JPH0310933B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel image forming method, and more particularly to an image forming method using a roller conveyance type automatic developing processor. Generally, in image formation, a silver halide photographic light-sensitive material is formed by processing a developing process, a fixing process, a washing process, and a drying process in this order. silver halide photographic optical materials in a developer containing an accelerator to strengthen the action of the developing agent such as soda carbonate and borax, and a preservative to increase the shelf life of the developing agent such as sodium sulfite. The exposed silver halide in the photosensitive layer of the photosensitive material is blackened and developed, and then in the fixing step, the developed photosensitive material is treated with a material containing sodium thiosulfate (hypo), etc. The unsensitized silver halide in the photosensitive layer of the photosensitive material is dissolved and fixed, and the photosensitive material is then subjected to a water washing process to remove the unexposed silver halide. After washing away, it is dried in a drying process, thereby forming a negative type image. Conventionally, as a method of obtaining a so-called high-contrast image with a large difference in shading, silver chloride was added at 60 mol%, preferably 75 mol%.
A silver halide photographic light-sensitive material is constructed by using an emulsion consisting of silver chlorobromide containing mol % or more of silver halide and coating it on a support and drying it to form a light-sensitive layer. A method of developing with a developer containing hydroquinone as a developing agent with a low concentration of sulfite ions is known. However, although this method yields high-contrast images, the low concentration of sulfite ions in the developer prevents it from fully functioning as a preservative, making the developer extremely unstable and the development effect not preserved. It has the disadvantage of a short period of time. In JP-A-52-18317, JP-A-53-17719, and JP-A-53-17720, the present inventors used a stable developer to provide extremely high-contrast images. disclosed a silver halide photographic light-sensitive material containing a tetrazolium compound, but it was subsequently discovered that the tetrazolium compound used therein had several problems. That is,
Although high-contrast images can be obtained using the above-mentioned light-sensitive materials, long-term development stability is a problem due to development problems such as uneven development and the tendency for dirt to adhere to the surface of the light-sensitive materials. The point is that it cannot be obtained sufficiently. In order to solve this problem, the present inventors disclosed in Japanese Patent Application No. 56-162770 a method of developing using a developer containing a nonionic activator, but this method still has the above-mentioned problems. It was found that the problem was not solved satisfactorily, and there was a strong desire for a method to reliably solve the problem. The present invention has been made based on the above-mentioned circumstances, and an object of the present invention is to be able to obtain high-contrast images using a silver halide photographic light-sensitive material containing a specific tetrazolium compound, and to obtain a long-lasting image. An object of the present invention is to provide an image forming method capable of obtaining images with little development unevenness and development stains over a period of time. A feature of the present invention is that an automatic processing machine is equipped with a developing tank, a fixing tank, and a washing tank arranged in sequence, and is equipped with a conveying means for continuously transporting the inside of each tank. In the method of forming an image by processing a material, the silver halide photographic light-sensitive material contains at least one compound represented by the following general formula [], [] or [], and the silver halide photographic material When the photosensitive material is continuously conveyed in the automatic processing machine, the surface of the photosensitive layer side of the silver halide photographic material contacts and does not contact the developing roller in the developer in the processing tank. The developer solution in the development processing tank is repeatedly transported seven times or more, and the time required for the developer solution in the development processing tank to be carried into the fixing processing tank via the waving transport roller after being carried out from the developer solution in the development processing tank. The point is that the time spent in transport is more than 10% and less than 35% of the time. (However, in the formula, R ₁ , R ₃ , R ₅ , R ₈ , R ₉ , R ₁₀ and
R ₁₁ is an alkyl group (e.g. methyl group, ethyl group, propyl group, dodecyl group, etc.), an allyl group,
Aryl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group, etc.), naphthyl group (e.g. α-naphthyl group, β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group) group, aminonaphthyl group, etc.), and heterocyclic groups (e.g., thiazolyl group, benzothiazolyl group, oxazolyl group, pyrimidinyl group, pyridyl group, etc.), all of which are groups that form metal chelates or complexes. But that's fine. _R2 , _R6
and R ₇ are allyl group, aryl group, naphthyl group, heterocyclic group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, mercaptomethyl group, mercaptoethyl group, etc.), hydroxyl group,
carboxyl group or a salt thereof, carboxyl alkyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), amino group (e.g. amino group, ethylamino group, anilino group, etc.), mercapto group,
represents a group selected from a nitro group and a hydrogen atom,
D represents a divalent aromatic group, E represents a group selected from an alkylene group, an arylene group, and an aralalkylene group, X represents an anion, and n represents 1 or 2. However, when the compound forms an inner salt, n is 1. ) The present invention will be specifically explained below with reference to the drawings. In the present invention, as shown in FIG. 1, the general formula [], [] or []
A silver halide emulsion comprising a silver halide containing a tetrazolium compound represented by dispersed in a hydrophilic colloid is dried to form a photosensitive layer 2, and a silver halide photographic light-sensitive material 3 is formed.
