JPH05273710A - Method for developing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide an image forming method which forms a super high contrast negative image and is excellent in image quality of void character in a system using no hydroquinone as a developing agent. CONSTITUTION:The objective method is a method for developing a sensitive material, containing >5X10<-5>mol. rhodium or ruthenium complex in a silver halide emulsion layer having >90mol.% silver halide and containing a compound expressed by formula (I) or (II) in the emulsion layer or the other layer, with ascorbic acid as a developing agent. In the formulae, each of A1, A2, A3 and A4 is non-metal atomic groups necessary for completing a nitrogen containing hetero ring and is the same with or different from each other, B is a 2-valent linking group, (m) is 0 or 1, each of R1, R2, R3 and R4 is alkyl group, X is a paired ion necessary for balancing electric charge and (n) is number of the paired ion necessary for balancing electric charge in the whole molecule and is 0 in the case of an intramolecular salt.

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 light-sensitive material and a super-high contrast negative image forming method using the same, and more particularly to a silver halide photographic light-sensitive material used in a photomechanical process. The present invention relates to a super-high contrast negative photographic light-sensitive material suitable for a room light-sensitive material.

[0002]

2. Description of the Related Art In the field of graphic arts, super-high contrast (especially manga
An image forming system showing a photographic characteristic of 0 or more) is required. As a method of obtaining a photographic characteristic of high contrast using a stable developing solution, US Pat. Nos. 4,224,401, 4,168,977, and 4,166,742 are disclosed.
No. 4,311,781, No. 4,272,606
No. 4,221,857, 4,332,878
No. 4, ibid. 4,634, 661, ibid. 4,618, 574
Issue No. 4,269,922, No. 4,650,746
No. 4,681,836 and the like, a method using a hydrazine derivative is known. According to this method, photographic characteristics with high contrast and high sensitivity can be obtained, and since it is permissible to add a high concentration of sulfite to the developing solution, the stability of the developing solution against air oxidation is Greatly improved in comparison.

The light-sensitive material for the bright room used in the plate collecting and reversing process is a developed film on which characters or halftone images are formed as an original, and these originals and the reversible photosensitive material are contact-exposed and exposed. It is a light-sensitive material used for negative image / positive image conversion or positive image / positive image conversion. A halftone image, a line image, and a character image are negative according to their halftone dot area, line width, and character image width. It is required to have the ability to convert images / positive images. It is required to have the ability to adjust the tone of halftone images and the line width of character / line images. Came. However, in the advanced image conversion work of forming a blank character image by overlapping and reversing, the conventional method using the light-chamber reversing process using the light-sensitive room light-sensitive material is different from the conventional method using the conventional light-room light-removing light-sensitive material. It has a drawback that the quality of the extracted character image is deteriorated as compared with the method by the process.

The method for forming a blank character image by reversing will be described in more detail. As shown in FIG. 1, transparent or semitransparent sticking bases (a) and (c) (usually having a thickness of about 100 μm). A polyethylene terephthalate film having a) is attached to each of them), and a film having a character or line image formed thereon (line drawing original) (b) and a film having a halftone image formed thereon (halftone original) (d) Then, an original is prepared by superimposing it on the halftone dot original, and the emulsion surface of the return light-sensitive material (e) is brought into close contact with the halftone original of (d) for exposure. Post-exposure development processing is performed to form a white blank portion of the line drawing in the halftone dot image. An important point in such a method of forming a blank character image is ideally that the negative image / positive image conversion is performed according to the halftone dot area and the line width of each halftone original and line drawing original. However, as is apparent from FIG. 1, the halftone dot original is exposed by directly contacting it with the emulsion surface of the light-sensitive material for return, while the line drawing original is stuck and the halftone original (ni) is printed. ) Will be exposed to the return light-sensitive material through the middle. For this reason, if the exposure amount for faithfully converting the halftone dot original image to the negative image / positive image is given, the line drawing original becomes the defocused exposure through the spacer by the embedding base (c) and halftone dot original (d). The line width of the white blank part of is narrowed. This is the reason that the quality of the extracted character image deteriorates.

In order to solve the above problems, systems using hydrazine are disclosed in Japanese Patent Laid-Open Nos. 62-80640 and 62-62.
No. 235938, No. 62-235939, No. 63-1
04046, 63-103235, 63-29.
No. 6031, No. 63-314541, No. 64-135
45. However, in this method, although the image quality is remarkably improved, since the pH of the developing solution is high, air oxidation is remarkably required, and a large amount of hydroquinone needs to be used, and it is necessary to keep the hydroquinone above a certain level. Therefore, a relatively low p-value that does not use hydroquinone as a developing agent.
A low contrast H image forming system is desired.

