JPH03132649A - Method for development processing of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease the silver stains generated in a developing tank and/or developing rack and roller by incorporating specific compds. into the silver halide photographic material. CONSTITUTION:The compds. of at least any of formula I or formulas II, III are incorporated into the silver halide photosensitive material in the case of development processing of the silver halide photosensitive material with a devel oping soln. contg. at least a developing agent of a hydroquione system and >=0.1mol/l sulfite component after the image weise development. In the formula I, B1 and D1 are respectively independently and aliphat. group, alicyclic group, arom. group, etc.; m1 and n1 are respectively independently 1 to 3 number; p is 1 or 2; A2, E2 are respectively independently the groups expressed by formu las -CO-O-M, -SO2-O-M, etc. In the formula II, R denotes a phenyl group or lower alkyl group. In the formula III, R' denotes a phenyl group or lower alky group; M denotes a hydrogen atom or alkaline metal. The silver stains sticking to the developing tank, the developing rack and the roller are decreased in this way.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a method for processing silver halide photographic materials, and more specifically, the present invention relates to a method for processing silver halide photographic materials, and more specifically, the present invention relates to a method for processing silver halide photographic materials, and more specifically, the present invention relates to a method for processing silver halide photographic materials, and more specifically, the present invention relates to a method for processing silver halide photographic materials, and more specifically, the present invention relates to a method for processing silver halide photographic materials, and more specifically, the present invention relates to a method for processing silver halide photographic materials, and more specifically, the present invention relates to a method for processing silver halide photographic materials. This invention relates to a method for reducing silver stains (also referred to as silver sludge) and facilitating daily maintenance of instruments and equipment.

<Conventional technology> Generally, when silver halide photographic materials are developed.

Depending on the amount of processing, the developing tank and vat, the wall of the developing tank of an automatic processor (hereinafter referred to as an automatic processor), the developing tank,
It has been known for a long time that silver adheres and accumulates on developing rollers. This is also called silver stain or silver sludge, and it adheres to the photosensitive material being processed and stains the image, necessitating periodic cleaning and maintenance of the equipment.

In addition, many of the latest silver halide photographic materials use minute silver halide grains to reduce the amount of silver coated, and this also results in better grain quality and improved photographic performance. .

On the other hand, in recent years, there has been an increasing demand for rapid processing in the development processing of silver halide photosensitive materials. In order to carry out rapid processing, the development temperature is generally increased in most cases in order to increase the development activity.

In this way, in both ■fine-grain silver halide and ■high-temperature development, the amount of silver halide dissolved in the developing solution increases, so the degree of silver staining becomes worse and maintenance becomes more frequent, which is a major disadvantage. There is.

To remove this silver stain each time, drain the developer from the developer tank and fill the tank with a very strong oxidizer solution, such as cerium sulfate. It must be left stirring for more than a minute. Furthermore, if traces of this oxidizing agent remain in the developing tank after this, the developing solution will be oxidized and deteriorated, so it must be thoroughly washed with water. This cleaning work is especially important for automatic processors.
This is one of the biggest burdens of daily maintenance, and improvements are desperately needed from the standpoint of work safety and the pollution burden of cleaning agents.

On the other hand, as a method to reduce this silver stain,
A method of adding a compound that reduces the amount of silver ions eluted into the developer and/or suppresses the reduction of silver ions to silver, such as i-λ≠3μ7, is known. However, this method has the disadvantage that it also inevitably inhibits the development itself, which is accompanied by a decrease in sensitivity. Moreover, since the sensitivity to this compound varies depending on the characteristics of the photosensitive material, no effect can be expected if it is used at a low rate. Also,
A decrease in sensitivity is a serious drawback for a photosensitive material/development processing system that is intended to be used with as high sensitivity as possible.

<Problems to be Solved by the Invention> Therefore, the purpose of the present invention is to first reduce silver stains that occur in the developing tank and/or developing rack and roller when developing silver halide photographic materials. to do,
The second K is to facilitate the maintenance of automatic processors and developing equipment, the third is to reduce silver contamination without affecting the photographic properties at all, and the fourth is to do so without compromising the stability of the developer. , to reduce silver stains.