As shown in FIG.
1 to the photosensitive material outlet 12 in order.
3. A fixing processing tank 14, a washing processing tank 15, and a drying processing tank 16 are provided, and in each tank, a developing transport roller 131 for transporting the photosensitive material, a fixing transport roller 141, A washing conveyance roller 151 and a drying conveyance roller 161 are provided, and among the development conveyance rollers 131 located in the developer in the development processing tank 13, the photosensitive layer is brought into contact with the photosensitive layer 2 side of the photosensitive material. The number of conveyance rollers 132 is 6 or more (for example, preferably 7).
An image is formed by developing the silver halide photographic material 3 in the following manner using an automatic processing machine 20 having a number of up to 30 pieces. That is, the silver halide photographic light-sensitive material 3 is passed through the light-sensitive material entrance 11.
The photosensitive layer conveying roller 132 and the photosensitive layer of the photosensitive material 3 are brought into contact with each other in the developing solution while being supplied from the developing tank 13 and conveyed by the developing conveying roller 131. - Repeating non-contact seven times or more (the time when the photosensitive layer 2 changes from a non-contact state to a contact state with the photosensitive layer transport roller 132 in the developer is counted as one time),
The photosensitive layer 2 side of the photosensitive material 3 is preferably transferred to the photosensitive layer conveying roller 13 about 7 to 30 times.
2, and after the photosensitive material 3 is separated from the developer in the developing tank 13, it passes through the waving conveyance roller 134 until it enters the fixer in the next fixing tank 14. (hereinafter referred to as "Watari time")
T ₁ is the time required for the photosensitive material 3 to pass through the developer in the development processing tank 13 (hereinafter referred to as "developer passing time"), so that T 1 is 10% or more and 35% of T ₂ . For example, when the photosensitive material 3 is transported at a constant speed, it is necessary to transport the photosensitive material 3 from the outlet end 133 at the developer level of the developing tank 13 to the fixing tank 14.
The passage distance of the photosensitive material 3 to the inlet end 142 at the fixing liquid level is set by configuring the axis of the wading conveyance roller 134 to be variable and moving the position of this axis, etc., and the photosensitive material 3 is conveyed. Processing tank 1
In the fixing tank 14, the fixing liquid is conveyed by the fixing conveyance roller 141 to dissolve unexposed silver halide in the photosensitive layer 2 of the photosensitive material 3, and then in the washing tank 15. The surface of the photosensitive layer 2 is washed to wash away the unexposed silver halide, and then sent to the drying tank 16 where it is dried to form a negative type image. Since the present invention employs the above-described method, it is possible to obtain a high-contrast image, and furthermore, as will be understood from the examples described later, an image with less uneven development and less development stains can be obtained. That is, since the tetrazolium compound represented by the general formula [], [] or [] is contained in the photosensitive layer of the silver halide photographic light-sensitive material, the image formed becomes high contrast, and the photosensitive layer side is Since contact and non-contact with the developing transport roller are repeated seven or more times in the developer, fresh developer is repeatedly applied to the surface of the photosensitive layer, resulting in uniform development of the entire photosensitive layer. As a result, uneven development can be extremely reduced, and since the wading time is less than 35% of the developer passage time, the time it takes for the developer to pass through the air from the development layer 13 to the fixing tank 14 is short. During this waving, the reduction of the tetrazolium compound, which is easily cyclized, is sufficiently suppressed, and as a result, the produced reduced product does not remain in the photosensitive material, so that development stains can be extremely reduced. In addition, since the wading time after development is 10% or more of the developer passage time, it is possible to transport the wading by the wading transport roller, and since the wading transport roller has a liquid draining function, the photosensitive The material reliably prevents the development processing solution from entering the fixing processing tank from