A method of increasing the contrast using an L-ascorbic acid developer is described in US Pat. No. T896,022, Japanese Examined Patent Publication No. 49.
-46939 etc. are disclosed. Further, JP-A-3-
249756 and 4-32838 disclose ultrahigh contrast systems.

[0007]

SUMMARY OF THE INVENTION The first object of the present invention is to treat a silver halide photographic light-sensitive material with a developing solution without using hydroquinone as a developing agent, so that the gamma (γ) exceeds 10. It is to provide a method for forming a super-high contrast negative image. The second object of the present invention is to
It is an object of the present invention to provide a light-sensitive silver halide photographic light-sensitive material excellent in blank characters and safe light image quality and a processing method thereof.

[0008]

The above-mentioned object of the present invention is to provide a developing method in which a light-sensitive material having at least one silver halide emulsion layer on a support is treated with a developer after exposure to light in the emulsion layer. At least 90 mol% is silver chloride, and contains 5 × 10 ⁻⁶ mol or more of rhodium or ruthenium complex per mol of silver. The silver halide grains in the emulsion layer or other hydrophilic colloid layer are as follows. A method for developing a silver halide photographic light-sensitive material, which contains at least one selected from compounds represented by general formulas (I) and (II), and the developer contains L-ascorbic acid as a developing agent. Achieved by

[0009]

[Chemical 3]

In the formula, A ₁ , A ₂ , A ₃ and A ₄ represent a non-metal atom group for completing the nitrogen-containing heterocycle,
Each may be the same or different. B represents a divalent linking group. m represents 0 or 1. R ₁ , R ₂ , R
₃ and R ₄ each represent an alkyl group. X represents a counter ion required to balance the charge. n represents the number of counterions required to balance the charge of the entire molecule, and n is 0 in the case of an inner salt.

The compounds represented by formulas (I) and (II) used in the present invention will be described in more detail. A ₁ , A ₂ , A ₃ and A ₄ represent a non-metal atom group for completing the nitrogen-containing heterocycle, and may contain an oxygen atom, a nitrogen atom or a sulfur atom, and even if the benzene ring is condensed. I don't care. The heterocycle composed of A ₁ , A ₂ , A ₃ and A ₄ may have a substituent, and each may be the same or different. As the substituent, an alkyl group,
Aryl group, aralkyl group, alkenyl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, carboxy group, hydroxy group, alkoxy group, aryloxy group, amide group, sulfamoyl group, carbamoyl group, ureido Represents a group, an amino group, a sulfonyl group, a cyano group, a nitro group, a mercapto group, an alkylthio group and an arylthio group. As preferred examples, A ₁ , A ₂ , A ₃ and A ₄ are 5- or 6-membered rings (for example, pyridine ring, imidazole ring, thiozole ring, oxazole ring, pyrazine ring, pyrimidine ring, etc.)
And a pyridine ring can be mentioned as a more preferable example. B represents a divalent linking group. The divalent linking group include an alkylene, arylene, _{alkenylene, -SO 2 -, - SO -} , - O -, - S -, -
_{CO -, - N (R 5} ) - (R 5 is an alkyl group, an aryl group, a hydrogen atom.) Represent those composed singly or in combination. Preferred examples of B include alkylene and alkenylene. R ₁ , R ₂ ,
R ₃ and R ₄ represent an alkyl group having 1 to 20 carbon atoms. R ₁ , R ₂ , R ₃ and R ₄ may be the same or different. The alkyl group represents a substituted or unsubstituted alkyl group, and the substituents include A ₁ , A ₂ ,
It is the same as the substituent mentioned as the substituent of A ₃ and A ₄ .

As a preferred example, R ₁ , R ₂ , R ₃ and R ₄ each represent an alkyl group having 4 to 10 carbon atoms. A further preferred example is a substituted or unsubstituted aryl-substituted alkyl group. X represents a counter ion required to balance the charge of the entire molecule. Examples thereof include chlorine ion, bromine ion, iodine ion, nitrate ion, sulfate ion, p-toluenesulfonate, and oxalate. n represents the number of counterions required to balance the charge of the entire molecule, and n is 0 in the case of an intramolecular salt. Specific examples of the compounds represented by formula (I) or formula (II) are listed below, but the present invention is not limited to these compounds.

