JP2001242582A - Silver halide photographic sensitive material and method for processing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having enhanced contrast/image quality, sensitivity and high density and to provide a rapid processing method by which stable performance is ensured even if the amount of a developing solution to be replenished is reduced. SOLUTION: In the silver halide photographic sensitive material with at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloidal layer on the base, the emulsion layer contains silver halide grains having a silver to gelatin ratio of >1 and containing a transition metal complex comprising a nitrosyl or thionitrosyl ligand and a transition metal selected from the groups V-VIII elements of the Periodic Table. The sensitive material does not contain a hydrazine derivative and contains a development accelerator in the emulsion layer and/or the hydrophilic colloidal layer. In the processing method, the sensitive material is processed while replenishing a small amount of a developing solution and a small amount of a fixing solution.

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 more particularly to an ultra-high contrast silver halide photographic light-sensitive material used for photolithography and a method of developing the same.

[0002]

2. Description of the Related Art In the field of plastic arts, images exhibiting ultra-high contrast (especially γ of 10 or more) exhibit photographic properties in order to improve reproduction of continuous tone images or line images by halftone images. A forming system is required. There has been a demand for an image forming system that can be developed with a processing solution having good storage stability and obtain ultra-high contrast photographic characteristics. One of them is U.S. Pat. Nos. 4,166,742 and 4,16.
No. 8,977, No. 4,221,857, No. 4,2
No. 24,401, No. 4,243,739, No. 4,
Nos. 272,606 and 4,311,781, a surface latent image type silver halide photographic material to which a specific acylhydrazine compound is added, and a sulfurous acid preservative of 0.15 mol / l or more. PH included 11.0-12.
A system for forming a negative image having a super-high contrast of more than 10 by processing with a developing solution of No. 3 was proposed. This new image forming system can use only silver chlorobromide having a high silver chloride content in the conventional ultra-high contrast image forming system, but can also use silver iodobromide or silver iodochlorobromide. There are features. Another characteristic is that the conventional squirrel developer can contain only a trace amount of a sulfite preservative, but can contain a large amount of a sulfite preservative, so that it has relatively good storage stability. However, when the replenishment amount during the development process is reduced, the stability of the processing solution is insufficient, and a photosensitive material using a nucleating agent such as a hydrazine compound cannot maintain stable performance. Was.

A photographic material containing no nucleating agent has a good processing latitude and a good processing stability, and is easy to use. In a flat bed type image setter in which the distance changes, the blackening density is greatly reduced. Therefore, these materials are not suitable for users seeking the highest dot quality and blackening density.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having improved contrast / image quality, high sensitivity and high density. Another object of the present invention is to provide a silver halide photographic light-sensitive material having quick and stable performance even when the replenishment amount of development is reduced.

[0005]

SUMMARY OF THE INVENTION The above object of the present invention is as follows.
This has been achieved by the following means. (1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support, the emulsion layer has a silver: gelatin ratio higher than 1. And a silver halide grain containing a transition metal complex selected from the elements of Groups V to VIII of the periodic table having a nitrosyl or thionitrosyl ligand, and the photosensitive material contains a hydrazine derivative. A silver halide photographic light-sensitive material characterized by containing a development accelerator in the emulsion layer and / or the hydrophilic colloid layer. (2) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support, the emulsion layer has a silver: gelatin ratio higher than 1. And a silver halide grain containing a transition metal complex selected from Group V to VIII elements of the periodic table having a cyan ligand, the photosensitive material does not contain a hydrazine derivative, and A silver halide photographic material comprising a development accelerator in the emulsion layer and / or the hydrophilic colloid layer. (3) The silver halide photographic material as described in (1) above, wherein the silver halide grains contain a transition metal selected from Group V to VIII elements of the periodic table having a cyanide ligand. (4) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support, the emulsion layer has a silver: gelatin ratio higher than 1. And a selenium compound and / or
Alternatively, the photosensitive material contains silver halide grains chemically sensitized with a tellurium compound, does not contain a hydrazine derivative, and contains a development accelerator in the emulsion layer and / or the hydrophilic colloid layer. A silver halide photographic light-sensitive material, characterized in that: (5) The silver halide photographic material as described in any one of the above items (1) to (3), wherein the silver halide grains are chemically sensitized with a selenium compound and / or a tellurium compound. (6) The silver halide photographic material as described in any one of the above items (1) to (5), wherein the development accelerator is an amine compound. (7) In the method of developing the silver halide photographic material according to any one of the above items (1) to (6) after exposure, the developing time is within 20 seconds, and the replenishing amount of the developing solution is used. Is 200 ml / m ² or less, and the replenishing amount of the fixing solution is 300 ml / m ² or less.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The silver halide emulsion according to the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide and silver iodobromide. Silver content 3
0 mol% or more is preferable, and 50 mol% or more is more preferable. Further, the content of silver iodide is preferably 5 mol% or less,
It is more preferably at most 2 mol%.

The shape of the silver halide grains may be any of cubic, tetradecahedral, octahedral, irregular, and tabular, but is preferably cubic or tabular.

[0008] The photographic emulsion used in the present invention is P. Glafki.
by des Chimie et Physique Photo-graphique (Paul Mon
tel, 1967), Photographic by GFDufin
Emulsion Chemistry (The Focal Press, 1966
Year), Making and Coating Photo by VLZelikman et al
graphic Emulsion (The Focal Press, 1964)
It can be prepared using the method described in, for example.

That is, any of an acidic method and a neutral method may be used, and the method of reacting a soluble silver salt with a soluble halide salt may be any of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Is also good. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. Further, it is preferable to form grains using a so-called silver halide solvent such as ammonia, thioether, or tetra-substituted thiourea. More preferred are tetra-substituted thiourea compounds.
No. 8, No. 55-77737. Preferred thiourea compounds are tetramethylthiourea and 1,3-dimethyl-2-imidazolidinthione. Particle size to the type and purpose of the addition amount of the compound used in the silver halide solvent varies depending halogen composition, ^10-5 to ^-2 mol per mol of silver halide is preferred. Also,
The particles may be formed in the presence of a nitrogen-containing heterocyclic compound that forms a complex with silver, and it is preferable to use compounds (N-1) to (N-59) described in JP-A-11-344788. The addition amount of these compounds varies over a considerable range under various conditions such as pH, temperature, and the size of silver halide grains.
0 ^{- 6-10 - 2} mol is preferred. The addition of these compounds can be appropriately performed at each stage before, during, or after the formation of the particles, and is particularly preferably performed at the time of the formation of the particles.

In the controlled double jet method and the grain formation method using a silver halide solvent, it is easy to prepare a silver halide emulsion having a regular crystal form and a narrow grain size distribution, and is used in the present invention. It is a useful tool for making silver halide emulsions. Also, in order to make the particle size uniform, British Patent No. 1,535,016,
As described in JP-B-48-36890 and JP-B-52-16364, a method of changing the addition rate of silver nitrate or alkali halide in accordance with the grain growth rate, and a method disclosed in British Patent No. 4,242,445, 55-158124
It is preferable to use the method of changing the concentration of the aqueous solution as described in the above item to grow the solution quickly within a range not exceeding the critical saturation. The emulsion of the present invention is preferably a monodispersed emulsion, and {(standard deviation of particle size) / (average particle size)} × 1.
The coefficient of variation represented by 00 is 20% or less, more preferably 15% or less. The average grain size of the silver halide emulsion grains is preferably 0.5 μm or less, more preferably 0.1 μm or less.
08 μm to 0.4 μm. Here, for the sake of convenience, the grain size of the silver halide grains is represented by a ridge length in the case of a cubic grain,
The other particles (octahedron, cubic tetrahedron, plate, etc.) are calculated by the projected area circle equivalent diameter.

[0011] The silver halide emulsion according to the present invention comprises
It is preferable to contain silver halide grains containing a transition metal belonging to Group VIII. In order to achieve high contrast and low fog, it is preferable to contain a rhodium compound, an iridium compound, a ruthenium compound, a rhenium compound, a chromium compound and the like. Preferred as these transition metals are metal coordination complexes, and hexacoordinate complexes represented by the following general formula. [M (NY) _m L _6-m ] ⁿ (wherein, M is a transition metal selected from the elements of Groups V to VIII of the Periodic Table of the Elements, L is a bridging ligand, and Y is Oxygen or sulfur, m = 0, 1, 2, n = 0,
-, 2-, 3-. ) Nitrosyl and thionitrosyl bridging ligands are preferred,
Other preferred specific examples of L include halide ligands (fluoride, chloride, bromide and iodide), cyanide ligand, cyanate ligand, thiocyanate ligand, selenocyanate ligand, Terrocyanate ligands, acid ligands and aquo ligands. If an aquo ligand is present, it preferably occupies one or two of the ligands. Particularly preferred specific examples of M are rhodium, ruthenium, rhenium, osmium and iridium.

The following are specific examples of the transition metal coordination complex. 1. [Ru (NO) Cl ₅ ] ^2-2 . [Ru (NO) ₂ Cl _4] ^- 3. _{[Ru (NO) (H 2 O} ) Cl 4 ] ² 4. [Rh (NO) Cl ₅ ] ^2-5 . [Re (NO) Cl ₅ ] ^2-6 . [Re (NO) CN ₅ ] ^2-7 . [Re (NO) ClCN ₄ ^2- 8. [Rh (NO) ₂ Cl _4] ^- 9. [Rh (NO) (H ₂ O) Cl ₄ ]-10. [Ru (NO) CN ₅ ] ^2-11 . (Ru (NO) Br ₅ ) ^2- 12. (Rh (NS) Cl ₅ ) ^2- 13. (Os (NO) Cl ₅ ) ^2- 14. (Cr (NO) Cl ₅ ) ^3- 15. (NO) Cl _5] ^- 16. _{[Os (NS) Cl 4 (TeCN} ) ] ^2- 17. [Ru (NS) I ₅ ^2- 18. _{[Re (NS) Cl 4 (SeCN} ) ] ^2- 19 [Os (NS) Cl (SeCN) ₄ ] ^2- 20. [Ir (NO) Cl ₅ ] ^2- These compounds are used by dissolving in water or a suitable solvent, but stabilize the compound solution. For this purpose, a method commonly used for forming a hydrogen halide solution, for example, an aqueous solution of hydrogen halide (eg, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.) or an alkali halide (eg, KCl, NaCl, KBr, NaBr)
Etc.) can be used. It is also possible to add and dissolve another silver halide grain doped with these compounds in advance. The addition amount of these compounds is 1 × 10 ⁻⁸ to 1 × 10 ⁻² mol, preferably 5 × 10 ⁻⁸ mol per mol of silver of the silver halide emulsion.
22 × 10 ^-4 mol. The above heavy metals may be used in combination, or may be used in combination with a heavy metal containing no nitrosyl or thionitrosyl ligand. The distribution of the heavy metal in the silver halide grains is not particularly limited, and may be a uniform distribution, a core-shell type having a different distribution between the surface and the inside, or a continuous distribution. These compounds can be appropriately added at the time of production of silver halide emulsion grains and at each stage before coating the emulsion, but it is particularly preferable to add them at the time of emulsion formation and to incorporate them into silver halide grains. .