the development processing tank, and as a result, the occurrence of uneven development and development stains can be suppressed over a long period of time. Note that it is practically impossible to provide a waving conveyance roller while making the waving time after development 10% or more of the developer passage time. Specific examples of the tetrazolium compound represented by the general formula [], [] or [] to be contained in the photosensitive layer of the silver halide photographic light-sensitive material in the present invention include those shown in (1) to (41) below. However, the present invention is not limited to these. (1) 2-(benzothiazol-2-yl)-3-phenyl-5-dodecyl-2H-tetrazolium-bromide (2) 2,3-diphenyl-5-(4-t-octyloxyphenyl)-2H -Tetrazolium-
Chloride (3) 2,3,5-triphenyl-2H tetrazolium (4) 2,3,5-tri(p-carboxyethyl phenyl)-2H-tetrazolium (5) 2-(benzothiazol-2-yl)- 3-Phenyl-5-(o-chlorophenyl)-2H
-Tetrazolium(6) 2,3-diphenyl-2H-tetrazolium(7) 2,3-diphenyl-5-methyl-2H-
Tetrazolium(8) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium(9) 2,3-diphenyl-5-ethyl-2H-
Tetrazolium(10) 2,3-diphenyl-5-n-hexyl-
2H-tetrazolium(11) 5-cyano-2,3-diphenyl-2H-
Tetrazolium(12) 2-(benzothiazol-2-yl)-5-phenyl-3-(4-tolyl)-2H-tetrazolium(13) 2-(benzothiazol-2-yl)-5-
(4-chlorophenyl)-3-(4-nitrophenyl)-2H-tetrazolium(14) 5-ethoxycarbonyl-2,3-di(3
-nitrophenyl)-2H-tetrazolium(15) 5-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium(16) 2,5-diphenyl-3-(p-tolyl)- 2H-tetrazolium (17) 2,5-diphenyl-3-(p-iodophenyl)-2H-tetrazolium (18) 2,3-diphenyl-5-(p-diphenyl)-2H-tetrazolium (19) 5- (p-bromophenyl)-2-phenyl-3-(2,4,6-trichlorophenyl)-2H-tetrazolium(20) 3-(p-hydroxyphenyl)-5-
(p-nitrophenyl)-2-phenyl-
2H-tetrazolium(21) 5-(3,4-dimethoxyphenyl)-3
-(2-ethoxyphenyl)-2-(4-methoxyphenyl)-2H-tetrazolium(22) 5-(4-cyanophenyl)-2,3-diphenyl-2H-tetrazolium(23) 3-( p-acetamidophenyl)-2,
5-diphenyl-2H-tetrazolium(24) 5-acetyl-2,3-diphenyl-
2H-tetrazolium (25) 5-(fur-2yl)-2,3-diphenyl-2H-tetrazolium (26) 5-(thien-2yl)-2,3-diphenyl-2H-tetrazolium (27) 2, 3-diphenyl-5-(pyrido-4
yl)-2H-tetrazolium(28) 2,3-diphenyl-5-(quinol-
2yl)-2H-tetrazolium(29) 2,3-diphenyl5-(benzoxazol-2yl)-2H-tetrazolium(30) 2,3-diphenyl-5-nitro-2H
-tetrazolium(31) 2,2',3,3'-tetraphenyl-5,
5'-1,4-butylene-di-(2H-tetrazolium) (32) 2,2',3,3'-tetraphenyl-5,
5'-p-phenylene-di-(2H-tetrazolium) (33) 2-(4,5-dimethylthiazol-2yl)-3,5-diphenyl-2H-tetrazolium(34) 3,5-diphenyl-2 -(triazin-2yl)-2H-tetrazolium(35) 2-(benzothiazol-2yl)-3-
(4-methoxyphenyl)-5-phenyl-
2H-tetrazolium(36) 1-methyl-2-phenyl-2H-1,
2,3-triazolium(37) 1-n-propyl-2-phenyl-2H
-1,2,3-triazolium(38) 2-(4-methoxyphenyl)-3-phenyl-2H-naphtho-[1,2-d]-1,2,
3-Triazolium (39) 1,5-di(9,10-anthraquinolyl)-bis-{2-[3-phenyl]-2H-naphtho-[1,2-d]-1,2,3- Triazolium} (40) 2,3-di-(4-methoxyphenyl)-
5-nitro-2H-naphtho[1,2-d]-1,
2,3-triazolium (41) 2-p-iodophenyl-3-p-nitrophenyl-5-phenyl-2H-tetrazolium The tetrazolium compound used in the present invention can obtain preferable properties when used alone, but different No matter how many of them are combined in any ratio, the desirable characteristics will not deteriorate. The tetrazolium compound used in the present invention can be added to an emulsion layer made of silver halide in a layer structure commonly used when it is incorporated into a silver halide photographic light-sensitive material. It may be added to the hydrophilic colloid layer directly adjacent to the hydrophilic colloid layer containing the compound, or to the hydrophilic colloid layer adjacent via an intermediate layer. Still another example is to dissolve the tetrazolium compound in a suitable organic solvent, for example, alcohols such as methanol or ethanol, or ethers or esters, and apply the overcoating method to the portion that will become the outermost layer of the silver halide photographic light-sensitive material. It can also be directly applied to and contained therein. The tetrazolium compound used in the present invention is 1 x 10 ^-4 to 10 mol per mol of silver halide contained in the silver halide photographic light-sensitive material,
In particular, it is preferable to use the amount within the range of 2×10 ⁻⁴ to 2×10 ⁻¹ mol. In the present invention, silver halide used in the silver halide photographic light-sensitive material includes silver bromide, silver chlorobromide,
Any of those used in conventional silver halide photographic emulsions, such as silver iodobromide, silver chloroiodobromide, and silver chloride, are included. In particular, when the material is used as a photosensitive material exposed in a bright room using a printer using a metal halide lamp or a high-pressure mercury lamp as a light source, silver chlorobromide containing 90 mol % or more of silver chloride is preferred as the silver halide composition. These silver halides may be coarse-grained or fine-grained, and can be prepared by any known method, such as U.S. Pat. No. 2,592,250;
