "Dry to Dry"
Preferably, the total time is about 20 to about 60 seconds. [0013] In this specification, the term "fixing time" refers to the time from immersion in a fixing tank liquid until immersion in the next washing tank liquid (stable tank liquid). Further, "washing time" refers to the time during which the product is immersed in the washing tank liquid. In addition, "drying time" is usually 35°C to 100°C, preferably 40°C.
The processing machine is equipped with a drying zone where hot air of ~80°C is blown, and this refers to the time the product is in the drying zone. A combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones is preferred as the developing agent used in the developer used in the development process, particularly in the black and white developer, since it is easy to obtain good performance. Of course, a p-aminophenol type developing agent may also be included. The dihydroxybenzene developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5
Examples include -dichlorohydroquinone, 2,3-dibromohydroquinone, and 2,5-dimethylhydroquinone, with hydroquinone being particularly preferred. The developing agent for the above 1-phenyl-3-pyrazolidone or its derivative is 1-phenyl-4,4-
Examples include dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone. The p-aminophenol developing agents include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. , 2-methyl-p-aminophenol, p-benzylaminophenol, etc. Among them, N-methyl-p-
Aminophenols are preferred. [0018] The developing agent is usually 0.01 mol/liter ~
Preferably, it is used in an amount of 1.2 mol/l. Sulfites are used as preservatives in developing solutions, and examples of such sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, and sodium formaldehyde bisulfite. Sulfite is 0.2 mol/
It is preferably at least 1 liter, particularly at least 0.4 mol/liter. Further, the upper limit is preferably 2.5 mol/liter. The pH of the developer is preferably in the range of 9 to 13, more preferably in the range of 10 to 12. Alkaline agents used for pH adjustment include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator. Buffers such as JP-A-61-28708 (borates), JP-A-60-93439 (e.g., sucrose, acetoxime, 5-sulfosalcylic acid, etc.), phosphates, carbonates, etc. may be used. . Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, and ethanol. ,
Organic solvents such as methanol: 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole-5-sulfonate, mercapto compounds such as lithium salts, indazole compounds such as 5-nitroindazole, 5-methyl It may contain an antifoggant such as a benztriazole compound such as benztriazole, and may further contain a toning agent, a surfactant, an antifoaming agent, a water softener, and JP-A-56
It may also contain the amino compound described in No.-106244. In the present invention, silver stain preventive agents such as compounds described in JP-A-56-24347 and amino compounds such as alkanolamines described in JP-A-56-106244 can be used in the developer. . Besides this, L.
F. A. “Photographic Processing” by Meson
"Chemistry", Focal Press (1966)
226-229, U.S. Pat. No. 2,193,015, U.S. Pat. The development temperature is preferably about 25°C to 50°C, more preferably 30°C to 40°C. The fixing solution used in the next fixing step is an aqueous solution containing thiosulfate, and preferably has a pH of 3.8 or higher, more preferably a pH of 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 fixing agent used can be varied as appropriate, and is generally about 0.1 to about 6 mol/liter. The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, ammonium sulfate, potassium alum, and the like. In the fixing solution, tartaric acid, citric acid, or their salts can be used alone or in combination of two or more. Those containing 0.005 mol or more of these compounds per liter of fixer are effective, particularly 0.01 mol/liter to 0.01 mol/liter.
0.3 mol/liter is 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 (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, nitric acid), a pH adjuster (eg, sulfuric acid), and a chelating agent with water softening ability. and the compounds described in Japanese Patent Application No. 60-213562. The fixing temperature is preferably about 20°C to about 50°C, more preferably 30°C to 40°C. In the present invention, the photosensitive material is subjected to water washing or stabilization treatment after being developed and fixed. Any method known in the art can be applied to the washing or stabilization treatment, and water containing various additives known in the art can also be used as the washing water or stabilizing liquid. By using water that has been treated with anti-mold measures as the washing water or stabilizing liquid, not only low replenishment processing becomes possible, but the piping for installing the automatic processing machine becomes unnecessary, and the number of stock tanks can be further reduced. [0027] As an anti-mildew means, Japanese Patent Application Laid-Open No. 60-2639