In the present invention, those containing at least four cyanide ligands can be used in combination. In a preferred embodiment, these compounds can be represented by the formula: _{[M (CN) 6 - y L} y ] Here ^n, M is a rhenium, ruthenium, osmium, iron, etc., L is a bridging ligand, y is an integer 0, 1 or 2, and n Is 2-, 3- or 4-.

Specific examples include the following. [Re (CN) ₆ ] ^4- [Ru (CN) ₆ ] ^4- [Os (CN) ₆ ] ^4- [ReF (CN) ₆ ] ^4- [RuF (CN) 5] ^4- [OsF (CN) _5] ^4- [ReCl (CN) _5] ^4- [RuCl (CN) _5] ^4- [OsCl (CN) _5] ^4- [ReBr (CN) _5] ^4- [RuBr (CN) _5] ^4- - [OsBr (CN) _5] ^4- [ReI (CN) _5] ^4- [RuI (CN) _5] ^4- [OSI (CN) _5] ^4- [ReF ₂ (CN) _4] ^4- [RuF ₂ ( CN) _5] ^4- [OSF ₂ (CN) _5] ^4- [ReCl ₂ (CN) _4] ^4- [RuCl ₂ (CN) _4] ^4- [OsCl ₂ (CN) _4] ^4- [RuBr ₂ ( CN) _4] ^4- [OSBR ₂ (CN) _4] ^4- [ReBr ₂ (CN) _4] ^4- [RuI ₂ (CN) _4] 4- [OSI ₂ (CN) _4] ^4- [Ru (CN ) ₅ (OCN)] ^4- [Os (CN) ₅ (OCN)] ^4- [Ru (CN) ₅ (SCN)] ^4- [Os (CN) ₅ (SCN)] ^4- _{[Ru (CN) 5 (N 3} ) ] ^4- [Os (CN) ₅ (N _3)] ^4- _{[Ru (CN) 5 (H 2} O) ] ^3- _{[Os (CN) 5 (H 2} O) ] ^3- [Fe (CN) _6] ^4- [Fe (CN) ₆ ] ^3-

The above iron, rhenium, ruthenium and osmium compounds are preferably added during the formation of silver halide grains. The addition position may be uniformly distributed in the particles, or may be localized in the initial, middle and late stages of the particle formation.
It is preferred to add after 0%, more preferably 80%, has been formed. The addition amount is 10 ^-3 mol or less, preferably 10 ^-6 to 10 ^-4 mol, per 1 mol of silver. In the present invention, other metals contained in Group VIII, that is, cobalt, nickel, palladium, platinum and the like may be used in combination.

The silver halide emulsion of the present invention is preferably chemically sensitized. As the method of chemical sensitization, known methods such as a sulfur sensitization method, a selenium sensitization method, a tellurium sensitization method, and a noble metal sensitization method can be used, and these are used alone or in combination. In particular, it is preferable to use selenium sensitization or tellurium sensitization. When used in combination, for example, sulfur sensitization and gold sensitization, sulfur sensitization and selenium sensitization and gold sensitization, sulfur sensitization and tellurium sensitization and gold sensitization, etc. Is preferred.

The sulfur sensitization used in the present invention is generally carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Known compounds can be used as the sulfur sensitizer, for example,
In addition to sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used. Other U.S. Pat. Nos. 1,574,944 and 2,410,689
No. 2,278,947 and No. 2,728,66
No. 8, No. 3,501, 313, No. 3,656, 9
No. 55, German Patent 1,422,869, JP-B-56-24937, JP-A-55-45016 and the like can also be used. Preferred sulfur compounds are thiosulfates and thiourea compounds. The amount of the sulfur sensitizer to be added depends on the pH during chemical ripening,
Temperature, varies under various conditions such as the size of the silver halide grains, per mol of silver halide 10 ^-7 to 10 ^-2
Mol, more preferably 10 ^-5 to 10 ^-3 mol.

The selenium sensitizer used in the present invention includes:
Known selenium compounds can be used. That is,
Usually, the method is carried out by adding an unstable and / or non-unstable selenium compound and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time. Examples of unstable selenium compounds include JP-B-44-15748 and JP-B-43-134.
No. 89, JP-A-4-25832, JP-A-4-109240
And compounds described in JP-A-4-324855 and the like. Specific labile selenium sensitizers include:
Isoselenocyanates (eg, aliphatic isoselenocyanates such as allyl isoselenocyanate), selenoureas, selenoketones, selenoamides, selenocarboxylic acids (eg, 2-selenopropiones, 2-selenobutyric acid), selenoesters , Diacyl selenides (eg, bis (3-chloro-2,6-dimethoxybenzoyl) selenide), selenophosphates, phosphine selenides, colloidal metal selenium, and the like. Although the preferred types of unstable selenium compounds have been described above, they are not intended to be limiting. Those skilled in the art will note that an unstable selenium compound as a sensitizer for a photographic emulsion is not very important as long as selenium is unstable, and the structure of the selenium sensitizer molecule is not important. It is generally understood that the moieties carry selenium and have no role other than to make them present in the emulsion in an unstable manner. In the present invention, an unstable selenium compound having such a broad concept is advantageously used. Non-labile selenium compounds used in the present invention include JP-B-46-4553,
JP-B-52-34492 and JP-B-52-3449
The compound described in No. 1 is used. Non-labile selenium compounds include, for example, selenous acid, potassium selenocyanide, selenazoles, quaternary salts of selenazoles, diaryl selenides, diaryl diselenides, dialkyl selenides, dialkyl diselenides, 2-selenazolidinediones, 2-selenooxazolidinethione and derivatives thereof. It is particularly preferable to use the compounds represented by formulas (VIII) and (IX) in JP-A-4-324855. Further, a low-decomposition active selenium compound can also be preferably used. The low-decomposition-active selenium compound includes: AgNO ₃ 10 mmol, selenium compound 0.5 mmol, 2- (N-morpholino) ethanesulfonic acid buffer 40 mmol, water / 1,4-dioxane volume ratio 1
/ 1 is a selenium compound having a half-life of 6 hours or more when reacted with a mixed solution (pH = 6.3) at 40 ° C. The selenium compound can be analyzed by HPLC or the like to determine the half-life. The low-decomposition active selenium compound is disclosed in JP-A-9-16684.
It is preferable to use the compounds of SE-1 to SE-8.

The tellurium sensitizer used in the present invention is a compound which forms silver telluride which is presumed to be a sensitizing nucleus on the surface or inside of silver halide grains. The formation rate of silver telluride in a silver halide emulsion is described in
It can be tested by the method described in US Pat.
Specifically, U.S. Pat. Nos. 1,623,499, 3,320,069, 3,772,031, British Patent 235,211 and 1,121,496
No. 1,295,462, No. 1,396,69
No. 6, Canadian Patent No. 800,958, JP-A No. 4-20
No. 4640, No. 4-271341, No. 4-33304
3, No. 5-303157, Journal of Chemical Society Chemical Communication (J. Chem. Soc. Chem. Commun.) 635 (1980), ibid
1102 (1979), ibid 645 (1979),
Journal of Chemical Society Perkin Transaction (J.Chem.Soc.Perkin.Trans.)
1,191 (1980), edited by S. Patai, The Chemistry of O, The Chemistry of Organic Selenium and Tellurium Company
rganic Serenium and Tellunium Compounds), Vol1 (1
986) and the compounds described in Vol. 2 (1987) can be used. Particularly, compounds represented by formulas (II), (III) and (IV) in JP-A-5-313284 are preferred.

The amount of the selenium and tellurium sensitizers used in the present invention varies depending on the silver halide grains to be used, the conditions of chemical ripening, etc., but is generally 10 ^-8 to 10 ^-2 mol per mol of silver halide. Preferably about 10 ^-7 to 10 ^-3 mol is used. The conditions of the chemical sensitization in the present invention are not particularly limited, but the pH is 5 to 8, the pAg is 6 to 11, preferably 7 to 10, and the temperature is 40 to 95 ° C, preferably 45 to 45 ° C. 85 ° C. Examples of the noble metal sensitizer used in the present invention include gold, platinum, palladium, and iridium, and gold sensitization is particularly preferable. As the gold sensitizer, the oxidation number of gold may be +1 or +3, and gold compounds generally used as gold sensitizers can be used. Representative examples include chloroaurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodooleate, tetracyano auric acid, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide and the like. About 10 ^-7 to 10 ^-2 mol can be used per mol of silver halide.
In the silver halide emulsion used in the present invention, a cadmium salt, a sulfite, a lead salt, a thallium salt, and the like may coexist in the process of forming silver halide grains or physical ripening. In the present invention, reduction sensitization can be used. Stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used as the reduction sensitizer. The silver halide emulsion of the present invention can be prepared by using a European Patent (E)
P) -293,917, a thiosulfonic acid compound may be added. The silver halide emulsion in the light-sensitive material used in the present invention may be only one type in the same layer, or two or more types, for example, those having different average grain sizes, those having different halogen compositions, the types and distribution of metal complexes. , Different contents, different crystal habits, different shapes, different types of chemical sensitizers, different amounts, different sensitizing conditions, different types of spectral sensitizing dyes, different amounts, different sensitizing conditions, etc. May be used in combination, and a multilayer structure of those layers may be used.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized to a relatively long wavelength blue light, green light, red light or infrared light by a sensitizing dye depending on the use of the light-sensitive material. Good. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo-holerocyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Useful sensitizing dyes for use in the present invention include, for example, RESEARCH DISCLOSURE
Item 17643 IV-A (p.2 December 1978
3), Item 18341X (p. 43, August 1979)
It is described in the literature described or cited in 7).
In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of the light source of various scanners, imagesetters and plate making cameras can be advantageously selected. For example, A) for an argon laser light source, compounds of (I) -1 to (I) -8 described in JP-A-60-162247;
No. 653, compounds of I-1 to I-28;
Compounds of I-1 to I-13 described in No.-330434,
Example described in U.S. Pat. No. 2,161,331.
Compounds from 1 to Example 14, West German Patent 936
Nos. 1 to 7 described in JP-A-071; B) For helium-neon laser and red laser diode light source, I-1 to I-3 described in JP-A-54-18726.
Compound No. 8, compounds I-1 to I-35 described in JP-A-6-75322, compounds I-1 to I-34 described in JP-A-7-287338, Patent Publication No. 2822
No. 138, compounds of 2-1 to 2-14, 3- (1) to 3- (14), 4-1 to 4-6, C) LED
For the light source, dyes 1 to 20 described in JP-B-55-39818 and I- described in JP-A-62-284343.
Compounds from 1 to I-37 and JP-A-7-287338
Nos. 1-1 to 1-34 described in JP-A No.
2-1 to 2-14, 3- (1) described in No. 22138
To 3- (14), 4-1 to 4-6, and D) for a semiconductor laser light source.
Compounds of I-1 to I-12 described in
Compounds I-1 to I-22 described in JP-A-0841, compounds I-1 to I-29 described in JP-A-4-335342, and compounds I-1 to I-29 described in JP-A-59-192242.
-18, a compound of (1) to (19) represented by the general formula [I] described in JP-A-55-45015 for a tungsten and xenon light source of a plate making camera; 4-A to 4-4-47
Compound of S, compound of 5-A to 5-Q, 6-A to 6
-T compound and JP-A-9-160185
Compounds I-1 to I-97 are advantageously selected,
The present invention is not limited to these.