Specification No. 3276877, Specification No. 3317322, Specification No. 2222264, Specification No. 3320069, Specification No.
3206313 specification or “Journal of
Photographic Science (J.Phot.Sci.)”
Volume 12, No. 5 (September, October issue), 1964, No. 242~
It can be adjusted by the method described on page 251, etc. It is also possible to mix and use silver halides prepared by different methods. In the present invention, the silver halide contained in the photosensitive layer has an average grain size of 0.05 to
1.5 microns, preferably 0.1 to 0.5 microns, and at least 75%, preferably 80% or more of the total particle number is 0.5 to 1.5 times the average particle size, preferably 0.6 to
It is desirable to include silver halide having a grain size of 1.4 times. The most preferred silver halide in the present invention is
The silver chloroiodobromide or silver chlorobromide has an average diameter of 0.1 to 0.3 microns, and 80% or more of all grains have a grain size of 0.6 to 1.4 times the average grain size. In the present invention, the silver halide photographic emulsion can be sensitized by containing various chemical sensitizers. Examples of chemical sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,N-dimethylselenourea, selenourea etc.), reduction sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chloro-oleite, potassium aurithiocyanate, potassium chlorooleate, 2-oresulfone benzothiazole methyl chloride, ammonium chloroparadate, potassium Various noble metal sensitizers represented by chloroplatinate, sodium chloroparadite, gold, etc. can be used alone or in combination of two or more. When using a gold sensitizer, rhodanammonium can also be used as an auxiliary agent. In addition, iridium, rhodium, osmium, bismuth, cobalt, nickel, palladium, ruthenium, iron,
Atoms such as copper, zinc, lead, and cadmium may be contained. When these atoms are contained, they are preferably contained in a proportion of 10 ^-8 to 10 ^-2 mol, particularly preferably 10 ^-6 to ^{10 -4} mol, per mol of silver halide. . Further, it may be a surface latent image type or an internal latent image type. Furthermore, silver halides prepared by various different methods may be mixed. Crystal shapes are hexahedral, octahedral,
There are no restrictions on the shape of the sphere. When the silver halide and tetrazolium compounds used in the present invention are added to the hydrophilic colloid layer, the hydrophilic colloid that is particularly advantageously used 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 U.S. Pat. No. 2,614,928;
Phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin as described in US Pat. No. 2,525,753, etc., or styrene acrylate as described in US Pat. Examples include gelatin graft-polymerized with polymerizable monomers having ethylene groups such as acrylic esters, methacrylic acid, and methacrylic esters, and these hydrophilic colloids can be used in layers containing no silver halide, For example, it can be applied to an antihalation layer, a protective layer, an intermediate layer, etc. Examples of the support in the silver halide photographic material include Paraita paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, polyester film such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide film, polypropylene film, and polycarbonate film. , polystyrene film, etc., and these supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material. The silver halide photographic material used in the present invention is
At least one hydrophilic colloid layer containing silver halide and the tetrazolium compound is coated on the support as described above, and the silver halide photographic light-sensitive material has a protective film having an appropriate thickness. Preference is given to applying a gelatin protective layer, preferably from 0.1 to 10 microns, particularly preferably from 0.8 to 2 microns. The hydrophilic colloid layer may contain various additives as necessary, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, anti-stain agents, PH regulators, antioxidants, and electrostatic charges. inhibitors, thickeners, graininess improvers, dyes, mordants, brighteners,
A developing speed regulator, a matting agent, etc. may be included within a range that does not impair the effects of the present invention. Among these additives, those that can be used particularly preferably as thickeners or plasticizers include those described in U.S. Pat. Kaisho
No. 48-6371, Japanese Patent Publication No. 45-15462, Belgian Patent No. 762833, U.S. Patent No.