Ultraviolet irradiation method described in No. 39, No. 60-263940
Method using a magnetic field described in No. 61-131632
A method of purifying water using an ion exchange resin as described in the issue,
Methods using antibacterial agents described in Japanese Patent Application No. 60-253807, No. 60-295894, No. 61-63030, and No. 61-51396 can be used. Furthermore, L. E. West"Water
Quality Criteria"PhtoSc
i&Eng. Vol. 9, No. 6 (1965), M.
W. Beach”Microbiological
Growths in Motion-Pictu
re Processing"SMPTE Jou
rnal Vol. 85, (1976). R. O. D
eegan,”Photo Proce 0029]ssing Wash Water
Biocides”J.ImagingTech.V
ol. 10, No. 6 (1984) and JP-A-57-8
No. 542, No. 57-58143, No. 58-10514
5, No. 57-132146, No. 58-18631, No. 57-97530, No. 57-157244, etc. Antibacterial agents, anti-bacterial agents, surfactants, etc. can also be used in combination. . Furthermore, in the water washing bath, R. T. Kreiman
Written by J. Image, Tech10, (6) 242 (19
The isothiazoline compound described in 84), RESE
ARCH DISCLOSURE Volume 205, I
Isothiazoline compounds described in tem20526 (May 1981 issue), Volume 228, Item 228
45 (April 1983 issue), compounds described in Japanese Patent Application No. 61-51396, etc. can also be used in combination as microbiocides. Further, specific examples of antifungal agents include phenol,
4-chlorophenol, pentachlorophenol, cresol, o-phenylphenol, chlorophene, dichlorophene, formaldehyde, glutaraldehyde, chloracetamide, p-hydroxybenzoic acid ester, 2-(4-thiazoline)-benzimidazole, benzo Isothiazolin-3-one, dodecyl-benzyl-
These include dimethylammonium chloride, N-(fluorodichloromethylthio)-phthalimide, 2,4,4'-trichloro-2'-hydroxydiphenyl ether, and the like. Furthermore, various surfactants can be added to the washing water for the purpose of stabilizing recorded images and preventing uneven water droplets. As the surfactant, any of cationic, anionic, nonionic, and amphoteric types may be used. Specific examples of surfactants include engineering books (
These include compounds listed in the "Surfactant Handbook" published by Co., Ltd. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, adjusting membrane pH (
various buffering agents (e.g. borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid) for pH 3 to 8). Typical examples include aldehydes such as formalin (used in combination with acids, etc.) and formalin. [0034] In addition, various additives such as chelating agents, bactericidal agents (thiazole type, isothiazole type, halogenated phenol, sulfanilamide, benzotriazole, etc.), surfactants, optical brighteners, and hardening agents are used. Alternatively, two or more of the same or different target compounds may be used in combination. Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate as membrane pH adjusters to the processing solution in order to improve image storage stability. The water washing or stabilizing bath temperature in the above method is preferably 0°C to 50°C, more preferably 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. Preferably, drying is performed at about 40<0>C to about 100<0>C. Typical methods for forming the conductive layer in the present invention include a method in which it is formed by containing a water-soluble conductive polymer, hydrophobic polymer particles, a curing agent, etc., and a method in which it is formed by containing a metal oxide. . Examples of the water-soluble conductive polymer used in the former method include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group. It will be done. The amount of conductive groups required is 5% by weight or more per polymer molecule. Water-soluble conductive polymers contain hydride [
It may contain a roxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, or a vinyl sulfone group. The molecular weight of the polymer is preferably 3,000 to 100,000, more preferably 3,500 to 70,000. Specific examples of water-soluble conductive polymers include compounds described in Japanese Patent Application No. 2-65831 and the like. These polymers can be synthesized by polymerizing monomers that are commercially available or obtained by conventional methods. The amount of these compounds added is 0.01g/m2
~10g/m2 is preferred, particularly preferably 0.1
g/m2 to 5 g/m2. These compounds can be used alone or mixed with various hydrophilic binders or hydrophobic binders to form a layer. Particularly advantageous hydrophilic binders include those commonly used as binders for silver halide emulsions, such as gelatin or polyacrylamide. The hydrophobic polymer particles that can be contained in the conductive layer are composed of so-called latex particles that are substantially insoluble in water, and the hydrophobic polymers include, but are not particularly limited to, styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, It is obtained by polymerizing monomers selected from olefin derivatives, halogenated ethylene derivatives, vinyl ster derivatives, acrylonitrile, etc. in any combination. Especially styrene derivatives, alkyl acrylates,