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

The compounds represented by formulas (I) and (II) of the present invention may be added to a silver halide emulsion or may be added to another hydrophilic colloid layer. When it is added to the silver halide emulsion, it may be added at any time from the physical ripening of the silver halide emulsion to the coating on the support, but it is most preferably added immediately before coating. The addition amount of the compound of the present invention varies depending on the composition or particle size of silver halide grains and the type of compound used, but is 5 × 10 ⁻⁴ to 1 × 1 per mol of silver halide.
It can be used in the range of 0 ^-1 mol. Preferably 2x
10 ⁻³ to 4 × 10 ⁻² mol, particularly preferably 1 ×
It is 10 ^{−3 to} 2 × 10 ⁻² mol.

The silver halide emulsion that achieves the object of the present invention contains 5 × 10 ^-6 mol of rhodium or ruthenium complex salt per mol of silver so that it can be handled in a bright room and realizes ultrahigh contrast. It is contained, and at least 90 mol% or more is silver chloride.

Preferred bridging ligands in rhodium and ruthenium complex salts are nitrosyl, thionitrosyl bridging ligands, halide ligands (fluoride, chloride, bromide and iodide), cyanide ligands, cyanate ligands. Order,
Examples include thiocyanate ligands, selenocyanate ligands, tellurocyanate ligands, azide ligands and core ligands. One of the ligands, if any, is present
It is preferable to occupy one or two.

Specific examples of the transition metal coordination complex are shown below. 1 [Ru (NO) Cl ₅ ] ^-2 2 [Ru (H ₂ O) Cl ₅ ] ^-1 3 [Ru (NO) (H ₂ O) Cl ₄ ] ^-1 4 [Rh (NO) Cl ₅ ] ^{- 2} 5 [Rh (H ₂ O) Cl _5] ^-2 6 [Rh (NO) CN _5] ^-2 7 [Rh (H ₂ O) ClCN _4] ^-2

The addition amount of the metal coordination complex of the present invention is 5
X10 ^-6 to 1 x 10 ^-4 mol / silver mol are preferred. The above metal complex can be added to the silver halide during grain preparation. The content of the metal in the silver halide grains of the present invention is at least 10 ^-6 mol, preferably 10 ^{-6 to} 5 × 10 ^-4 mol, particularly 1 × 10 ^{-5 to} 5 per mol of silver halide. It is × 10 ^-4 mol. The distribution of the metal in the silver halide grain is not particularly limited, but it is preferable that a large amount of the metal be present outside the grain.

The silver halide emulsion of the silver halide photographic light-sensitive material used in the present invention is silver chlorobromide or silver chloroiodobromide containing 90 mol% or more of silver chloride. If the proportion of silver bromide or silver iodide is increased, the safety of safelight in a bright room is deteriorated or γ is decreased, which is not preferable. The silver halide used in the present invention is preferably a so-called core / shell type silver halide, and particularly preferably a core / shell type silver halide having a higher content of transition metal in the share than that of the core. In order to allow the above water-soluble metal complex salt to be present in the silver halide grains, when the water-soluble silver salt and the water-soluble halide solution are simultaneously mixed, a method of adding them in the water-soluble silver salt or in the halide solution is used. preferable. Alternatively, when the silver salt and the halide solution are mixed at the same time, the third solution is 3
The silver halide grains may be prepared by a liquid simultaneous mixing method. The grain size of the silver halide emulsion of the present invention is 0.20.
It is preferably μ or less. In the present invention, in order to prepare fine silver halide grains, the reaction temperature is 50 ° C. or less as a mixing condition.
Preferably 40 ° C or lower, more preferably 30 ° C or lower,
Good results can be obtained by preparing at a silver potential of 70 mV or more, preferably 80 mV to 120 mV, under a condition of sufficiently high stirring speed so as to uniformly mix. The silver halide emulsion used in the present invention is a monodisperse emulsion, preferably a coefficient of variation of 20.
% Or less, particularly preferably 15% or less. Here, the coefficient of variation (%) is calculated by dividing the standard deviation of the particle diameter by the average value of the particle diameter, which is 1
It is a value multiplied by 00. The silver halide grains of the present invention preferably have regular crystal bodies such as cubes and octahedra. The silver halide emulsion of the present invention has the following general formula [A]
By forming particles in the presence of the compound represented by the formula (3), it is possible to obtain even higher performance. General formula [A]