Examples include substances described in Specification No. 3767410 and Belgian Patent No. 558143, such as styrene-sodium maleate copolymer, textolan sulfate, and the like. Hardening agents include aaldehyde, epoxy, ethyleneimine,
Various hardening agents such as active halogen type, vinyl sulfone type, isocyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, and acyloyl type can be mentioned. Examples of ultraviolet absorbers include compounds described in US Pat. No. 3,253,921, British Patent No. 1,309,349, etc.
In particular, 2(2'-hydroxy-5-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)benzotriazole, 2-(2'-hydroxy-3' -tertiary butyl-5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-
Examples include tertiary butylphenyl)-5-chlorobenzotriazole. As dyes, US Patent No. 2072908 and West German Patent No.
107990 specification, US Patent No. 3048487 specification,
Compounds described in US Pat. No. 515,998 and the like can be used, and these compounds may be contained in a protective layer, an emulsion layer, an intermediate layer, or the like. Furthermore, coating aids, emulsifiers, permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of silver halide photographic materials include British Patent No. 548532. specification, US Patent No. 1216389, US Patent No. 3026202, US Patent No. 3514293,
Special Publication No. 44-26580, Publication No. 43-17922,
Publication No. 43-17926, Publication No. 43-13166, Publication No. 48-
Publication No. 20785, French Patent No. 202588, Belgian Patent No. 773459, Japanese Unexamined Patent Publication No. 101118/1973
It is possible to use anionic, cationic, nonionic or amphoteric compounds described in the above publications. In addition, as an antistatic agent,
-24159, JP 48-89979, JP 2882157, JP 2972535, JP 48-20785, JP 48-43130, JP 48
−90391 Publication, Special Publication No. 46-24159, 46−
Publication No. 39312, Publication No. 48-43809, Japanese Unexamined Patent Publication No. 1987-
Compounds described in Publication No. 33627 and the like can be mentioned. Further, as a matting agent, for example, British Patent No. 1221980, US Patent No. 2992101, US Patent No. 2956884, French Patent No. 1395544
In particular, silica gel with a particle size of 0.5 to 20 microns, polymers of polymethyl methacrylate with a particle size of 0.5 to 20 microns, etc., are mentioned. Can be done. In the present invention, the following may be mentioned as the developer contained in the developer. Typical HO-(CH=CH) _o -OH type developers include catechol, pyrogal and its derivatives, and ascorbic acid, such as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, 2,3-dibromohydroquinone,
2,5-dihydroxyacetophenone, 2,5
-diethylhydroquinone, 2,5-di-p-phenethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-chlorocatechol, 3-phenylcatechol, 4-phenylcatechol, 3-methoxycatechol, 4-
Acetylpyrogal, 4(2'-hydrobenzoyl)
Examples include pyrogar and sodium ascorbic acid. Typical HO-(CH=CH) _o -NH ₂ type developers include ortho and para aminophenols or aminopyrazolones, such as 4-aminophenol, 2-amino-6-phenylphenol, -amino-4-chloro-6-phenylphenol, 4-amino-2-phenylphenol, 3,4-diaminophenol, 3-methyl-
4,6-diaminophenol, 2,4-diaminoresorcinol, 2,4,6-triaminophenol, N-methyl-P-aminophenol, N-
β-hydroxyethyl-p-aminophenol,
Examples include p-hydroxyphenylaminoacetic acid and 2-aminonaphthol. Examples of the H ₂ N-(C=C) _o -NH ₂ type developer include 4-amino-2-methyl-N,N-diethylaniline, 2,4-diamino-N,N-diethylaniline, and N- (4-amino-3-methylphenyl)-morpholine, p-phenylenediamine, 4
-Amino. N,N-dimethyl-3-hydroxyaniline, N,N,N',N'-tetramethylparaphenylenediamine, 4-amino-N-ethyl-N
-(β-hydroxyethyl)-aniline, 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-(β-methoxyethyl)-3- Methyl-aniline, 4-amino-3-methyl-N-ethyl-N-
(β-methylsulfonamidoethyl)-aniline,
4-Amino-N-butyl-N-γ-sulfobutylaniline, 1-(4-aminophenyl)-pyrrolidine, 6-amino-1-ethyl, 1,2,3.4-tetrahydroquinoline, 9-aminoeurodeine, etc. can be mentioned. Examples of the hetero type developer include 1-phenyl-3-pyrazolidone, 1-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-
3-amino-2-pyrazoline, 1-phenyl-3
-Methyl-4-amino-5-pyrazoline, 5-aminouracil, 5-amino-2,4,6-trihydroxyphyrimidene, and the like. Other examples include The
The Theory of the Photographic Process 4th Edition
Process, Fourth Edition) No. 291-334 and Journal of the American Chemical
Society (Journal or the American Chemic
73, page 3100 (1951) (1951). These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in appropriate combination. These developers also contain sulfites such as sodium sulfite, potassium sulfite, ammonium sulfite, etc.