It is preferable that the alkyl methacrylate content is at least 30 mol %, particularly preferably 50 mol % or more. To make a hydrophobic polymer into a latex, emulsion polymerization is carried out (emulsion polymerization method), and after dissolving the solid polymer in a low boiling point solvent and finely dispersing it, the solvent is distilled off (dispersion method).
There are two methods, both of which can be adopted.
Emulsion polymerization is preferred because it produces particles with fine and uniform particle sizes. The molecular weight of the hydrophobic polymer may be 3000 or more, and there is almost no difference in transparency depending on the molecular weight. Specific examples of hydrophobic polymers include Japanese Patent Application No.
-65831 and the like are mentioned. The amount of hydrophobic polymer added is preferably 0.01 g/m2 to 1
0g/m2, particularly preferably 0.1g/m2 to 5g
/m2. As the activator used in the emulsion polymerization or the dispersant used in the dispersion method, a nonionic activator is used, and a polyalkylene oxide compound is preferably used. Specific examples of the polyalkylene oxide compound optionally used in the present invention include compounds described in Japanese Patent Application No. 2-65831 and the like. As the curing agent that can be used in the conductive layer, hydroxy-containing epoxy curing agents are preferred, and reaction products of polyglycidol and epihalohydrin are more preferred. The preferable addition amount of each of the above reaction products is 1 to 10
00 g/m2 is preferred. Next, a method of forming a conductive layer using a metal oxide will be explained. Crystalline metal oxide particles are preferred as the metal oxide, but those containing oxygen vacancies and those containing a small amount of foreign atoms that form donors for the metal oxide used are generally used. In other words, it is particularly preferred because it has high conductivity, and the latter one containing a small amount of a foreign atom that forms a donor for the metal oxide used is particularly preferred because it does not cause fog in the silver halide emulsion. Examples of metal oxidation include ZnO2, Ti
O2, SnO2, Al2O3, In2O3
, SiO2, MgO, BaO, MoO3, V2O
5 or their composite oxides are preferred, especially Zn
O2, TiO2 and SnO2 are preferred. Examples of the addition of different atoms include Sb, etc. to SnO, or Nb to TiO2.
, Ta, etc. are effective. The amount of these different atoms added is preferably in the range of 0.01 to 30 mol%, but 0.1
A range of 10 mol % to 10 mol % is particularly preferred. [0048] The metal oxide particles used in the present invention are:
It has electrical conductivity, and its volume resistivity is 107
It is preferably Ωcm or less, particularly 10 5 Ωcm or less. Regarding this oxide, JP-A-56-143431
No. 56-120519, No. 58-62647, etc. [0049] The metal oxide particles are used after being dispersed or dissolved in a binder. The binder that can be used is not particularly limited as long as it has film-forming ability, but
For example, those commonly used as binders for silver halide emulsions are preferred, such as proteins such as gelatin and casein, synthetic polymers such as carboxymethylcellulose, hydroxyethylcellulose, acetylcellulose, agar, and N-vinylpyrrolidone. In order to use the metal oxide more effectively and lower the resistance of the conductive layer, it is preferable that the volume content of the metal oxide in the conductive layer is high. Since a binder of at least 5% is required to provide this, the volume percentage of the metal oxide is preferably in the range of 5 to 95%. [0051] The amount of metal oxide used is 0.05g/m2
~10g/m2 is preferable, more preferably 0.01
g/m2 to 5 g/m2. This provides antistatic properties. In the present invention, the conductive layer is provided between the silver halide emulsion layer and the support and/or on the opposite side of the support with respect to the emulsion layer. That is, it may be provided on the photosensitive emulsion side of the transparent support, or it may be provided on the opposite side of the transparent support with respect to the photosensitive emulsion surface, so-called the back surface. Such a conductive layer is formed by coating on a transparent support that may or may not be subjected to a corona discharge treatment or the like. The composition of the silver halide emulsion for forming at least one layer of the silver halide photographic light-sensitive material used in the present invention is one containing at least 60 mol % of silver chloride. In particular, the composition is preferably silver chloride or silver chlorobromide. The emulsion has an average grain size of 0.05 μm.