These sensitizing dyes may be used alone or in combination. The combination of sensitizing dyes is often used particularly for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosur.
e) Vol. 176, Volume 17643 (December 1978) No. 23
Section IV on page IV, or the aforementioned JP-B-49-25500,
43-4933, JP-A-59-19032, and 59-19032.
192242.

Two or more sensitizing dyes may be used in combination in the present invention. The sensitizing dyes may be added to the silver halide emulsion by dispersing them directly in the emulsion or by using water, methanol, ethanol, propanol, acetone, methylcellosolve, 2,2,3,3 Solvent alone such as tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol, 3-methoxy-1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide Alternatively, it may be dissolved in a mixed solvent and added to the emulsion. Further, as disclosed in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, and the solution is dispersed in water or a hydrophilic colloid. A method of adding to an emulsion, Japanese Patent Publication No. 44-23389,
As disclosed in JP-A-44-27555 and JP-A-57-22091, a dye is dissolved in an acid and the solution is added to the emulsion, or the solution is added to the emulsion as an aqueous solution in the presence of an acid or base. US Patent No. 3,822,135
No. 4,006,025, etc., a method of adding an aqueous solution or a colloidal dispersion in the presence of a surfactant to an emulsion,
JP-A-51-723, and JP-A-58-105141, a method in which a dye is directly dispersed in a hydrophilic colloid and the dispersion is added to an emulsion.
As disclosed in Japanese Patent No. 74624, a method in which a dye is dissolved using a compound that causes a red shift, and the solution is added to an emulsion can also be used. Also, ultrasonic waves can be used for the solution.

The sensitizing dye used in the present invention may be added to the silver halide emulsion of the present invention at any stage of the emulsion preparation which has been found to be useful. For example, U.S. Patent Nos. 2,735,766, 3,628,960, 4,183,756, 4,225,666, and JP-A-58-184142.
As disclosed in the specifications of JP-A No. 60-196,749, the start of chemical ripening during the step of forming silver halide grains and / or before desalting, during and / or after desalting. Previous period, Japanese Patent Application Laid-Open No. 58-113920
As disclosed in the specification of JP-A No. 195/1992, it may be added at any time during the process immediately before or during chemical ripening, at any time after chemical ripening and before coating until the emulsion is coated. . No. 4,225,666.
As disclosed in the specification of JP-A No. 58-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the particle forming step, during the chemical ripening step, or when the chemical ripening is completed. May be added separately, such as before or after chemical ripening or during the process and after completion, or may be added by changing the type of compound and compound combination to be added and divided. Good.

The amount of the sensitizing dye of the present invention varies depending on the shape and size of silver halide grains, the halogen composition, the method and degree of chemical sensitization, the type of antifoggant, and the like. And 4 × 10 ^-6 to 8 × 10 ^-3 mol. For example, when the size of the silver halide grains is 0.2 to 1.3 μm, the addition amount is preferably 2 × 10 ^{−7 to} 3.5 × 10 ⁻⁶ mol per 1 m ² of the surface area of the silver halide grains. An addition amount of 0.5 × 10 ^{−7 to} 2.0 × 10 ⁻⁶ mol is more preferable.

The silver halide photographic light-sensitive material of the present invention does not contain a hydrazine derivative. That is, it means that the silver halide photographic light-sensitive material of the present invention does not contain a nucleating agent.

In the present invention, it is preferable to incorporate a development accelerator into the light-sensitive material. Examples of the development accelerator used in the present invention include an amine derivative, an onium salt, a disulfide derivative, and a hydroxymethyl derivative. In the present invention, an amine derivative (also referred to as an “amine compound”) is preferably used. Hereinafter, examples of the amine compound acting as a development accelerator are listed. Examples of the amine compound include the compounds described in paragraph 0093 described in JP-A-7-77783, specifically, the compounds described in paragraph 0095.
Compounds A-1 to A-23 and A described in
-68 to 73, Chemical formula 21, Chemical formula 22 and Chemical formula 23 described in JP-A-7-84331, Formula [Na] and exemplified compounds Na-1 to Na described in JP-A-7-104426.
-22, general formula (1), general formula (2), general formula (3), general formula (4) described in JP-A-8-272023,
Compounds represented by the general formulas (5), (6) and (7), specifically, 1-1 to 1 described in the same specification.
-19, 2-1 to 2-22, 3-1 to 2-1
Compound of 3-36, compound of 4-1 to 4-5, 5-1 to
Compounds of 5-41, compounds of 6-1 to 6-58, compounds of 7-1 to 7-38, and H-1 to H- of paragraphs 0220 to 0254 described in JP-A-9-297377.
Fourteen compounds can be listed. In the present invention, other development accelerators such as an onium salt, a disulfide derivative or a hydroxymethyl derivative can be used in addition to the amine compound. As these development accelerators,
Compounds described in paragraph 0093 of JP-A-7-77783, specifically, compounds A-24) to A-67) described in paragraphs 0095 to 0105); and a compound represented by the general formula [Nb] described in JP-A-7-104426 And Nb-1 to Nb-1 described in paragraphs 0089 to 0081.
Compound 2; paragraph 0220 of JP-A-9-297377
Development accelerators E-1 to E-42, and F
-1 to F-27. These development accelerators can be used alone or in combination with an amine compound.

Specific examples of the development accelerator used in the present invention are shown below. However, the present invention is not limited to the following compounds.

[0029]

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[0030]

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The development accelerator of the present invention may be any suitable water-miscible organic solvent such as alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide, methylcell It can be used by dissolving it in Solve or the like. Also, by an already well-known emulsification dispersion method, dissolution is performed using an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone, and mechanically emulsified and dispersed. An object can be prepared and used. Alternatively, the powder of the development accelerator can be dispersed in water by a ball mill, a colloid mill, or ultrasonic waves and used by a method known as a solid dispersion method.

The development accelerator of the present invention may be added to any layer of the silver halide emulsion layer on the side of the silver halide emulsion layer with respect to the support or any other hydrophilic colloid layer. It is preferably added to the silver halide emulsion layer or the hydrophilic colloid layer adjacent thereto. The addition amount of the development accelerator of the present invention is 1 × 10 ⁻⁶ to 2 × per mol of silver halide.
10 ⁻² mol is preferred, 1 × 10 ⁻⁵ to 2 × 10 ⁻² mol is more preferred, and 2 × 10 ⁻⁵ to 1 × 10 ⁻² mol is most preferred. Further, two or more development accelerators can be used in combination.

The support used in the present invention includes, for example, baryta paper, polyethylene coated paper, polypropylene synthetic paper,
Glass plate, cellulose acetate, cellulose nitrate, for example, polyester film such as polyethylene terephthalate, JP-A-7-234478, and US
A support comprising a styrenic polymer having a syndiotactic structure described in Japanese Patent No.
No. 8, US 4,645,731, US 4,933,2
No. 67, SU4, 954, and 430, a support obtained by coating a polyester film with a vinylidene chloride copolymer. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

As a binder for the silver halide emulsion layer and other hydrophilic colloid layers of the present invention, gelatin is preferably used, but polymers described in paragraph No. 0025 of JP-A-10-268644 can also be used. The coating amount of the binder is such that the amount of the binder in the entire hydrophilic colloid layer on the side having the silver halide emulsion layer is 3 g / m ² or less (preferably 1.0 to 3.0 g / m ² ), and the silver halide emulsion The total amount of binder in the total hydrophilic colloid layer on the side having the layer and the total hydrophilic colloid layer on the opposite side is 7.0 g.
/ M ² or less, and preferably 2.0 to 7.0 g / m ² . The preferred range of silver: gelatin in the emulsion layer is 1
It is larger and smaller than 5, more preferably 1.5 or more and 3.5 or less, most preferably 2.5 or more and 3.5 or less.

In the present invention, in order to control the surface roughness of the outermost layer surface of the silver halide light-sensitive material, fine particles of inorganic and / or organic polymer (hereinafter referred to as a matting agent) are contained in a hydrophilic colloid layer. ) Is used. The surface roughness of the outermost layer surface of the light-sensitive material having the silver halide emulsion layer and the outermost layer surface opposite to the emulsion layer should be controlled by variously changing the average particle size and the amount of the matting agent. Can be. The layer containing the matting agent may be any layer of the light-sensitive material constituting layer, but the side having the silver halide emulsion layer is preferably contained in a layer farther from the support to prevent pinholes, particularly The outermost layer is preferred.

The matting agent used in the present invention may be any solid particles which do not adversely affect the photographic properties. Specifically, Japanese Patent Application Laid-Open No. 10-26846
No. 4, paragraphs 0009 to 0013 are mentioned. The average particle size of the preferred matting agent in the present invention,
It is 20 μm or less, particularly in the range of 1 to 10 μm.
In the present invention, the preferable addition amount of the matting agent is 5 to 40.
0 mg / m ^2, in particular from 10 to 200 mg / m ^2. The surface roughness of the light-sensitive material of the present invention is such that at least one of the surface having the emulsion layer and the outermost layer surface opposite thereto, preferably both have a Bekk smoothness of 4000 seconds or less,
More preferably, it is 10 seconds to 4000 seconds. The Beck smoothness is determined by Japanese Industrial Standards (JIS) P8119 and TAP
It can be easily obtained by the PI standard method T479.

In the present invention, the matting agent sinks during coating and drying of the silver halide light-sensitive material, or a pressure increase / decrease sensation during handling during automatic conveyance / exposure / development.
Colloidal inorganic particles can be used in a silver halide emulsion layer, an intermediate layer, a protective layer, a back layer, a back protective layer, etc. for the purpose of improving curl balance, scratch resistance, adhesion resistance and the like. Preferred colloidal inorganic particles include JP-A-10-268644, paragraphs 0008 and 0014.
The described elongated silica particles, colloidal silica, and pearl-like (pearl necklace-shaped) colloidal silica manufactured by Nissan Chemical Industries, Ltd .: “Snowtex-PS”.

The amount of the colloidal inorganic particles used in the present invention is 0.01 to 2.0, preferably 0.1 to 0.1 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added. -0.6.

In the present invention, a polyhydroxybenzene compound described in JP-A-3-39948, page 10, lower right, line 11 to page 12, lower left, line 5 is used for the purpose of improving the sense of pressure increase and decrease. Is preferred. In particular,
Compounds (III) -1 to 25 described in the publication are mentioned.

In the present invention, a polymer latex can be used for the purpose of improving brittleness, dimensional stability, pressure increase / decrease sensation and the like. As the polymer latex, U.S. Pat. Nos. 2,763,652, 2,852,382, JP-A-64-538, JP-A-62-115152, JP-A-5-66512, JP-A-5-80449, Tokiko Sho 60-
No. 15935, No. 6-64058 and No. 5-450
Polymer latexes composed of various monomers such as alkyl acrylates and alkyl methacrylates described in JP-B No. 14 and No. Sho.
7, JP-A-50-73625, JP-A-7-1521
12, a polymer latex copolymerized with a monomer having an active methylene group and a monomer such as an alkyl acrylate described in JP-A-8-137060. Particularly preferably, JP-A-8-248548,
It is a polymer latex having a core / shell structure having a repeating unit composed of an ethylenically unsaturated monomer containing an active methylene group in a shell portion described in JP-A-8-208767 and JP-A-8-220669. These core / shell polymer latexes having an active methylene group in the shell part do not reduce the wet film strength of the photographic light-sensitive material, but are brittle, have dimensional stability, and are difficult to adhere to each other. And the latex itself has improved shear stability. The amount of the polymer latex used is 0.01 to 4.0, preferably 0.1 to 2.0 in terms of dry weight ratio to the binder (eg, gelatin) of the layer to be added.