[0025]

[Chemical 10]

In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each is a hydrogen atom; unsubstituted or substituted, which may have a ring having 1 to 20 carbon atoms or a branch. Alkyl group; monocyclic or bicyclic unsubstituted or substituted aryl group; unsubstituted or substituted amino group; hydroxy group; alkoxy group having 1 to 20 carbon atoms;
An alkylthio group of 6; a carbamoyl group which may be substituted with an aliphatic group or an aromatic group; a halogen atom; a cyano group; a carboxy group; an alkoxycarbonyl group having 2 to 20 carbon atoms; or a nitrogen atom, an oxygen atom or a sulfur atom A heterocyclic residue containing a 5-membered or 6-membered ring having such a hetero atom is represented. R ¹ and R ² or R ² and R ³ together are 5 members or 6
You may form a member ring. However, at least one of R ¹ and R ³ represents a hydroxy group. Examples of the unsubstituted alkyl group are methyl group, ethyl group, n-propyl group, i-
Propyl group, n-butyl group, t-butyl group, hexyl group, cyclohexyl group, cyclopentylmethyl group, octyl group, dodecyl group, tridecyl group and heptadecyl group. Examples of the substituent in the substituted alkyl group include a monocyclic or bicyclic aryl group, a heterocyclic residue, a halogen atom, a carboxy group, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 20 or less carbon atoms, and a hydroxy group. And specific examples of the substituted alkyl group are a benzyl group, a phenethyl group, a chloromethyl group, a 2-chloroethyl group, a trifluoromethyl group, a carboxymethyl group, a 2-carboxyethyl group, a 2- (methoxycapbonyl) ethyl group, An ethoxycarbonylmethyl group, a 2-methoxyethyl group, a hydroxymethyl group, a 2-hydroxyethyl group and the like.
Examples of the above-mentioned unsubstituted aryl group are a phenyl group and a naphthyl group, and examples of the substituent when the aryl group is substituted are an alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a carboxy group, and a carbon number. Include an alkoxycarbonyl group having 2 to 6 and a hydroxy group and an alkoxy group having 1 to 6 carbon atoms, and specific examples of the substituted aryl group include p-tolyl group, m-tolyl group, p-chlorophenyl group and p-bromophenyl. Group, o-chlorophenyl group, m-nitrophenyl group, p-carboxyphenyl group, o-carboxyphenyl group, o- (methoxycarbonyl) phenyl group, p-
Hydroxyphenyl group, p-methoxyphenyl group, m-
For example, ethoxyphenyl group. The amino groups represented by R ¹ , R ² , R ³ and R ⁴ may be substituted,
Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, butyl group) and an acyl group (eg, acetyl group, methylsulfonyl group, etc.). Specific examples of the substituted amino group include dimethylamino group, diethylamino group,
A butylamino group and an acetylamino group. R ¹ ,
Specific examples of the alkoxy group represented by R ² , R ³ and R ⁴ include a methoxy group, an ethoxy group, a butoxy group and a heptadecyloxy group. R ¹ , R ² , R ³ and R
^The carbamoyl group represented by ⁴ can have one or two alkyl groups having 1 to 20 carbon atoms and aryl groups having 2 or less rings as a substituent. Specific examples of the substituted carbamoyl group include a methylcarbamoyl group, a dimethylcarbamoyl group, an ethylcarbamoyl group and a phenylcarbamoyl group. Specific examples of the alkoxycarbonyl group represented by R ¹ , R ² , R ³ and R ⁴ are a methoxycarbonyl group, an ethoxycarbonyl group and a butoxycarbonyl group. Specific examples of the halogen atom represented by R ¹ , R ² , R ³ and R ⁴ are a fluorine atom, a chlorine atom and a bromine atom. The heterocyclic residue represented by each of R ¹ , R ² , R ³ and R ⁴ may have a monocyclic ring or a condensed ring of 2 to 3 rings, and specifically includes a furyl group, a pyridyl group, 2- (3-
And a methyl) benzothiazolyl group and a 1-benzotriazolyl group. Examples of the ring formed by R ¹ and R ² or R ² and R ³ include a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a benzene ring, a furan ring, a pyrrolidine ring and a thiophene ring. Specific examples of the compound represented by the general formula [A] are shown below.