m to 0.3 μm is preferable, more preferably 0.06 μm
m to 0.2 μm. Various methods are known for producing such silver halide grains, and any method may be used, but it is more preferable to produce silver halide grains in a reaction vessel at a relatively low temperature. One example is the so-called function-addition control double jet method, which changes the supply amount of silver nitrate and halide in proportion to the growth speed. In addition, p in the reaction vessel during silver halide production
H may be at any pH, but is more preferably between pH 1 and
The acid method carried out in 4 is mentioned. Furthermore, a method of producing silver halide grains by adsorbing nucleic acid decomposition products such as adenine, benzyladenine, adenosine, etc., tetrazaindene compounds, or mercapto compounds onto silver halide in a reaction vessel is also a method of grain formation related to the present invention. This is a preferred mode for. In this specification, the grain size of silver halide grains is conveniently expressed by the edge length of cubic grains having the same volume. The present invention can be applied to various photosensitive materials such as printing, X-ray, general negative, general reversal, general positive, direct positive, etc., but extremely high dimensional stability is required. Particularly remarkable effects can be obtained when applied to photosensitive materials for printing. The silver halide emulsion used in the present invention is disclosed in, for example, US Pat. No. 2,444,607, US Pat.
No. 716,062, No. 3,512,982, West German Application No. 1,189,380, No. 2,058,6
No. 26, No. 2,118,411, Special Publication No. 43-41
No. 33, U.S. Patent No. 3,342,596, Special Publication No. 1973
-4417, West German Application Advertisement No. 2,149,789, Japanese Patent Publication No. 39-2825, Japanese Patent Publication No. 13566-1982, Japanese Patent Publication No. 40665-1985, Japanese Patent Application Publication No. 1987-19814
Compounds described in each specification or publication such as No. 7,
Preferably, 5,6-trimethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5,6-
Tetramethylene-7-hydroxy-S-triazolo (1
, 5-a) Pyrimidine, 5-methyl-7-hydroxy-
S-triazolo(1,5-a)pyrimidine, 7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-
Methyl-6-bromo-7-hydroxy-S-triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, gallic acid
58] Propyl acid, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2
Stabilization using mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), benzimidazoles (6-nitrobenzimidazole), disulfides, phosphorus quaternary salt compounds, etc. Can be done. In addition, the present invention provides photographic additives commonly added to silver halide emulsions,
For example, sensitizers, antifoggants, curing agents, etc. can be added. The hydrophilic colloid used in the present invention is gelatin, but hydrophilic colloids other than gelatin include, for example, colloidal albumin, agar, gum arabic,
Alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, such as US Pat. No. 2,614,928, US Pat. No. 2,525,753. Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in the specifications of U.S. Pat. No. 2,548,520, U.S. Pat.
Polymerizable monomers having ethylene groups such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester, as described in the specifications of No. 831, 767, are graft-polymerized onto gelatin. These hydrophilic colloids can be used in silver halide-free layers, such as antihalation layers, protective layers,
It can also be applied to the middle class. Supports used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, and polycarbonate films. , polystyrene film, etc. are included as typical examples. These supports are appropriately selected depending on the intended use of the silver halide photographic material. [Examples] Specific examples of the present invention will be shown below, but the present invention is not limited thereto. Example 1 [Preparation of support having a conductive layer] After corona discharge was applied to a 100 μm thick undercoated polyethylene terephthalate support, a solution of a conductive layer composition having the following composition was applied in the following amount. Application was performed using a roll-fit coating pan and an air knife at a speed of 70 m/min. Water-soluble conductive polymer (A-1)
0.6g/m2
Hydrophobic polymer (B-1)
0.2g/m2
Polyethylene oxide compound (molecular weight 500)
0.6g/m2 Hardening agent (C
-1)
0.2 g/m2 After drying this at 90°C for 2 minutes and heat-treating it at 140°C for 90 seconds, a solution of this conductive layer composition was applied to only one side and both sides of the support to form a support having a conductive layer. was formed. ##STR1## (Preparation of coating solution for emulsion layer and protective layer above emulsion layer) Solution A Water