In the present invention, in order to lower the pH of the coating film for the purpose of improving the storage stability of the silver halide light-sensitive material and improving the sensitivity to pressure fluctuation, the same method as described in JP-A-7-104413, p. It is preferable to use the acidic polymer latex described on line 30 on the right side of the page. Specifically, compounds II-1) to II-9) described on page 15 of the publication. JP-A-2-103
No. 536, page 18, lower right, line 6 to page 19, upper left, first line, compounds having an acid group. The pH of the coating film on the side having the silver halide emulsion layer is preferably from 6 to 4.

In the present invention, at least one of the constituent layers of the silver halide light-sensitive material has a surface resistivity of 25 ° C. and 25%.
It can have a conductive layer of 10 ¹² Ω or less under an atmosphere of RH. Examples of the conductive substance used in the present invention include those described in JP-A-2-18542, page 2, lower left, line 13 to page 3, upper right, line 7. In particular,
The metal oxides described on page 2, lower right, line 2 to the lower right, line 10 of the same publication, and compounds P-1 to P-
7. The conductive polymer compound of 7. U.S. Pat. No. 5,575,957, JP-A-10-142938, paragraph numbers 0034 to 0043,
JP-A-11-223901, paragraph numbers 0013 to 001
Needle-like metal oxides described in No. 9 can be used.

In the present invention, in addition to the above-mentioned conductive material, JP-A-2-18542, page 4, upper right, second line to page 4, lower right, lower third line, JP-A-3-39948, No. 12 A better antistatic property can be obtained by using the fluorine-containing surfactant described in the sixth line from the lower left of the page to the fifth line on the lower right of the page 13 of the publication.

In the present invention, the silver halide emulsion layer or other hydrophilic colloid layer may contain a coating aid, a dispersing / solubilizing agent for additives, an improvement in lubricity, prevention of adhesion and an improvement in photographic properties (for example, development acceleration). Various surfactants can be used for the purpose of, for example, high contrast, sensitization, and storage stability). For example, surfactants described in JP-A-2-12236, page 9, upper right line, line 7 to lower right line, line 3 of the same page. JP-A-2-103
No. 536, page 18, lower left line, line 4 to lower left line, line 7, the PEG surfactant. Specifically, compounds VI-1 to VI-15 described in the publication. JP-A-2-1854
No. 2, page 4, upper right, line 2 to page 4, lower right, lower third line; JP-A-3-39948, page 12, lower left, line 6 to page 13, lower right, line 5 Fluorinated surfactant.

In the present invention, various slip agents can be used for the purpose of improving the transportability of the silver halide light-sensitive material in an automatic transporter, the scratch resistance, the sensitivity to pressure fluctuation, and the like.
For example, JP-A-2-103536, page 19, upper left
From the fifth line to the upper right line on page 19 of the same publication,
A lubricant described in No. 4551, paragraphs 0006 to 0031.

In the present invention, a compound described in JP-A-2-103536, page 19, upper left, line 12 to page 19, upper right, line 15 is contained as a plasticizer for the coating film of the silver halide photosensitive material. be able to.

In the present invention, as a crosslinking agent for the hydrophilic binder, JP-A-2-103536, page 18, upper right line 5 to line 17, upper right line, JP-A-5-297508
The compounds described in paragraphs [0008] to [0011] can be used. The swelling ratio of the hydrophilic colloid layer including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention is 5
The range is preferably from 0 to 200%, more preferably from 70 to 200%.
It is in the range of 180%. The swelling ratio of the hydrophilic colloid layer is
The thickness (d0) of the hydrophilic colloid layer including the emulsion layer and the protective layer in the silver halide photographic light-sensitive material was measured, and the silver halide photographic light-sensitive material was immersed in distilled water at 25 ° C. for 1 minute to swell. (△ d) was measured and the swelling ratio (%) = △
It is obtained by the formula of d ÷ d0 × 100.

In the present invention, drying when drying after coating the silver halide light-sensitive material, environment, processing, heat treatment and the like when wound up in a roll after drying are described in JP-A-10-26.
It is preferably carried out by the method described in paragraph number 0026 to 0032 of No. 8464.

Hereinafter, processing agents such as a developing solution and a fixing solution in the present invention, a processing method, and the like will be described. Needless to say, the present invention is not limited to the following description and specific examples.

In the development processing of the present invention, any of a known method and a known developing machine can be used, and a known processing solution can be used. The developing process of the present invention is preferably a developing process using an automatic developing machine, and it is preferable that a processing solution such as a developing solution is replenished according to the photosensitive material to be processed and / or the elapsed time. The replenishing amount can be automatically replenished by controlling the pH, conductivity and the like of the developer.

The developing solution used in the present invention (hereinafter, both the developing start solution and the developing replenisher are collectively referred to as a developing solution).
The developing agent used for (1) is not particularly limited, but preferably contains dihydroxybenzenes, ascorbic acid derivatives, and hydroquinone monosulfonates, and may be used alone or in combination. In particular, it is preferable to contain a dihydroxybenzene-based developing agent and an auxiliary developing agent showing superadditivity with the dihydroxybenzene-based developing agent. Examples include a combination of an ascorbic acid derivative and a p-aminophenol. As the developing agent used in the present invention, hydroquinone as a dihydroxybenzene developing agent,
Chlorohydroquinone, isopropylhydroquinone,
There are methylhydroquinone and the like, but hydroquinone is particularly preferred. Further, ascorbic acid derivative developing agents include ascorbic acid and isoascorbic acid and salts thereof, and sodium erythorbate is particularly preferred from the viewpoint of material cost.

The developing agent of 1-phenyl-3-pyrazolidone or a derivative thereof used in the present invention includes 1-phenyl-3
-Pyrazolidone, 1-phenyl-4, 4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and the like. N-methyl-p-aminophenol, p-aminophenol, N- (β-hydroxyphenyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine as a p-aminophenol-based developing agent used in the present invention; There are o-methoxy-p- (N, N-dimethylamino) phenol, o-methoxy-p- (N-methylamino) phenol and the like. Among them, N-methyl-p-aminophenol, Aminophenols described in JP-A-297377 and JP-A-9-297378 are preferred.

The dihydroxybenzene-based developing agent is usually 0.1
It is preferably used in an amount of from 05 mol / l to 0.8 mol / l. When a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-aminophenols is used, the former is used in an amount of 0.05 mol / L to 0.6 mol / L, preferably 0.10 mol / L to 0.5 mol / L, It is preferred to use the latter in an amount of 0.06 mol / l or less, preferably 0.03 mol / l to 0.003 mol / l.

The ascorbic acid derivative developing agent is usually 0.1
It is preferably used in an amount of from 01 mol / l to 0.5 mol / l, more preferably from 0.05 mol / l to 0.3 mol / l. When a combination of an ascorbic acid derivative and a 1-phenyl-3-pyrazolidone or a p-aminophenol is used, the ascorbic acid derivative may be used in an amount of 0.01 to 0.5 mol / l, 1-phenyl-3-pyrazolidone or p-aminophenol. -Aminophenols
It is preferably used in an amount of from 0.005 mol / l to 0.2 mol / l.

The developer for processing the light-sensitive material in the present invention can contain commonly used additives (for example, a developing agent, an alkaline agent, a pH buffer, a preservative, a chelating agent, etc.). These specific examples are shown below, but the present invention is not limited thereto. As a buffer used in the developer when developing the photosensitive material in the present invention,
Carbonate, boric acid described in JP-A-62-186259, JP-A-60-186259
Saccharides (eg, saccharose), oximes (eg, acetoxime), phenols (eg, 5-sulfosalicylic acid), and tertiary phosphates (eg, sodium salt, potassium salt) described in 93433, and preferably carbonates , Boric acid is used. The amount of buffer, especially carbonate, used is preferably at least 0.05 mol / l, in particular 0.08
1.01.0 mol / liter.

In the present invention, both the developing solution and the replenishing solution have the property that "the pH rise when 0.1 mol of sodium hydroxide is added to 1 liter of the solution is 0.5 or less". Is preferred. As a method for confirming that the developing solution or replenisher used has this property, the pH of the developing solution or replenisher to be tested is adjusted to 1
The solution was adjusted to 0.5, and then 0.1 mol of sodium hydroxide was added to 1 liter of the solution. The pH value of the solution at this time was measured. It is determined to have properties. In the present invention, it is particularly preferable to use a development start solution and a development replenisher whose rise in pH value in the above test is 0.4 or less.

The preservatives used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, formaldehyde sodium bisulfite and the like. The sulfite is preferably used in an amount of 0.2 mol / l or more, particularly 0.3 mol / l or more. However, if added in an excessive amount, it causes silver stain in the developing solution.
Desirably, it is 1.2 mol / liter. Particularly preferably, it is 0.35 to 0.7 mol / liter. As the preservative of the dihydroxybenzene-based developing agent, a small amount of the ascorbic acid derivative may be used in combination with a sulfite. Above all, it is preferable to use sodium erythorbate from the viewpoint of material cost. The amount added is preferably in the range of 0.03 to 0.12, more preferably in the range of 0.05 to 0.10. When an ascorbic acid derivative is used as a preservative, it is preferable that the developer contains no boron compound.

Other additives to be used include development inhibitors such as sodium bromide and potassium bromide, organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol and dimethylformamide;
Development accelerators such as alkanolamines such as diethanolamine and triethanolamine, imidazole and derivatives thereof, and heterocyclic mercapto compounds (eg, 3- (5-
Sodium mercaptotetrazol-1-yl) benzenesulfonate, 1-phenyl-5-mercaptotetrazole) and the compounds described in JP-A-62-212651 can also be added as physical development unevenness inhibitors. Further, a mercapto-based compound, an indazole-based compound, a benzotriazole-based compound, or a benzimidazole-based compound may be contained as an antifoggant or a black pepper (black pepper) inhibitor. Specifically, 5-nitroindazole, 5-p-nitrobenzoylaminoindazole, 1-methyl-5-nitroindazole, 6-nitroindazole, 3-methyl-5-nitroindazole, 5-nitrobenzimidazole,
Isopropyl-5-nitrobenzimidazole, 5-nitrobenzotriazole, 4-((2-mercapto-1,3,4-
Sodium thiadiazol-2-yl) thio) butanesulfonate, 5-amino-1,3,4-thiadiazole-2-thiol, methylbenzotriazole, 5-methylbenzotriazole, 2-mercaptobenzotriazole and the like can be mentioned. . The amount of these additives is usually 0.01 to 10 mmol, more preferably 0.1 to 2 mmol, per liter of the developer.

Further, various kinds of organic,
Inorganic chelating agents can be used alone or in combination. As the inorganic chelating agent, for example, sodium tetrapolyphosphate, sodium hexametaphosphate and the like can be used. On the other hand, as organic chelating agents, mainly organic carboxylic acids, aminopolycarboxylic acids, organic phosphonic acids, aminophosphonic acids and organic phosphonocarboxylic acids can be used. Examples of the organic carboxylic acid include acrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, acyelinic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, and maleic acid. Acids, itaconic acid, malic acid, citric acid, tartaric acid and the like can be mentioned.