[0027]

[Chemical 11]

[0028]

[Chemical 12]

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination for chemical sensitization. Good. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, platinum, palladium, iridium and other complex salts may be contained. Specific examples are US Patent 2,44
No. 8,060, British Patent 618,061 and the like. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. Further, it may be chemically sensitized by using a selenium compound or a tellurium compound.

There are no particular restrictions on the various other additives used in the light-sensitive material of the present invention, and for example, those described in the following sections can be preferably used. Item Applicable place 1) Hydrazine production JP-A-2-12236, page 2, upper right column, line 19 to nucleating agent, page 7, upper right column, line 3, line 3-174143, page 20, lower right column General formula (II) and compounds II-1 to II-54 from line 1 to page 27, upper right column, line 20. 2) Nucleation accelerator JP-A-2-103536, page 9, upper right column, line 13 to page 16, upper left column, line 10 from general formulas (II-m) to (II-p) and compound II- 1 to II-22, compounds described in JP-A-1-179939. 3) Silver halide milk, JP-A-2-97937, page 20, lower right column, line 12 or agent and its manufacturing method, page 21, left lower column, line 14; JP-A-2-12236, page 7, upper right column. The selenium sensitization method described from line 19 to page 12, lower left column, line 12, and Japanese Patent Application No. 3-189532. 4) Spectral sensitizing dye JP-A-2-12236, page 8, lower left column, line 13 to same, lower right column, line 4; JP-A-2-103536, page 16, lower right column, line 3 to page 17, lower left Spectral sensitizing dyes described in column 20, line 20 and JP-A-1-112235, JP-A-2-124560, JP-A-3-7928, and Japanese Patent Application Nos. 3-189532 and 3-41-1064.

5) Surfactant JP-A-2-12236, page 9, upper right column, line 7 to same, lower right column, line 7 and JP-A-2-18542, page 2, lower left column, line 13 Page 4, lower right column, line 18. 6) Antifoggant JP-A-2-103536, page 17, lower right column, line 19 to page 18, upper right column, line 4 and lower right column, lines 1 to 5, further JP-A-1-237538 The thiosulfinic acid compound described in the official gazette. 7) Polymer Latte JP-A-2-103536, page 18, lower left column, line 12 to line 20. 8) Chemical compound having an acid group JP-A-2-103536, page 18, lower right column, line 6 to compound 19 at the same line, upper left column, line 1. 9) Matting agent / slip JP-A-2-103536, page 19, upper left column, line 15 From agent / plasticizer, page 19 upper right column, line 15 10) Hardeners, JP-A-2-103536, page 18, upper right column, lines 5 to 17; 11) Dyes Dyes in the lower right column, lines 1 to 18 of page 17 of JP-A-2-103536, solid dyes described in JP-A-2-294638 and JP-A-3-185773. 12) Binder JP-A-2-18542, page 3, lower right column, lines 1 to 2. 13) Anti-black spot agent Compounds described in U.S. Pat. No. 4,956,257 and JP-A-1-118832 14) Redox compound Compounds represented by the general formula (I) of JP-A-2-301743 (especially compound) Examples 1 to 50), the general formulas (R -1), (R-2) and (R-3) described in JP-A 3-174 143, page 3 to page 20, compound examples 1 to 75, Furthermore, the compounds described in Japanese Patent Application Nos. 3-69466 and 15648. 15) Monomethine compound Compounds of general formula (II) described in JP-A-2-287532 (particularly compounds II-1 to II-26). 16) Dihydroxybe Compounds described in JP-A-3-39948, page 11, upper left column to twelfth genus, page lower left column, and EP452772A.

The developer used in the present invention uses L-ascorbic acid as a developing agent. It is preferable to contain p-aminophenols as an auxiliary developing agent. It is desirable to contain a preservative and an alkali in addition to the above components. The p-aminophenols used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2 -Methyl-p-aminophenol, p-benzylaminophenol, etc., among which N-methyl-p
-Aminophenol is preferred. Developing agent is usually 0.0
It is preferably used in an amount of 5 mol / liter to 0.8 mol / liter. When a combination of L-ascorbic acids and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is 0.05 mol / liter to 0.5 mol / liter and the latter is 0.06 mol. /
It is preferably used in an amount of liter or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite is preferably 0.15 mol / liter or more, and particularly preferably 0.5 mol / liter or more. The upper limit is 2.
It is preferably up to 5 mol / liter.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
It contains a pH adjusting agent and a buffering agent such as potassium carbonate, sodium triphosphate and potassium triphosphate. The pH of the developer is set between 10.5 and 12.3. As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide; ethylene glycol, diethylene glycol, toluethylene glycol, dimethylformamide, methyl cellosolve , Hexylene glycol, ethanol, organic solvents such as methanol; 1-phenyl-5
An antifoggant such as mercaptotetrazole, an indazole-based compound such as 5-nitroindazole, a benztriazole-based compound such as 5-methylbenztriazole, or an anti-foggant (black pepper) inhibitor may be included, and the color may be further added if necessary. A preparation, a surfactant, an antifoaming agent, a water softener, a film hardener, an amino compound described in JP-A-56-106244 may be contained. Particularly preferred compounds are indazole-based compounds and benztriazole-based compounds, and in the present invention, it is possible to further increase the contrast and improve the image quality of blank characters. A preferred compound is JP-A-53-166.
No. 23, No. 54-37732, and the addition amount is in the range of 1 mg to 200 mg, preferably 5 mg to 100 mg per liter of the developing solution.