9.7 liters sodium chloride

20g
gelatin

105g Solution B Water

3.8 liters sodium chloride

94g
gelatin

365g potassium bromide

450g 0.01% aqueous solution of hexachloroiridate potassium salt


28ml 0.01% aqueous solution of potassium hexabromorodate salt

1.0ml Solution C Water

3.8 liters silver nitrate

1700g [
[0068] In the above solution A kept at 40°C, a pH of 3.
, while maintaining the pAg at 7.7, the above solution B and solution C were added functionally at the same time over 60 minutes, and after continued stirring for an additional 10 minutes, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, and 20% magnesium sulfate was added. 2 liters of aqueous solution and 2.55 liters of a 5% aqueous solution of polynaphthalene sulfonic acid are added, and the emulsion is flocculated at 40° C., decanted and washed with water to remove excess aqueous salt. Next, 3.7 liters of water was added to it to disperse it, and again 20% magnesium sulfate aqueous solution was added.
Add 9 liters and remove excess salt from the aqueous solution in the same manner. Add 3.7 liters of water and 141 g of gelatin thereto and disperse at 55° C. for 30 minutes. As a result, silver bromide was 32 mol%, silver chloride was 68 mol%, and the average grain size was 0.25μ.
m, an emulsion with a monodispersity of 9 is obtained. Take 2,600 ml of this emulsion, add 40 ml of a 1% citric acid aqueous solution and 100 ml of a 5% potassium bromide aqueous solution,
pH and pAg were adjusted. To the emulsion thus obtained, 20 ml of an aqueous solution of 0.1% sodium thiosulfate and 30 ml of an aqueous solution of 0.1% chloroauric acid are added and aged at 60°C for about 3 hours to achieve maximum sensitivity. . A 0.5% solution of 1-phenyl-5-mercaptotetrazole was added to the above emulsion as an antifoggant.
5 ml, 600 ml of a 1% solution of 4-hydroxy-6-methyl 1,3,3a,7-tetrazaindene as a stabilizer, and 960 ml of a 10% aqueous solution of gelatin.
After adding ml and stopping ripening, the obtained milk [
Furthermore, hydroquinone 2 is used as an antifoggant.
70 ml of 0% solution, 60 ml of 20% saponin aqueous solution as a spreading agent, 130 ml of 4% aqueous solution of styrene-maleic acid polymer as a thickener, and 84 g of ethyl acrylate polymer latex. Add and stir, and then add 35 ml of a 1% citric acid aqueous solution and 60 ml of a 5% potassium bromide aqueous solution.
ml was added and the pH and pAg were adjusted. The coating solution for the protective layer was prepared as follows. That is, 105 ml of a 10% potassium bromide aqueous solution is added to an aqueous solution containing 600 g of gelatin, and 375 ml of a 1% aqueous solution of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate as a spreading agent is added. Compound II, which will be described later, was added to the solution thus obtained at a concentration of 45 mg/m 2 and stirred. [Backing layer] Latex polymer: Butyl acrylate-styrene copolymer
0.5g/m2 Styrene-maleic acid copolymer
100mg/m2 citric acid (adjusted to pH 5.4 after application)
40mg/m2 Saponin

200mg/m2
lithium nitrate salt

30mg/m2 Compound of formula 1 according to the invention
50mg/m
2 Backing dye (a)
40
mg/m2 Backing dye (b)

30mg/m2 Backing dye (c)

30mg/m2 alkali-treated gelatin
2.0g/m2 Bis(vinylsulfonylmethyl)ether
15 mg/m2 [Chemical Formula 2] [Chemical Formula 3] [Backing Layer Protective Film] Additives were prepared in the amounts shown below and were simultaneously coated on the top of the backing layer. Dioctylsulfosuccinate ester
200mg/m2 Matting agent: Polymethyl methacrylate (average particle size 4.0μm
)50mg/m2 Alkali-treated gelatin (isoelectric point 4.9)
1.0g/m2 Sodium fluorinated dodecylbenzenesulfonate
50mg/m2 Bis(vinylsulfonylmethyl)ether
20 mg/m2 The pH of the coating solution was adjusted to 5.4 beforehand before coating. [Preparation of sample] Of the emulsion layer, the protective layer above the emulsion layer, the backing layer, and the coating solution for the protective layer above the backing layer prepared as above, the coating solution for the protective layer above the emulsion layer was Adding formalin and an aqueous solution of sodium salt of 2,4-dichloro-6-hydroxytriazine and bisvinylsulfonyl methyl ether as a hardening agent to the solution,
Glyoxal and bisvinylsulfonyl methyl ether are added as a hardening agent to the coating solution for the backing layer, and glyoxal and bisvinylsulfonyl methyl ether are added as a hardening agent to the coating solution for the protective layer above the backing layer. After that, a corona discharge was applied to one side of the support with an energy of 300 W/m2 ·min-1, and the emulsion layer was heated to a silver content of 4.25.
A protective layer was simultaneously coated on top of the protective layer so that the amount of gelatin was 1.36 g/m2. And on the opposite side to the emulsion layer, 300W
After corona discharge with an energy of /m2 ・min-1, the backing layer was formed with a gelatin amount of 2.26 g/m2.
A protective layer was simultaneously coated on top of the protective layer so that the amount of gelatin was 1.34 g/m2. [Development processing conditions] The formulations of the developer and fixer used are shown below. [Developer prescription] Pure water (ion exchange water)
Approximately 300ml potassium sulfite