As the aminopolycarboxylic acid, for example,
Iminodiacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, ethylenediaminemonohydroxyethyltriacetic acid, ethylenediaminetetraacetic acid, glycol ether tetraacetic acid,
1,2-diaminopropanetetraacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, 1,3-diamino-2-propanoltetraacetic acid, glycol ether diaminetetraacetic acid, and other JP-A-52-25632, 55-67747, same
57-102624, and JP-B-53-40900.

Examples of the organic phosphonic acid include, for example, US Pat. Nos. 3,214,454 and 3,794,591 and West German Patent Publication 2227369.
And the like, and research disclosure, vol. 181, Item 18170 (19)
May 1979) and the like. Examples of the aminophosphonic acid include aminotris (methylenephosphonic acid), ethylenediaminetetramethylenephosphonic acid, and aminotrimethylenephosphonic acid.
Other examples include compounds described in Research Disclosure 18170, JP-A-57-208554, JP-A-54-61125, JP-A-55-29883, and JP-A-56-97347.

Examples of the organic phosphonocarboxylic acid include, for example, JP-A-52-102726, JP-A-53-42730, JP-A-54-121127 and JP-A-55-102127.
-4024, 55-4025, 55-126241, 55-65955, 55-65
956 and the compounds described in the aforementioned Research Disclosure 18170 and the like.

[0063] These organic and / or inorganic
The agent is not limited to those described above. Also,
Can be used in the form of alkali metal salt or ammonium salt
No. The amount of these chelating agents added is 1 liter of developer.
Preferably 1 × 10 per title ^-Four~ 1 × 10^-1Mole, more
Preferably 1 × 10^-3~ 1 × 10^-2Is a mole.

Further, as a silver stain inhibitor in the developer,
For example, JP-A-56-24347, JP-B-56-46585, JP-B-62
849, JP-A-4-362942, JP-A-8-6215, and triazines having at least one mercapto group (for example, Japanese Patent Publication No. 6-23830, JP-A-3-282457, JP-A-7-175178).
And the pyrimidines (eg, 2-mercaptopyrimidine, 2,6-dimercaptopyrimidine, 2,4-
Dimercaptopyrimidine, 5,6-diamino-2,4-dimercaptopyrimidine, 2,4,6-trimercaptopyrimidine, compounds described in JP-A-9-274289, and the like pyridines (for example, 2-mercaptopyridine, 2 , 6-dimercaptopyridine, 3,5-dimercaptopyridine, 2,4,6-trimercaptopyridine, the compounds described in JP-A-7-248587, and the like pyrazines (eg, 2-mercaptopyrazine, 2,6- Dimercaptopyrazine, 2,3-dimercaptopyrazine, 2,3,5-trimercaptopyrazine and the like (e.g., 3-mercaptopyridazine, 3,4-dimercaptopyridazine, 3,5-dimercaptopyridazine, 3 , 4,6-trimercaptopyridazine, etc.)
Compounds described in 7-175177, polyoxyalkyl phosphonates described in US Pat. No. 5,457,011, and the like can be used. These silver stain inhibitors can be used alone or in combination of two or more.
It is preferably from 05 to 10 mmol, more preferably from 0.1 to 5 mmol. Further, compounds described in JP-A-61-267759 can be used as a dissolution aid. Further, if necessary, a color tone agent, a surfactant, an antifoaming agent, a hardening agent and the like may be contained.

The pH of the developer is preferably from 9.0 to 12.0, particularly preferably from 9.0 to 11.0, more preferably from 9.5 to 12.0.
It is in the range of 11.0. As the alkali agent used for adjusting the pH, a common water-soluble inorganic alkali metal salt (eg, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc.) can be used.

As cations in the developer, potassium ions do not suppress development and are less jagged around a blackened portion called fringes as compared with sodium ions. Further, when stored as a concentrated solution, the potassium salt is generally preferred because of its higher solubility. However,
In the fixer, potassium ions inhibit fixation to the same extent as silver ions, so if the potassium ion concentration in the developer is high, the potassium ion concentration in the fixer will increase due to the developer being brought in by the photosensitive material. Is not preferred. From the above, the molar ratio of potassium ion to sodium ion in the developer is preferably between 20:80 and 80:20. The ratio of potassium ion to sodium ion can be arbitrarily adjusted within the above range using a counter cation such as a pH buffer, a pH adjuster, a preservative, and a chelating agent.

The replenishing amount of the developing solution is 3 per 1 m ² of the photosensitive material.
90 ml or less, preferably 200 to 30 ml, most preferably 180 to 30 ml. The development replenisher may have the same composition and / or concentration as the development initiator, or may have a different composition and / or concentration than the developer.

As the fixing agent of the fixing agent in the present invention, ammonium thiosulfate, sodium thiosulfate and sodium ammonium thiosulfate can be used. The amount of the fixing agent can be changed as appropriate, but is generally from about 0.7 to about
3.0 mol / l.

The fixing solution of the present invention may contain a water-soluble aluminum salt and a water-soluble chromium salt acting as a hardener, and a water-soluble aluminum salt is preferred. Examples thereof include aluminum chloride, aluminum sulfate, potassium alum, aluminum ammonium sulfate, aluminum nitrate, and aluminum lactate. These are used as an aluminum ion concentration of 0.01 to 0.15 mol /
It is preferably contained in liters. When the fixing solution is stored as a concentrated solution or a solid agent, the fixing solution may be composed of a plurality of parts having a hardening agent and the like as separate parts, or may be a one-part composition containing all components.

If desired, preservatives (for example, sulfites, bisulfites, metabisulfites, etc.) may be used in the fixing treatment agent in an amount of 0.015
Mol / l or more, preferably 0.02 mol / l ~
0.3 mol / l), pH buffer (eg acetic acid, sodium acetate, sodium carbonate, sodium bicarbonate,
0.1 mol / L to 1 mol / L, preferably 0.2 mol / L, of phosphoric acid, succinic acid, adipic acid and the like
0.7 mol / liter), compounds with aluminum stabilizing or water softening ability (eg gluconic acid, iminodiacetic acid, 5-sulfosalicylic acid, glucoheptanoic acid, malic acid, tartaric acid, citric acid, oxalic acid, maleic acid, glycolic acid) Benzoic acid, salicylic acid, tyrone, ascorbic acid, glutaric acid, aspartic acid, glycine, cysteine, ethylenediaminetetraacetic acid, nitrilotriacetic acid and derivatives thereof and their salts and saccharides in an amount of 0.001 mol /
Liter to 0.5 mol / liter, preferably 0.005 mol / liter
Liters to 0.3 moles / liter),
From the viewpoint of environmental protection in recent years, it is better not to include a boron compound.

In addition, compounds described in JP-A-62-78551, pH adjusters (eg, sodium hydroxide, ammonia, sulfuric acid, etc.), surfactants, wetting agents, fixing accelerators and the like can also be included. Examples of the surfactant include an anionic surfactant such as a sulfated sulfone oxide, a polyethylene-based surfactant, and an amphoteric surfactant described in JP-A-57-6840. Can also. Examples of the wetting agent include alkanolamine and alkylene glycol. As a fixing accelerator, JP-A-6-30
Alkyl- and allyl-substituted thiosulfonic acids and salts thereof described in 8681, and JP-B-45-35754, 58-12253.
5, thiourea derivatives described in 58-122536, alcohols having a triple bond in the molecule, thioether compounds described in U.S. Pat.
645 and the mercapto compound described in 3-101728, 4-1
70539, which may comprise a thiocyanate.

The pH of the fixing solution in the present invention is preferably 4.0 or more, more preferably 4.5 to 6.0. The pH of the fixer is increased by mixing with a developer due to the treatment. In this case, the pH is 6.0 or less, preferably 5.7 or less for a hardened fixer, and 7.0 or less, preferably 6.7 or less for a non-hardened fixer.

The replenishment rate of the fixing solution is 50 per m ² of the photosensitive material.
0 ml or less, preferably 300 ml or less, more preferably 270 to 80 ml. The replenisher may have the same composition and / or concentration as the starting solution, or may have a different composition and / or concentration than the starting solution.

The fixing solution can be reused by a known fixing solution regenerating method such as recovery of electrolytic silver. As the reproducing apparatus, there is, for example, FS-2000 manufactured by Fujifilm. Also, using an adsorption filter such as activated carbon,
It is also preferable to remove dyes and the like.

When the developing and fixing agent in the present invention is a liquid, it is preferable to store it in a packaging material having a low oxygen permeability as described in, for example, JP-A-61-73147. Further, when these liquids are concentrated liquids, they are used after being diluted at a ratio of 0.2 to 3 parts of water with respect to 1 part of the concentrated liquid so as to have a predetermined concentration.

Although the same results can be obtained even when the developing agent and the fixing agent in the present invention are solidified, the solid processing agent will be described below. The solid preparation in the present invention can be in a known form (powder, granule, granule, lump, tablet, compactor, briquette, plate, rod, paste, etc.). These solid agents may be coated with a water-soluble coating agent or film to separate components that react with each other upon contact, or may separate components that react with each other in a multilayer structure. These may be used in combination.

Known coating agents and granulating auxiliaries can be used, but polyvinylpyrrolidone, polyethylene glycol, polystyrenesulfonic acid and vinyl compounds are preferred. In addition, JP-A-5-45805, column 2, line 48 to column 3
You can refer to the 13th line.

In the case of forming a plurality of layers, components that do not react even if they come into contact with each other may be sandwiched between components that react with each other, and processed into tablets, briquettes, or the like. It may be packaged in a similar layer configuration. These methods are described in, for example, JP-A-61-259921, JP-A-4-16841,
4-78848 and 5-93991.

The bulk density of the solid processing agent is 0.5 to 6.0 g / cm ³
It is preferred, in particular tablets is preferably 1.0 to 5.0 g / cm ^3,
Granules are preferably 0.5 to 1.5 g / cm ³ .

As a method for producing the solid processing agent in the present invention, any known method can be used. For example, JP-A-61-259921, JP-A-4-15641, JP-A-4-16841, and 4-328
37, 4-78848, 5-93991, JP-A-4-85533, 4-8553
4, 4-85535, 5-134362, 5-97070, 5-04098,
5-224361, 6-138604, 6-138605, 8-286329 and the like can be referred to.

More specifically, tumbling granulation, extrusion granulation, compression granulation, crushing granulation, stirring granulation, spray drying, melt solidification, briquetting, roller compaction Ing method or the like can be used.

The solubility of the solid agent in the present invention can be adjusted by changing the surface state (smoothness, porousness, etc.), partially changing the thickness, or forming a hollow donut.
Further, a plurality of granules can be formed in a plurality of shapes in order to impart different solubilities to the plurality of granules or match the solubilities of materials having different solubilities. Further, a multilayer granulated material having a different composition between the surface and the inside may be used.

The packaging material for the solid preparation is preferably a material having low oxygen and moisture permeability, and the packaging material may be a known one such as a bag, a tube, or a box. Also, JP-A-6-242585-
6-242588, 6-247432, 6-247448, 6-301189,
The foldable shape as disclosed in 7-5664, 7-5666 to 7-5669 is also preferable for reducing the storage space of the waste packaging material. For these packaging materials, screw caps, pull tops, aluminum seals may be attached to the processing agent outlet, or the packaging materials may be heat sealed,
Other known materials may be used, and there is no particular limitation. Further, in terms of environmental conservation, it is preferable to recycle or reuse the waste packaging material.