The compounds described in JP-A-56-24,347 can be used in the developer of the present invention as a silver stain preventing agent. As a solubilizing agent to be added to a developing solution, Japanese Patent Laid-Open No.
The compounds described in 1-267759 can be used. Furthermore, as a pH buffering agent used in a developing solution, JP-A-60 is used.
-93,433 or the compound described in JP-A-62-
The compounds described in No. 186259 can be used.

The fixer is an aqueous solution containing a hardener (eg, a water-soluble aluminum compound), acetic acid and a dibasic acid (eg, tartaric acid, citric acid or salts thereof) in addition to the fixing agent, and preferably. , PH 3.8 or higher, and more preferably 4.0 to 5.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1.
Is about 5 mol / liter. The water-soluble aluminum salt mainly used as a hardening agent in the fixing solution is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum. As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. It is effective that these compounds contain 0.005 mol or more per liter of the fixer, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective. Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like.

If desired, the fixer may further contain preservatives (eg, sulfite, bisulfite), pH buffers (eg, acetic acid, boric acid), pH adjusters (eg, ammonia, sulfuric acid), and improve image preservation. Agents (eg potassium iodide) and chelating agents can be included. Here, the pH buffer is p of the developing solution.
Since H is high, it is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter. The fixing temperature and time are the same as in the case of development, that is, 10 to 50 ° C. at about 20 ° C.
Seconds to 1 minute are preferred. In addition, the washing water may contain an antifungal agent (see, for example, "Chemistry of Antibacterial and Antifungal" by Horiguchi, JP-A-62-1).
The compound described in the specification of No. 15154), a water washing accelerator (such as sulfite), and a chelating agent may be contained.

According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and the temperature is about 20 ° C.
10 seconds to 3 minutes at about 50 ° C is preferred. About 40 ℃
It is carried out at about 100 ° C., and the drying time can be appropriately changed depending on the ambient conditions, but is usually about 5 seconds to 3 minutes and 30 seconds.
US Patent No. 30 for a roller transport type automatic processor
No. 25559, No. 3545971, and the like, and is referred to simply as a roller transport type processor in the present specification. The roller transport type processor comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. .. Here, in the water washing step, a water saving treatment can be performed by using a countercurrent water washing method of two or three stages.

The developing solution used in the present invention is disclosed in JP-A-61-161.
It is preferable to store the packaging material having low oxygen permeability described in No. 73147. As the developing solution used in the present invention, the auxiliary system described in JP-A-62-91939 can be preferably used. The present invention will be further described below with reference to examples.

[0040]

【Example】

Example 1 Emulsions [A] to [G] were prepared by the following method. [Emulsion A] An aqueous solution of silver nitrate and 5 × 10 ⁻⁵ mol of (NH ₄ ) ₃ Rh (H ₂ O) C per 1 mol of silver were added to an aqueous gelatin solution kept at 40 ° C.
An aqueous sodium chloride solution containing ₁₅ was added simultaneously for 3 minutes, and the potential during that period was controlled to 95 mV to prepare 0.08 μm of core particles. Then, 1.5 × 10 ⁻⁴ mol of (NH ₄ ) ₃ per mol of silver nitrate aqueous solution and silver
An aqueous solution of sodium chloride containing Rh (H ₂ O) Cl ₅ was added at the same time for 6 minutes, and the potential was controlled to 100 mV during that time to obtain an average particle size of 0.15μ and total (NH ₄ ) ₃ Rh (H
Cubic silver chloride grains having an amount of ₂ O) Cl ₅ of 5 × 10 ⁻⁵ mol / mol Ag were prepared. 1 × 10 ⁻³ mol / mol Ag as a stabilizer
6-Hydroxy-4-methyl-1,3,3a, 7-tetrazaindene was added to remove the solubility by the flocculation method, and then gelatin was added. Emulsions [B] to [E] were prepared in the same manner.