Alternatively, hydroxylamine, hydrazide compounds, etc. can be included as a preservative. Furthermore, it is necessary to adjust the pH using caustic alkali, alkali carbonate, or amin, which are used in general black-and-white developers, and provide a buffer function, as well as inorganic development inhibitors such as promukari, organic development inhibitors such as benztriazole, and metals such as ethylenediaminetetraacetic acid. Ion scavenger, methanol, ethanol,
Development accelerators such as benzyl alcohol and polyalkylene oxide, sodium alkylarylsulfonate, surfactants such as natural sabonin, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin and glyoxal, sodium sulfate. It is also possible to contain an ionic strength adjusting agent such as. In the present invention, the development temperature of the silver halide photographic light-sensitive material is preferably 50°C or lower, particularly 20°C to 35°C.
is preferred. Further, the development processing time is generally within 3 minutes, but is particularly preferably within 2 minutes. Furthermore, it is optional to employ processing steps other than development, such as washing, stopping, stabilizing, fixing, and if necessary, prehardening and neutralization, and these steps can be omitted as appropriate. The automatic processing machine that can be used in the present invention may be a so-called squirrel-type processing machine commonly used for plate making, or a rapid access processing machine, but the latter is suitable for rapid processing. is preferable. Further, a deep tank type development tank is preferable because it is less susceptible to oxidation over time. As the transportation method, a roller transportation method such as a facing roller method, a staggered roller method, or a combination of a belt and rollers can be used. Here, the materials for the conveyance roller include Bakelite, ABS resin, Teflon resin,
Stainless steel or the like can be used, and a material that does not easily attract dirt to the Japanese roller is preferable. It is also possible to use a roller whose surface is grooved at regular intervals to prevent dirt from adhering to it. In this case, the roller diameter is preferably 1 to 10 cm, particularly 1.5 to 6 cm, but is not limited thereto. In the present invention, either a roller type or a guide type can be adopted as the waving mechanism of the automatic processing machine, and the waving time may be set within the scope of the present invention. FIG. 3 shows another example of a roller conveyance type automatic developing processing machine, and in this example, the developing conveyance roller 1
31, a fixing conveyance roller 141, a washing conveyance roller 151, and a drying conveyance roller 161 are driven by belts 31, 41, 51, and 61, respectively. Examples of the present invention will be described below, but the technical scope of the present invention is not limited thereto, and various embodiments are possible. The following examples will particularly explain the case where a low-sensitivity silver halide photographic material, a so-called bright room type silver halide photographic material, is used. Examples Prior to coating a silver halide photographic light-sensitive material, the following adjustments are made. [Preparation of emulsion solution] Solution A: Pure water 3.5 Gelatin 160g Solution B: Pure water 4.7 Potassium bromide 56g Sodium chloride 413g Potassium hexachlororhodium hydrochloride decahydrate 266mg Solution C: Pure water 4.7 Silver nitrate 1Kg Solution A of the above formulation was heated to 42°C. A silver chlorobromide emulsion (composition: silver chloride 90 mol%, silver bromide 10 mol%) with an average grain size of 0.18 microns was produced by a simultaneous mixing method in which liquids B and C of the above formulation were added over a period of 30 minutes while maintaining the temperature. Adjust. Five minutes after the end of physical ripening, 3 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added to stop the particle growth, and after repeating desalination water washing three times, the dispersion After gelatin was added and dispersed for 30 minutes at a temperature of 50°C, 0.16 g of sodium thiosulfate was added as a chemical sensitizer, and ripened for another 60 minutes. At the end of ripening, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3g
After adding 160 g of 10% aqueous gelatin solution, pure water was added to prepare emulsion solution No. 5. Next, this emulsion solution No. 5 is divided into two equal parts and each is used to prepare emulsion coating solutions _D1 and _D2 as follows. [Preparation of emulsion coating solution D ₁ ] Add one side of the chemically aged emulsion solution divided into two equal parts.