The method for dissolving and replenishing the solid processing agent of the present invention is not particularly limited, and a known method can be used. Examples of these methods include a method of dissolving and replenishing a fixed amount with a dissolution apparatus having a stirring function, and a method disclosed in
A method of dissolving with a dissolving apparatus having a dissolving part and a part for storing a completed liquid as described in 9-80718 and replenishing from the stock part, JP-A-5-119454, JP-A-6-19102, JP-A-7
-Dissolving and replenishing by adding a processing agent to the circulating system of an automatic developing machine as described in -261357. However, any other known method can be used. Further, the processing agent may be charged manually, or may be automatically opened and automatically loaded by a dissolving apparatus or an automatic developing machine having an opening mechanism as described in JP-A-9-138495. The latter is preferred from the point of view. Specifically, a method of piercing the outlet, a peeling method, a cutting method, a pushing method,
2, the method described in 6-95331, and the like.

The photosensitive material which has been subjected to development and fixing is then washed or stabilized (hereinafter, unless otherwise specified, washing including the stabilization is performed. ). Water used for washing may be tap water, ion-exchanged water, distilled water, or a stabilizing liquid. The replenishment amount is generally about 17 liters to about 8 liters per 1 m ² of the light-sensitive material, but the replenishment amount can be less. In particular, when the replenishment amount is 3 liters or less (including 0; that is, washing with water), not only water saving processing can be performed, but also piping for installing an automatic developing machine can be eliminated. When washing with a small amount of water is performed, it is more preferable to provide a squeezing roller and a crossover roller washing tank described in JP-A-63-18350 and JP-A-62-287252. Various oxidizing agents (for example, ozone, hydrogen peroxide, sodium hypochlorite, active halogen, chlorine dioxide, sodium carbonate hydrogen peroxide, etc.) to reduce pollution load and prevent water scale, which are problems when washing with a small amount of water. You may combine addition and filter filtration.

As a method of reducing the replenishing amount of washing, a multi-stage countercurrent method (eg, two-stage, three-stage, etc.) has been known for a long time, and the replenishing amount of washing is preferably 200 to 50 ml per 1 m ² of the photosensitive material. This effect can be similarly obtained by an independent multi-stage system (a method in which a new liquid is individually replenished in a multi-stage washing tank without using countercurrent).

Further, in the method of the present invention, means for preventing water scale may be provided in the washing step. As the scale prevention means, known means can be used, and there is no particular limitation. There are a method of applying a magnetic field, a method of sonication, a method of applying heat, and a method of emptying the tank when not in use. These scale prevention means may be performed in accordance with the processing of the photosensitive material, may be performed at regular intervals irrespective of the use condition, or may be performed only during a period during which processing is not performed, such as at night. Alternatively, it may be preliminarily applied to the washing water and replenished. Further, it is also preferable to perform different scale prevention means at regular intervals in order to suppress the generation of resistant bacteria. As a water-saving scale device, an apparatus AC-1000 manufactured by Fuji Photo Film Co., Ltd. and AB-5 manufactured by Fuji Photo Film Co., Ltd. as a scale inhibitor may be used.
The method of 31485 may be used. The protective agent is not particularly limited, and a known one can be used. In addition to the above-mentioned oxidizing agents, there are chelating agents such as glutaraldehyde and aminopolycarboxylic acid, cationic surfactants, mercaptopyridine oxides (eg, 2-mercaptopyridine-N-oxide and the like) and the like. But it is good. As a method of energizing, JP-A-3-224685, JP-A-3-2246
87, 4-16280, and 4-18980 can be used.

In addition, known water-soluble surfactants and defoamers may be added to prevent unevenness of water bubbles and transfer of dirt. Further, a dye adsorbent described in JP-A-63-163456 may be provided in a water washing system to prevent contamination by a dye eluted from the light-sensitive material.

A part or all of the overflow solution from the washing step can be mixed with a processing solution having a fixing ability as described in JP-A-60-235133. In addition, microbial treatment (for example, sulfur oxidizing bacteria, activated sludge treatment, treatment with a filter in which microorganisms are supported on a porous carrier such as activated carbon or ceramic), or oxidation treatment with an electric current or an oxidizing agent is carried out to obtain a biochemical oxygen demand. Water (BOD), chemical oxygen demand (COD), iodine consumption, etc. before draining, or forming a filter using a polymer with affinity for silver or forming a sparingly soluble silver complex such as trimercaptotriazine It is also preferable from the viewpoint of preserving the natural environment that the silver concentration in the wastewater is reduced by adding a compound to the mixture to precipitate silver and filtering the precipitate with a filter.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, JP-A-2-201357 and JP-A-2-13243.
Baths containing the compounds described in 5, No. 1-102553 and JP-A-46-44446 may be used as the final bath of the light-sensitive material. If necessary, this stabilizing bath also contains ammonium compounds, metal compounds such as Bi and Al, fluorescent brighteners, various chelating agents, membrane pH regulators, hardeners, bactericides, deterrents, alkanolamines and surfactants. Agents can also be added.

Additives such as deterrents and stabilizing agents to be added to the washing and stabilizing baths and the stabilizing agents can be solid agents as in the above-mentioned developing and fixing agents.

It is preferable that the waste liquid of the developing solution, fixing solution, washing water and stabilizing solution used in the present invention is incinerated. In addition, these waste liquids are, for example, Japanese Patent Publication No. 7-83867, US5439560
It is also possible to dispose after concentrating or liquefying or solidifying with a concentrating device such as described in US Pat.

In order to reduce the replenishment amount of the processing agent, it is preferable to reduce the opening area of the processing tank to prevent evaporation of the liquid and oxidation of the air. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971 and the like, and are simply referred to herein as roller transport type automatic developing machines. This self-developing machine comprises four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most preferably follows these four steps. Furthermore, during development and fixing and
A rinsing bath may be provided between the fixing and washing with water.

In the development processing of the present invention, the time from the start of processing to the time after drying (dry to dry) is preferably 25 to 160 seconds, and the development and fixing time is 40 seconds or less, preferably 6 to 35 seconds. 25 to 50 ° C is preferred, and 30 to 40 ° C is preferred. The temperature and time of the water washing are preferably 0 to 50 ° C. and 40 seconds or less. According to the method of the present invention, the photosensitive material that has been developed, fixed, and washed may be washed with washing water, that is, dried through a squeeze roller. Drying is performed at about 40 to about 100 ° C,
The drying time can be appropriately changed depending on the surrounding conditions. Any known drying method can be used, and there is no particular limitation.Hot air drying and JP-A-4-15534, JP-A-5-2256, and JP-A-5-2256
There are heat roller drying and far infrared drying as disclosed in 89294, and a plurality of methods may be used in combination.

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 Preparation of Emulsion A 1 solution 750 ml water 20 g gelatin 20 g sodium chloride 3 g 1,3-dimethylimidazolidin-2-thione 20 mg sodium benzenethiosulfonate 10 mg citric acid 0.7 g 2 solutions water 300 ml silver nitrate 150 g 3 solutions water 300 ml chloride Sodium 38g Potassium bromide 32g Potassium hexachloroiridate (III) (0.005% KCl 20% aqueous solution) 5ml Ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) 7ml Potassium hexachloroiridate (III) used for 3 liquids
(0.005% KCl 20% aqueous solution) and ammonium hexachlororhodate (0.001% NaCl 20% aqueous solution) dissolve the powder in KCl 20% aqueous solution and NaCl 20% aqueous solution, respectively.
It was prepared by heating at 40 ° C. for 120 minutes.

One solution maintained at 38 ° C. and pH 4.5 was added with 2
The liquid and the three liquids were each added in an amount corresponding to 90% with stirring over a period of 20 minutes to form 0.16 μm core particles. Subsequently, the following liquids 4 and 5 were added over 8 minutes, and the remaining 10% of the liquids 2 and 3 were added over 2 minutes to grow to 0.21 μm. further,
0.15 g of potassium iodide was added and the mixture was aged for 5 minutes to complete the particle formation. Fourth liquid water 100ml Silver nitrate 50g Five liquid water 100ml Sodium chloride 13g Potassium bromide 11g Thereafter, water was washed by flocculation according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated. (PH 3.
Then, about 3 liters of the supernatant was removed (first rinsing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing).
Repeat the same operation as the second washing one more time (third washing)
The washing and desalting process was completed. To the emulsion after water washing and desalting, 30 g of gelatin was added to adjust the pH to 5.6 and pAg 7.5. Chemical sensitization to obtain optimum sensitivity at 100 ° C, 1,3,3a, 7-tetraazaindene 100 mg as a stabilizer and proxel as a preservative (trade name, I
CI Co. , Ltd. 100 mg). Finally, a silver iodochlorobromide cubic grain emulsion containing 70 mol% of silver chloride and 0.08 mol% of silver iodide and having an average grain size of 0.22 μm and a variation coefficient of 9% was obtained. (Finally, pH = 5.
7, pAg = 7.5, conductivity = 40 μS / m, density =
The viscosity was 1.2 × 10 ⁻³ kg / m ³ and the viscosity was 60 mPa · s. )

Preparation of non-photosensitive silver halide grains 1 liquid 1 liter of water 20 g of gelatin 20 g of sodium chloride 20 g of 1,3-dimethylimidazolidin-2-thione 20 mg 8 mg of sodium benzenethiosulfonate 2 liquids 400 ml of silver nitrate 100 g 3 liquids Water 400 ml Sodium chloride 13.5 g Potassium bromide 45.0 g Potassium hexachlorodimate (III) (0.001% aqueous solution) 860 ml

Solution 1, Solution 2 and Solution 3 kept at 70 ° C. and pH 4.5 were added simultaneously with stirring over 15 minutes.
Core particles formed. Subsequently, the following liquids 4 and 5 were added over 15 minutes. Further, 0.15 g of potassium iodide was added to terminate the particle formation. 4th liquid 400ml Silver nitrate 100g 5th liquid 400ml Sodium chloride 13.5g Potassium bromide 45.0g

Thereafter, the resultant was washed with water by a flocculation method according to a conventional method. Specifically, the temperature was lowered to 35 ° C., 3 g of the following anionic precipitant-1 was added, and the pH was lowered using sulfuric acid until silver halide precipitated.
(The pH was in the range of 3.2 ± 0.2) Next, about 3 liters of the supernatant was removed (first washing). An additional 3 liters of distilled water was added and then sulfuric acid was added until the silver halide settled. Again, 3 liters of the supernatant was removed (second washing). The same operation as the second washing was repeated one more time (third washing) to complete the washing / desalting process. 45 g of gelatin was added to the emulsion after washing with water and desalting, pH 5.7, pAg
Was adjusted to 7.5, and phenoxyethanol was added as a preservative. Finally, it contained 30 mol% of average silver chloride and 0.08 mol% of silver iodide. A dispersion of cubic iodine iodochlorobromide cubic milk particles was obtained. (Finally, as an emulsion, pH = 5.7, pAg
= 7.5, conductivity = 40 μS / m, density = 1.3 × 10
^-3 kg / m ³ and viscosity = 50 mPa · s. )

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Preparation of Coated Samples On a polyethylene terephthalate film support having the following two sides, each of which is composed of an undercoat of a moisture-proof layer containing vinylidene chloride, a UL layer / emulsion layer / a lower layer of a protective layer / an upper layer of a protective layer were formed. This was applied to prepare Sample 1-1.