The emulsions [F to [G] were prepared by the following method. (Emulsion F) 1 × 10 in gelatin aqueous solution kept at 40 ° C.
Compound Example 6 of the general formula (III) corresponding to ^-3 mol / mol Ag
5,6-trimethine-7-hydroxy-s-triazolo (2,3-a) pyrimidine, which was added, was added, and then 5 × 10 ⁻⁵ mol of (NH ₄ ) ₃ Rh (H
_An aqueous solution of sodium chloride containing ₂ O) Cl ₅ was simultaneously added over 3 minutes, and the potential during that period was controlled to 95 mV to prepare 0.07 μm of core particles. After that, 1.5 × 10 ⁻⁴ mol of (N
H ₄ ) ₃ Rh (H ₂ O) Cl ₅ containing sodium chloride aqueous solution at the same time,
The average particle size was 0.12μ and the total (NH ₄ ) ₃
Nearly spherical octahedral silver chlorobromide grains of Rh (H ₂ O) Cl ₅ 5 × 10 ⁻⁵ mol / mol Ag were prepared. Then, after removing the solubility by the flocculation method, gelatin was added.
Emulsion [G] was prepared in the same manner. Emulsion [A] ~
The features of [G] are summarized in Table 1.

[0042]

[Table 1]

The compounds of the present invention and the comparative compounds (a) and (b) were added to the emulsions [A] to [E] as shown in Table 2.

[0044]

[Chemical 13]

Then 2 × 10 ^-4 mol of 1 per mol of silver
-Phenyl-5-mercaptotetrazole, polyethyl acrylate latex as solid content to gelatin 30 wt
%, 1,3-divinylsulfonyl-2-propanol (150 mg / m ² ) was added as a hardening agent, and it was coated on a polyethylene terephthalate film so that the Ag amount was 3.0 g / m ² , A sample was prepared by coating a protective layer upper layer, a protective layer lower layer, a backing layer, and a back protective layer having the following formulations on the upper layer.

[0046]

[Table 2]

[0047] Protective layer underlying] Gelatin 1 g / m ² thioctic acid 6 g / m ² ethyl Tito acid sodium salt 4 mg / m ² Dye [a] 100 mg / m ²

[0048]

[Chemical 14]

1,5-dihydroxy-2-benzaldoxime 35 mg / m ² dodecylbenzene sulfonic acid sodium salt 10 mg / m ² polystyrene sulfonic acid sodium salt 20 mg / m ² ethyl acrylate latex (average particle size 0.05 μ) 2 mg / m ²

[Upper layer of protective layer] Gelatin 0.6 g / m ² Polymethylmethacrylate fine particles (average particle size 2.5 μ) 20 mg / m ² Silicon dioxide fine particles (average particle size 2.8 μ) 30 mg / m ² N-perfluoro Octanesulfonyl-N-propylene glycine potassium salt 3 mg / m ² dodecylbenzenesulfonic acid sodium salt 20 mg / m ² [back layer] gelatin 2.5 g / m ² dye- [b] 0.26 g / m ² 〃- [c ] 30 mg / m ² 〃- [d] 40 mg / m ² 〃- [e] 90 mg / m ²

[0051]

[Chemical 15]

[0052] dihexyl -α- sulfosuccinates sodium salt 30 mg / m ² sodium dodecylbenzenesulfonate 35 mg / m ² 1,3-divinyl-sulfonyl-2-propanol 130 mg / m ² ethyl acrylate latex (average particle size 0.05μ ) 0.5 g / m ² conductive compound SnO ₂ / Sb (weight ratio 9/1, particle size 0.2 μ) 0.1 g / m ²

[Back protective layer] Gelatin 0.8 g / m ² Polymethylmethacrylate fine particles (average particle size 3.4 μ) 40 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 15 mg / m ² Dodecylbenzenesulfonic acid sodium salt 15mg / m ² Fluorosurfactant 5mg / m ²

[0054]

[Chemical 16]

Sodium acetate 40 mg / m ²

The exposure is carried out with a manuscript structure as shown in FIG. 1 of JP-A-58-190943, Dainippon Screen Co., Ltd.
It is exposed by a photo-making room printer P607, and it is exposed at 38 ° C. for 20 minutes with an automatic developing machine FG-660F manufactured by Fuji Photo Film Co., Ltd.
Processing was performed under the condition of seconds. Development was performed with a developer having the following composition.