60g Disodium ethylenediaminetetraacetate
2g potassium hydroxide

10.5g 5-methylbenzotriazole
300m
g diethylene glycol

25g 1-phenyl-4,4-dimethyl-3-pyrazolidone 300mg
1-phenyl-5-mercaptotetrazole
60mg 0085
] Potassium bromide

3.5g hydroquinone

20g potassium carbonate

Add 15g pure water (ion exchange water) and make 1,000 yen
Make it to ml. The pH of this developer is approximately 10.
It was 8. [Fixer formulation] (Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution)
240ml sodium sulfite

17g Sodium acetate trihydrate
6.
5g boric acid

6g Sodium citrate dihydrate
2g acetic acid (90% W/V aqueous solution)
13.6ml 0087
] (Composition B) Pure water (ion exchange water)
17ml sulfuric acid (50% W/W aqueous solution)

4.7g aluminum sulfate (aqueous solution with Al2O3 equivalent content of 8.1% W/V)

26
．． 5 g [0088] When using the fixer, the above composition A and composition B were dissolved in 500 ml of water in that order, and the final volume was made up to 1 liter. The pH of this fixer was about 4.3. The automatic developing machine used was Konica GR-26SR. The development processing conditions are shown below. Development: 32°C
15 seconds fixation 32℃
Wash with water for 15 seconds at 20℃
Dry for 10 seconds at 50℃
The samples thus obtained for 10 seconds were tested for cracking and decolorization, and the results are shown in Table 1. [0090]
Table 1
No. compound crack
remaining color
1-
× ×
2 (1
) 〇
〇 3
(2) 〇
〇
4 (3)
〇 〇
5 (4)
〇
[Method for evaluating cracks] The obtained sample was placed in a desiccator containing silica gel and left at 30° C. for 7 days. This sample was visually evaluated for cracks. 〇: No cracking occurred. △: Slight occurrence at the edges of the film. There is no problem in practical use. ×: Cracks occur. impractical level. [Decolorization evaluation method] The obtained sample was
After conditioning the humidity for one day at 50% RH, the film was developed under the following development conditions. This sample was visually evaluated. 〇: No residual color. △: A slight residual color is observed, but it is at a level that poses no practical problem. ×: Some color remains. Impractical level. Example 2 [Preparation of support having conductive layer] After corona discharge was applied to a subbed-treated polyethylene terephthalate support having a thickness of 100 μm, a conductive layer having the following composition was coated. gelatin

35mg/m2 SnO2 /Sb (8/2)
(particle size 0.3μm) 250mg/
m2 ##STR4## This was dried at 90.degree. C. for 2 minutes and heat treated at 140.degree. C. for 90 seconds. This conductive layer was coated on only one side of the support and on both sides, respectively. In exactly the same manner as in Example 1, an emulsion layer, an emulsion protective layer, a backing layer,
Samples were prepared with a backing protective layer. The sample obtained in this way has excellent decolorization from the backing layer,
Moreover, no cracks in the backing layer were observed. [0096] Effects of the Invention [0096] In the present invention, by containing the compound represented by formula 1 in the backing layer provided on the support surface, the dye added to the layer can be easily decolored, and the backing layer can be easily decolorized. It has the excellent effect of being resistant to cracking.

Claims (3)

[Claims] 1. A method for producing a silver halide photographic material comprising at least one light-sensitive silver halide emulsion layer on a support and at least one backing layer on the opposite side of the emulsion layer, wherein A method for producing a silver halide photographic material, which comprises adding a compound represented by the following formula 1 to at least one layer. Formula 1M2 SO
4.nH2O [In the formula, M represents an alkali metal, and n is an integer of 0 to 3. ] 2. The method for producing a silver halide photographic material according to claim 1, further comprising at least one conductive layer containing a water-soluble conductive polymer, a hydrophobic polymer, and a hardening agent. 3. The method for producing a silver halide photographic material according to claim 1, further comprising at least one conductive layer containing a metal oxide.