The preparation method, coating amount and coating of each layer are described below.
Here's how. <Emulsion layer> Sensitizing dye (sd-1) 5.7 × 10^-FourMol /
Molar Ag was added for spectral sensitization. Further KBr 3.4
× 10^-FourMol / mol Ag, compound (cpd-1) 2.0 × 10^-FourMole
/ Mol Ag, compound (cpd-2) 2.0 × 10^-FourMol / mol A
g, compound (cpd-3) 8.0 × 10 ^-FourMole / mole Ag,
Mix well. Then 1,3,3a, 7-tetraazaindene 1.2
× 10^-FourMol / mol Ag, hydroquinone 1.2 × 10^-2Mole
/ Mol Ag, citric acid 3.0 × 10^-FourMol / mol Ag, development
80 mg / m of accelerator (A-4)^Two, 2,4-dichloro-6-hydroxy
Cy-1,3,5-triazine sodium salt 90mg / m^Two,gelatin
Colloidal silicide with a particle size of 10 μm
Mosquito, aqueous latex (aqL-6) 100mg / m^Two, Polyethyl
150mg / m acrylate latex^Two, Methyl acrylate
And 2-acrylamido-2-methylpropanesulfonic acid
Latte of thorium salt and 2-acetoxyethyl methacrylate
X copolymer (weight ratio: 88: 5: 7) at 150 mg / m^Two,
Asher type latex (core: styrene / butadiene
Polymer (weight ratio 37/63), shell: styrene / 2-a
Sethoxyethyl acrylate (weight ratio 84/16),
A / shell ratio = 50/50) to 150 mg / m^TwoAgainst gelatin
And add 4wt% compound (cpd-7) and use citric acid
The pH of the coating solution was adjusted to 5.6. Prepared in this way
The emulsion layer coating solution was coated with 3.4 g / m of Ag on the following support.^Two, Ze
Latin 1.1g / m^TwoIt was applied so that

<Protective Layer Upper Layer> Gelatin 0.3 g / m ² 3.5 μm average amorphous silica matting agent 25 mg / m ² Compound (Cpd-8) (gelatin dispersion) 20 mg / m ² Particle size 10-20 μm Colloidal silica (Nissan Chemical Snowtex C) 30 mg / m ² compound (Cpd-9) 50 mg / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² compound (Cpd-10) 20 mg / m ² compound (Cpd-11) 20 mg / M ² preservative (Proxel (trade name, manufactured by ICI Co., Ltd.)) 1 mg / m ²

<Lower Layer of Protective Layer> Gelatin 0.5 g / m ² Non-light-sensitive silver halide grains 0.1 g / m ² 1,5-dihydroxy-2-benzaldoxime 10 mg / m ² polyethyl acrylate latex as Ag content 150 mg / m ² Compound (Cpd-13) 3 mg / m ² Preservative (Proxel) 1.5 mg / m ²

<UL layer> Gelatin 0.5 g / m ² Polyethyl acrylate latex 150 mg / m ² Compound (Cpd-7) 40 mg / m ² Compound (Cpd-14) 10 mg / m ² Preservative (Proxel) 1.5 mg / M ²

The viscosity of the coating solution for each layer was adjusted by adding a thickener represented by the following structure (Z).

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The sample used in the present invention has a back layer and a conductive layer having the following compositions. <Back layer> Gelatin 3.3 g / m ² compound (Cpd-15) 40 mg / m ² compound (Cpd-16) 20 mg / m ² compound (Cpd-17) 90 mg / m ² Compound (Cpd-18) 40 mg / m ² compounds (Cpd-19) 26 mg / m ² 1,3-divinylsulfonyl-2-propanol 60 mg / m ² Fine particles of polymethyl methacrylate (average particle size 6.5 μm) 30 mg / m ² Liquid paraffin 78 mg / m ² Compound (Cpd -7) 120 mg / m ² Calcium nitrate 20 mg / m ² Preservative (Proxel) 12 mg / m ² <Conductive layer> Gelatin 0.1 g / m ² Sodium dodecylbenzenesulfonate 20 mg / m ² SnO ₂ / Sb (9/1) (Weight ratio, average particle size 0.25μ) 200 mg / m ² Preservative (Proxel) 0.3 mg / m ²

[0108]

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[0109]

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[0110]

Embedded image <Support> An undercoat layer having the following composition on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm)
A layer and a second layer were applied.

<One Layer of Undercoat Layer> Core-shell type vinylidene chloride copolymer 15 g 2,4-dichloro-6-hydroxy-s-triazine 0.25 g Polystyrene fine particles (average particle size 3 μ) 0.05 g Compound (Cpd) -20) 0.20 g Colloidal silica (Snowtex ZL: particle size 70-100 μm, manufactured by Nissan Chemical Co., Ltd.) 0.12 g 100 g by adding water Further, 10% by weight of KOH was added to adjust to pH = 6. The solution was dried at a drying temperature of 180 ° C. for 2 minutes, and the dry film thickness was 0.1 mm.
It was applied to 9 μm.

<Undercoat Layer Second Layer> Gelatin 1 g Methylcellulose 0.05 g Compound (Cpd-21) 0.02 g C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₀ H 0.03 g Proxel 3.5 × 10 ^{− 3} g Acetic acid 0.2 g Water was added and 100 g This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness became 0.1 μm. <Coating method> On the support on which the above-mentioned undercoat layer has been formed, four layers of an UL layer, an emulsion layer, a protective layer lower layer, and a protective layer upper layer are sequentially maintained at 35 ° C from the side closer to the support as the emulsion surface side. While applying a hardener solution by a slide bead coater method and applying a multilayer coating simultaneously and passing through a cold air set zone (5 ° C.), the conductive layer and the back layer are arranged on the opposite side to the emulsion surface from the side closer to the support. In this order, simultaneous multi-layer coating was performed while adding a hardener solution by a curtain coater method, and the coating solution was passed through a cold air set zone (5 ° C.). At the time of passing through each set zone, the coating liquid showed sufficient setting properties. Subsequently, both surfaces were simultaneously dried in the drying zone under the following drying conditions. In addition, after coating the back surface side, it was conveyed in a non-contact state with a roller and other parts until winding up. The coating speed at this time was 210 m / min.

[0113]

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<Drying conditions> After setting, the mixture was dried with a drying air at 30 ° C until the weight ratio of water / gelatin became 800%.
After drying 200 to 200% with a dry air at 35 ° C and 30% RH, the air is directly applied, and 30 seconds after the surface temperature reaches 34 ° C (assuming that the drying is completed), 48 ° C and 2% RH.
For 1 minute. At this time, the drying time is 50 seconds from the start of drying to a water / gelatin ratio of 800%, and 800 to 20%.
35 seconds from 0% to 5 seconds from 200% to the end of drying.

This photosensitive material is wound up at 25 ° C. and 55% RH.
Next, the sample was cut under the same environment, and conditioned in a barrier bag conditioned for 6 hours at 25 ° C. and 50% RH for 8 hours.
Samples shown in Table 1 were prepared by sealing with cardboard conditioned for 2 hours at% RH. When the humidity inside the barrier bag was measured, it was 45% RH. The pH of the film surface on the emulsion layer side of the obtained sample was 5.5 to 5.8, and the film surface pH on the back side was 6.
0 to 6.5. The absorption spectra on the emulsion layer side and the back layer side were as shown in FIG.

Preparation of Emulsions B and C Emulsion A was prepared in the same manner as Emulsion A except that the amount of K ₂ [Ru (NO) Cl ₅ ] was added instead of adding ammonium hexachlororhodate during the preparation of Emulsion A. And Emulsions B and C were obtained. Preparation of Emulsions D and E Emulsion D was prepared in the same manner as Emulsion A except that the amount of K ₂ [Os (NO) Cl ₅ ] was added instead of adding ammonium hexachlororhodate during the preparation of Emulsion A. , E.

Preparation of Coated Samples 1-2 to 1-5 Coated samples 1-2 to 1-5 were prepared in exactly the same manner except that emulsions B to D were used instead of emulsion A when preparing coated sample 1. did. Preparation of Coating Sample 1-6 Coating Sample 1-6 was prepared in exactly the same manner except that the coating sample 1-4 was prepared without adding an amine compound. Preparation of coating samples 1-7 to 1-11 Ag 3.4 g / m when preparing coating samples 1-1 and 1-2
^2. Coated samples 1-7 to 1-11 were prepared in exactly the same manner as in 2, except that the silver: gelatin ratio was changed to 3.1 to 0.9. Table 1 shows the type of heavy metal, the amount of addition, the presence or absence of addition of the amine compound, and the silver: gelatin ratio of each sample.

The evaluation was performed by the following method. The obtained sample was exposed to xenon flash light having an emission time of 10 ^-6 seconds through an interference filter having a peak at 667 nm and a step wedge. Then, using a developer (A) and a fixer (B) having the following formulation, FG-680AG
Using an automatic processor (Fuji Photo Film Co., Ltd.), 3
The film was processed under development conditions of 5 ° C. and 30 ″.

Developer (A) The composition per 1 L of the concentrated solution is shown. Potassium hydroxide 60.0 g Diethylenetriamine / pentaacetic acid 3.0 g Potassium carbonate 90.0 g Sodium metabisulfite 105.0 g Potassium bromide 10.5 g Hydroquinone 60.0 g 5-Methylbenzotriazole 0.53 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 2.3 g 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.15 g 2-mercaptobenzimidazole-5-sulfonic acid Sodium 0.45 g Sodium erythorbrate 9.0 g Diethylene glycol 7.5 g pH 10.79 In use, the mother liquor was prepared by adding 1 part of water to 2 parts of the above concentrated liquid.
The replenisher was diluted at a ratio of 3 parts of water with respect to 4 parts of the concentrated solution, and the pH of the replenisher was 10.62.

Fixer (B) Formulation The formula per 1 L of the concentrated solution is shown. Ammonium thiosulfate 360 g Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.09 g Sodium thiosulfate / pentahydrate 33.0 g Sodium metasulfite 57.0 g Sodium hydroxide 37.2 g Acetic acid (100%) 90. 0 g tartaric acid 8.7 g sodium gluconate 5.1 g aluminum sulfate 25.2 g pH 4.85 For use, dilute 2 parts of water to 1 part of the above concentrated liquid. The pH of the working solution is 4.8. The replenisher used was the same dilution as the above-mentioned use solution, and was used at 258 ml per 1 m ^{2 of} the light-sensitive material.

[Evaluation of photographic properties] The reciprocal of the exposure amount giving a density of 1.5 is defined as the sensitivity and expressed as relative sensitivity, and γ is ((1.5−
0.3) / log (exposure dose giving a density of 1.5) -lo
g (exposure amount giving a density of 0.3).

[Evaluation of practical skill density] Using an image setter FT-R5055 manufactured by Dainippon Screen Co., Ltd., 175
A test step is output while changing the light amount in lines / inch, and development processing is performed under the processing conditions described above.
%, And the Dmax portion when the exposure was performed at an LV value of% was determined as the actual density. Note that the net% and the actual skill concentration are Macbe
th TD904.