Developer Formulation N-Methyl-p-aminophenol 2.5 g Sodium sulfite 19.0 L-Sodium ascorbate 10.0 Sodium metaborate 35.0 NaCl 0.6 Water was added to 1000 ml pH 9.6

The following methods were used to evaluate the gradation (γ), the extracted character image quality, and the safelight safety. γ; (3.0-0.3)-{log (exposure amount giving density 0.3) -log (exposure amount giving density 3.0)}

Extracted character image quality; JP-A-58-19094
As described in No. 3, the embedding base / the film on which the positive image of the line drawing was formed (line drawing original) / the embedding base /
Films on which halftone images were formed (halftone originals) were superposed in this order, and the protective layer of each film sample and the halftone originals were closely contacted so as to overlap face-to-face. When an appropriate exposure to obtain a halftone dot area of 50% is given on the upper side and processed as described above, 30
Characters that can reproduce characters with a width of μm are defined as 5, and characters that can reproduce characters with a width of 150 μm or more are defined as 1, and a rank of 4, 3, 2 is provided between 5 and 1 by sensory evaluation.
2 is the limit of practical use.

Fog after safelight irradiation: Fog after irradiation for 30 minutes under 20 lux of a white fluorescent lamp (El40SW) manufactured by Toshiba, and then development processing. As can be seen from Table 2, the samples 2, 3, 5, 6, 8, 9 of the present invention are
γ, the image quality of blank characters and the safelight property are also good.

(Example 2) Emulsions [B], [F] and [G]
Samples 20 to 32 were prepared by dividing and dividing and adding the compound of the general formula [I] or [II] of the present invention and the same additive as in Example 1 and coating. These samples were exposed and developed in the same manner as in Example 1 to evaluate the performance. The results are shown in Table 3. The developer has the formulation shown in Table 4.

[0062]

[Table 3]

[0063]

[Table 4]

As is clear from Table 3, the general formula (II
Samples 23-28 using emulsions G, F prepared in the presence of the compound of I) show good performance. Further, in Nos. 29 to 31 treated with a developer containing a benzotriazole or nitroindazole compound in the developer, γ was remarkably increased, and the image quality of the extracted characters was also good.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location G03C 5/305

Claims (3)

[Claims] 1. A development method in which a light-sensitive material having at least one silver halide emulsion layer on a support is processed with a developing solution after exposure, and at least 90 mol% of silver halide grains in the emulsion layer are contained. It is silver chloride and contains 5 × 10 ⁻⁶ mol or more of rhodium or ruthenium complex per mol of silver and is represented by the following general formulas (I) and (II) in the emulsion layer or other hydrophilic colloid layer. A method for developing a silver halide photographic light-sensitive material, which contains at least one compound selected from the compounds, and the developer contains L-ascorbic acid as a developing agent. [Chemical 1] In the formula, A ₁ , A ₂ , A ₃ and A ₄ represent a non-metal atom group for completing the nitrogen-containing heterocycle, and each may be the same or different. B represents a divalent linking group. m represents 0 or 1. R ₁ , R ₂ , R ₃
And R ₄ each represent an alkyl group. X represents a counter ion required to balance the charge. n represents the number of counterions required to balance the charge, and is 0 in the case of an intramolecular salt.
Is. 2. Development of a silver halide photographic light-sensitive material according to claim 1), wherein the silver halide in the emulsion layer is grain-formed in the presence of the compound of the following general formula (III). Method. General formula (III): In the formula, R ¹ , R ² , R ³ and R ⁴ may be the same or different and each is a hydrogen atom, an alkyl group, an aryl group, an amino group, a hydroxy group, an alkoxy group, an alkylthio group, a carbamoyl group or a halogen atom. Represents a cyano group, a carboxy group, an alkoxycarbonyl group or a heterocyclic residue, and R ¹ and R ² or R ² and R ³ may together form a 5-membered or 6-membered ring. However, at least ^one of R ¹ and R ³ represents a hydroxy group. 3. The method for developing a silver halide photographic light-sensitive material according to claim 1, wherein the developing solution contains a benzotriazole compound or a nitroindazole compound.