As a compound represented by the above general formula [], 2,
300 c.c. of a 1% aqueous solution of 3,5-triphenyl-2H-tetrazolium chloride, 300 c.c. of a 3% aqueous solution of sodium dipropyl-naphthalene-disulfonate as a coating aid, and styrene as a thickener.
Coating solution D ₁ for finishing emulsion was prepared by adding 10 g of maleic acid copolymer. [Preparation of coating solution D ₂ for emulsion] Coating for emulsion was carried out in the same manner as in the preparation of coating solution D ₁ for emulsion, except that 30 c.c. of a 20% aqueous solution of saponin was added instead of sodium dipropyl-naphthalene-sulfonate. Solution _D2 was prepared. Next, protective film solutions P ₁ and P ₂ for emulsion were prepared as follows. [Preparation of protective film liquid P ₁ for emulsion] Add 10 g of pure water to 1 kg of gelatin, and after swelling the temperature
After heating to 40°C, add a 1% aqueous solution of sodium diethylsulfosuccinate sulfonate as a coating aid, and add the following structural formula (A) and as a filter dye.
One portion of a 10% aqueous solution of each of the compounds shown in (B) was added, and 30 g of a copolymer of methyl acrylic acid having an average particle size of 0.1 to 0.3 microns was added as a matting agent dispersed in gelatin to give a final product of 20. [Preparation of protective film liquid P ₂ for emulsion] 500 cc of a 20% aqueous solution of saponin was added to the protective film liquid P ₁ for emulsion to prepare protective film liquid P ₂ for emulsion. Next, the coating liquids Q ₁ and Q ₂ for the back surface were prepared as follows. [Adjustment of back coating liquid Q ₁ ] Add 20% pure water to 1kg of gelatin, and after swelling the temperature
After heating to 40°C, 10% aqueous solutions of the compounds represented by the above structural formulas (a) and (b) used as additives in the preparation of emulsion protective film liquid P ₁ (800 c.c. and 2, respectively) were added.
% aqueous solution, 1200 c.c. of a 5% aqueous solution of a compound represented by the following structural formula (c) as a dye, and 16 g of a styrene-maleic acid copolymer as a thickener. After adding 16 g of sodium dipropylnaphthalene disulfonate as a coating aid, pure water was added to make a final solution of 30. [Adjustment of back coating liquid Q ₂ ] Prepare back coating liquid Q ₂ in the same manner as in the preparation of back coating liquid Q ₁ , except that 250 c.c. of a 20% saponin aqueous solution was added instead of sodium dipropylnaphthalate. adjusted. [Adjustment of backside protective film liquids P ₃ and P ₄ ] From the above emulsion protective film liquids P ₁ and P ₂ , the above structural formula
The compounds shown in (a) and (b) were removed to prepare backside protective film solutions P ₃ and P ₄ , respectively. [Preparation of silver halide photographic light-sensitive material] A coating liquid for the back side and a protective film liquid for the back side are combined on one side of the undercoated polyethylene terephthalate, and the amount of gelatin attached is 2 g/m 2 for the former and 2 g/m ² for the latter. After simultaneous multilayer coating to give a coating weight of 10 g/m ² , on the other side of the polyethylene terephthalate, combine an emulsion coating liquid and a protective film liquid for emulsion,
In addition, the coating was applied so that the amount of silver attached was 3 g/m ² and the amount of gelatin attached as the protective film was 1 g/m ² , and the following
Test samples of the combinations shown in the table were obtained. At the time of coating, the protective film was hardened using a combination of three hardeners: formaldehyde, mucochloric acid, and ethyleneimine.