[Evaluation of Sharpness of Halftone Dots] Imagesetter FT-R manufactured by Dainippon Screen Co., Ltd.
Exposure was performed at 175 lines / inch using 5055, and the sharpness of the image quality at the fringe portion of the halftone dot where the intermediate halftone dot was 50% was evaluated. Performed by visual sensory evaluation of 1 to 5 points (5 points are better in image quality), with the image quality of HL manufactured by Fuji Photo Film Co., Ltd. being 5 points and the image quality of LS-4500 being 3 points. Was.

[0124]

[Table 1]

As can be seen from the results in the table, the light-sensitive material of the present invention has high sensitivity, high contrast, high blackening density in practical use, and good dot quality.

Example 2 An experiment similar to that of Example 1 was performed using the following solid developer (C) and solid fixing agent (D). Performance.

Formulation of solid developer (C) Sodium hydroxide (beads) 99.5% 11.5 g Potassium sulfite (raw powder) 63.0 g Sodium sulfite (raw powder) 46.0 g Potassium carbonate 62.0 g Hydroquinone (briquette) Diethylenetriamine / pentaacetic acid 2.0 g 5-methylbenzotriazole 0.35 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.5 g 4- (N-carboxymethyl -N-methylamino) -2,6-dimercaptopyrimidine 0.2 g 3- (5-mercaptotetrazol-1-yl) sodium benzenesulfonate 0.1 g sodium erythorbate 6.0 g potassium bromide 6.6 g Dissolve in water to make 1 liter. pH 10.65

Here, in the form of raw materials, raw powders were used as general industrial products, and commercially available beads of alkali metal salts were used. When the raw material was in the form of a briquette, a plate-like material obtained by pressurizing and compressing using a briquetting machine was crushed and used. For minor components, each component was blended before briquetting. 10 liters of the above treating agent was filled in a foldable container made of high-density polyethylene, and the outlet was sealed with an aluminum seal. For dissolution and replenishment, JP-A-9-80718 and JP-A-9-9-1
A dissolution replenisher with an automatic opening mechanism as disclosed in US Pat.

Formulation of solid fixing agent (D) Formulation A (solid) Ammonium thiosulfate (compact) 125.0 g Anhydrous sodium thiosulfate (raw powder) 19.0 g Sodium metabisulfite (raw powder) 18.0 g Anhydrous sodium acetate (raw) Powder) 42.0 g Agent B (liquid) Ethylenediamine / tetraacetic acid / 2Na / dihydrate 0.03 g Tartaric acid 2.9 g Sodium gluconate 1.7 g Aluminum sulfate 8.4 g Sulfuric acid 2.1 g Dissolve in water to make up to 50 ml. . The fixing solution (D) was prepared by dissolving the agent A and the agent B in water and adjusting the solution to 1 liter. pH was 4.8. The replenisher was prepared in the same manner as the fixer (D), and was used at a rate of 258 ml per 1 m ^{2 of} the light-sensitive material.

As ammonium thiosulfate (compact), a flake product prepared by a spray-drying method was pressed and compressed by a roller compactor and crushed into amorphous chips of about 4 to 6 mm in size, and blended with anhydrous sodium thiosulfate. For other bulk powders, general industrial products were used. 10 liters of both Agent A and Agent B were filled in a foldable container made of high-density polyethylene, and the outlet of Agent A was sealed with an aluminum seal. The mouth of the agent B container was sealed with a screw cap. For dissolving and replenishing, a dissolving and replenishing device having an automatic opening mechanism disclosed in JP-A-9-80718 and JP-A-9-138495 was used.

Example 3 Coating sample 2-1 was prepared in the same manner as in Example 1 except that the metal complex contained in the emulsion as shown in Table 2, the amount thereof, the type of the accelerator added to the coating sample, and the silver: gelatin ratio were changed. ~ 2-9 was created.
The following developer (E) was used instead of the developer (A) of Example 1.
The same experiment as in Example 1 was carried out using the same. As in Example 1, the light-sensitive material having the structure of the present invention showed good performance.

The composition per liter of the concentrated solution of the developer (E) is shown below. Potassium hydroxide 105.0 g Diethylenetriamine / pentaacetic acid 6.0 g Potassium carbonate 120.0 g Sodium metabisulfite 120.0 g Potassium bromide 9.0 g Hydroquinone 75.0 g 5-Methylbenzotriazole 0.25 g 4-Hydroxymethyl-4- Methyl-1-phenyl-3-pyrazolidone 1.35 g 4- (N-carboxymethyl-N-methylamino) -2,6-dimercaptopyrimidine 0.3 g 2-mercaptobenzimidazole-5-sodium sulfonate 0.45 g Sodium erythorbrate 9.0 g Diethylene glycol 60.0 g pH 10.7 Before use, dilute the concentrate at a ratio of 2 parts of water to 1 part of the concentrated liquid. PH of working solution is 10.5

[0133]

[Table 2]

Example 4 Coated sample 3-1 was prepared in the same manner as in Example 1 by changing the metal complex contained in the emulsion as shown in Table 3, the amount thereof, the type of the accelerator added to the coated sample, and the silver: gelatin ratio. ~ 3-10 was created. When the same experiment as in Example 1 was performed using the following developer (F) and fixing solution (G) in place of the developer (A) of Example 1, the structure of the present invention was similar to that of Example 1. Of the photosensitive material showed good performance.

The composition per liter of the concentrated solution of the developer (F) is shown below. Diethylenetriamine-5 acetic acid 4 g Potassium carbonate 50 g Sodium carbonate 60 g Potassium hydrogen carbonate 76 g Sodium erythorbate 90 g 2- (3-hydroxypropyl ether) -4- (N, N-dimethylamino) phenol 2 g KBr 4 g 5-methylbenzotriazole 0.0 g 008 g 1-phenyl-5-mercaptotetrazole 0.04 g sodium sulfite 20 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 3 g 4- (N-carboxymethyl-N-methylamino-2,6-di Mercaptopyrimidine 0.36 g 2- (N-carboxymethyl-N-methylamino-4,6-dimercaptopyrimidine 0.12 g Add water to 1 liter and adjust the pH to 9.9. With liquid The pH was 9.7 after adding water 1 to the above solution 1. The composition per liter of the concentrated solution of the fixing solution (G) is shown below: Sodium thiosulfate pentahydrate 580.0 g meta Sodium bisulfite 49.1 g NaOH 4.59 g Ethylenediaminetetraacetic acid 2Na dihydrate 0.09 g pH (prepared with sulfuric acid or sodium hydroxide) 5.42 Add water 1 liter Add 1 liter of water to 1 of the above liquid It was used as a mother liquor (starting solution) and a replenisher and had a pH of 5.62, and the replenishment amount of the fixing solution was 162 ml per m2 of the light-sensitive material.

[0136]

[Table 3] Metal complex species Rh: [RhCl ₆ ] ^3- Ru: [Ru (NO) Cl ₅ ] ^2- Os: [Os (NO) Cl ₅ ] ^2- cyanide (ligand metal) complex species Fe: [Fe (CN) ) ₆ ] ^4- Ru: [Ru (CN) ₆ ] ^4- chemical sensitizer species S: sulfur sensitization; Se: selenium sensitization;
Te: tellurium sensitization: Au: gold sensitization.

Example 5 Using the developing solutions (A), (E) and (F) of Examples 1, 3 and 4,
A scanner film HL made by Fuji Photo Film with a blackening of 80% per day, in large size (50.8 cm x 61 cm)
By processing a total of 300 sheets while replenishing the amount shown in Table 4 and performing this process continuously for 4 days, a large amount of film was processed, whereby the pH was lowered, and the developer having an increased bromine ion concentration was obtained. Obtained.

The same experiment as in Examples 1, 3, and 4 was carried out using the developer of the fatigue developer as described above. It showed good performance.

[0139]

[Table 4] PH of each developer fatigue solution

Example 6 In Examples 1 to 5, the developing temperature was 38 ° C. and the fixing temperature was 37.
When the processing was carried out at a temperature of 20 ° C. and a developing time of 20 seconds, the same results as in Examples 1 to 5 were obtained, and the effects of the present invention were not lost.

Example 7 In Examples 1 to 5, the automatic machine was replaced by FG-680AS manufactured by the company.
, And the same processing was performed with the photosensitive material transport speed set to a linear speed of 1500 mm / min to obtain similar results.

Example 8 Imagesetter FT-R5055 manufactured by Dainippon Screen Co., Ltd.
Instead of using the Select Set 5000, Avantra 25 or Accu Set 1000 manufactured by Agfagewald, Dreb 45 manufactured by Cytex Corporation.
0, or Dreb 800, Rhino 630, Quasar, Hercules Elite, or Signa Setter manufactured by Heidel Co., Ltd., Lux Setter RC-5600V, manufactured by Fuji Photo Film Co., Ltd., or Raxel F-9000, or Prepress Co., Ltd. The same evaluation was performed using any one of the Panther Pro 62 models, and the same effect was obtained with the sample of the present invention.

[Brief description of the drawings]

FIG. 1 is an absorption spectrum of each of an emulsion layer side and a back layer side in Example 1 of the present invention.

[Explanation of symbols]

The vertical axis indicates absorbance (0.1 interval), and the horizontal axis is 350 nm.
From 950 to 950 nm. The solid line shows the absorption spectrum on the emulsion layer side, and the broken line shows the absorption spectrum on the back layer side.

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

Claims (7)

[Claims] 1. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support, wherein the emulsion layer has a silver: gelatin ratio higher than 1. And V- of the periodic table having a nitrosyl or thionitrosyl ligand
The photosensitive material contains silver halide grains containing a transition metal complex selected from Group VIII elements, does not contain a hydrazine derivative, and contains a development accelerator in the emulsion layer and / or the hydrophilic colloid layer. A silver halide photographic light-sensitive material characterized by containing: 2. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support, wherein the emulsion layer has a silver: gelatin ratio higher than 1. Having silver halide grains containing a transition metal complex selected from the elements of Groups V to VIII of the periodic table having a cyan ligand, wherein the photosensitive material does not contain a hydrazine derivative. A silver halide photographic material comprising a development accelerator in the emulsion layer and / or the hydrophilic colloid layer. 3. The periodic table having a cyanide ligand having a number V
2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide grains contain a transition metal selected from the group consisting of Group-VIII elements. 4. A silver halide photographic material having at least one photosensitive silver halide emulsion layer and at least one hydrophilic colloid layer on a support, wherein the emulsion layer has a silver: gelatin ratio higher than 1. And silver halide grains chemically sensitized with a selenium compound and / or tellurium compound. The light-sensitive material does not contain a hydrazine derivative, and a development accelerator is added to the emulsion layer and / or Alternatively, a silver halide photographic material, which is contained in the hydrophilic colloid layer. 5. Silver halide grains chemically sensitized with a selenium compound and / or a tellurium compound.
4. The silver halide photographic light-sensitive material according to any one of items 1 to 3. 6. The silver halide photographic material according to claim 1, wherein the development accelerator is an amine compound. 7. A method for developing a silver halide photographic light-sensitive material according to claim 1 after exposure, wherein the developing time is within 20 seconds and the replenishment amount of the developing solution is less than 20 seconds. A method for developing a silver halide light-sensitive material, wherein the amount is 200 ml / m ² or less, and the replenishing amount of the fixing solution is 300 ml / m ² or less.