[Table] Each of these samples 1 to 4 was printed using an ultraviolet bright room printer "HMW-25" that uses an ultra-high pressure mercury lamp as a light source.
(manufactured by ORC Seisakusho) and exposed it by back-baking it at a light intensity of 10 mJ. The original used for this exposure was a halftone original with a blackening rate of about 70%, and the blackening rate of Samples 1 to 4, which were reprinted, was about 30%. The sensitized samples 1 to 4 were processed using a roller conveyance type automatic developing machine configured as shown in FIG.・Processing was performed under the following conditions while varying the number of times of non-contact. Developer solution Ethylenediaminetetraacetic acid disodium salt 2g Potassium sulfite 50% aqueous solution 100ml Potassium carbonate 70g Hydroquinone 10g Phenidone 0.25g 5-Nitroindazole 0.12g 1-Phenyl-5-mercaptotetrazole
0.03g diethylene glycol 120ml Finish with 1 with pure water. Development processing conditions: Temperature: 30°C, time: 30 seconds Fixing processing conditions: Temperature: 28°C, time: 20 seconds Washing processing conditions: Temperature: room temperature, time: 20 seconds Drying processing conditions: Temperature: 50°C, time: 20 seconds Samples 1 to 4 after development
Development unevenness and development stains were observed. The observations were ranked by visual evaluation as follows. A; Best B; Good C; Somewhat poor D;
Inferior The results are as shown in Table 2.

[Table] As is clear from the results, it can be seen that good results can be obtained according to the present invention.

[Brief explanation of the drawing]

FIG. 1 is an explanatory cross-sectional view showing an example of the configuration of a silver halide photographic light-sensitive material, and FIGS. 2 and 3 are explanatory cross-sectional views showing one example and other examples of the configuration of a roller conveyance type automatic processing machine, respectively. It is a diagram. DESCRIPTION OF SYMBOLS 1...Support, 2...Photosensitive layer, 3...Silver halide photographic material, 13...Development treatment tank, 14
...Fixing treatment tank, 15...Washing treatment tank, 16...
Drying processing tank, 131...Developing conveyance roller, 13
4... Conveyance roller for wading, 141... Conveyance roller for fixing, 151... Conveyance roller for washing, 161
... Conveyance roller for drying, 132 ... Conveyance roller for photosensitive layer, 20 ... Automatic development processing machine, 31, 4
1, 51, 61...belt.

Claims (1)

[Scope of Claims] 1. A silver halide photographic light-sensitive material is processed in an automatic processing machine that has a developing tank, a fixing tank, and a washing tank arranged in sequence, and is provided with a conveying means for continuously transporting the inside of each tank. In a method of processing to form an image,
The silver halide photographic light-sensitive material contains at least one compound represented by the following general formula [], [] or [], and the silver halide photographic light-sensitive material is continuously conveyed by the automatic processing machine. When the surface of the silver halide photographic light-sensitive material on the photosensitive layer side is repeatedly brought into contact and non-contact with the developing roller seven or more times in the developer in the development tank, the surface is conveyed into the development tank. The time required from the time it is taken out of the developer until it is transported into the fixer in the fixing tank via the waving transport roller is 10% or more of the time it takes to be transported in the developer in the developing tank, which is 35%.
An image forming method characterized by the following. (However, in the formula, R ₁ , R ₃ , R ₅ , R ₈ , R ₉ , R ₁₀ and
R ₁₁ each represents a group selected from an alkyl group, an allyl group, an aryl group, a naphthyl group, and a heterocyclic group, and any of these may be a group that forms a metal chelate or a complex. R ₂ , R ₆ and R ₇ are each an allyl group, an aryl group, a naphthyl group, a heterocyclic group, an alkyl group, a hydroxyl group, a carboxyl group or a salt thereof, a carboxyalkyl group, an amino group,
represents a group selected from a mercapto group, a nitro group, and a hydrogen atom, D represents a divalent aromatic group, and E
represents a group selected from an alkylene group, an arylene group, and an aralalkylene group, X represents an anion, and n represents 1 or 2. However, when the compound forms an inner salt, n is 1. )