Another object of the present invention is to provide a developing method that ensures high sensitivity and fine grain shape and is completely free from silver stains when processing a silver halide photosensitive material using an automatic processor.

<Means for solving the problem> (1) When a silver halide sensitive material is developed with a developer having at least the following components (a) and (b) after image exposure, (a) a hydroquinone-based developing agent; Φ) 0.1 mol/1 or more of sulfite This can be achieved by containing at least one of the following (X) or (Y) in the silver halide sensitive material.

(2) In addition, when performing the above-mentioned development treatment, 30% to 700% of the silver halide grains in the entire emulsion of the silver halide photosensitive material have a grain size of O1! This can be achieved more preferably by containing at least one of the following (X) or ('l) in a sensitive material consisting of particles with a particle size of less than μ, o, or more than iμ.

(X) Compound (I) represented by the following general formula (I) (8) p Di (E2) nl of 5-Bl (-A2) ITII Totally seven.

(Y) The following (yl) and (yl) (yl) Compound H R-CHCH2-COOH represented by the following general formula (■) [In the formula, R represents a phenyl group or a lower alkyl group. ] (yl) A compound represented by the following general formula (In) or an amine (lower) alkanethiosulfonic acid or an alkali metal salt thereof [wherein R' is a phenyl group or a lower alkyl group, and M is a hydrogen atom or Represents an alkali metal. ] Among the compounds represented by the general formula (I), preferred ones can be represented by the general formulas (IV) and (V).

General formula (II/, ) General formula (V) /\ R, R5 In general formula (IV), R1 and R3 are hydrogen atoms, optionally substituted alkyl groups with 7 to 2 carbon atoms, alkenyl groups,
represents an aralkyl group, a cycloalkyl group, an optionally substituted phenyl group, a one- or two-membered heterocycle containing 7 to 3 nitrogen atoms, one oxygen atom, or seven sulfur atoms, or a carboxylic acid group; R2 represents a direct bond or an optionally substituted alkylene group, alkylidene group,
Represents a phenylene group, an aralkylene group, or -CONHCH2-, A3 is -COOM or -8O3M (M has the same meaning as general formula (I)), m2 is l
Or it is Ko.

In general formula (V), R4 and R5 represent a hydrogen atom or a methyl group.

M is preferably a hydrogen cation or an alkali metal ion (such as Na' or Ni0).

Among the compounds represented by the general formula (IV), the general formula (■
) is even more preferred.

General formula (■) In general formula (Vl), R6 and R7 are hydrogen atoms, optionally substituted alkyl groups (e.g. -CH3, -C2H5, -C
H20H1-CH2CooH, etc.), a phenyl group that may be substituted with a cycloalkyl group (e.g., cycloynthyl group, cyclohexyl group, etc.) ((Fllttf phenyl group, tolyl group, p-chlorophenyl L p-aminophenyl group, p-sulfophenyl group, p-sulfonamidophenyl group, g) !- or Δ-membered heterocycle containing 7 to 3 nitrogen atoms, or 7 oxygen atoms or 7 sulfur atoms (e.g., furyl group, thienyl group, etc.), or It represents a carboxylic acid group, and R6 and R7 may be the same or different.

l is l, 2.3, or μ.

Next, in the general formulas (I) and (II), the lower alkyl group represented by 'R, R/ is a methyl group, ethyl group, propyl group, etc., and the amino(lower) alkanethiosulfonic acid is aminoethyl group. Thiosulfonic acid, etc.

Specific examples of the compound of general formula (1) are listed below.

Thiolactic acid α-mercaptoinbutyric acid HOOC (CH2)2-8 8 (CH2)2COO
HHOOC(CH2)3-8-8-(CH2)3COO
HHOOC-H2C-8-8-a-COOHH3C-
HC-8-8-mark-0 (3 HOOCC0OH OH3 OH3) IU [knee] 12t; Specific examples of the compound of the 8-8-CH2-COOH general formula (■) or (III) are listed below.

Methods for synthesizing the compounds represented by formulas (I), (n), and (III) are described in Japanese Patent Publication No. 21 of Sho R+-4 Tg, RRT No. 21. ≠! It is stated in No. 2, etc.

When the above compounds (X) and (Y) are added to the emulsion layer, the total amount added is 0.00% per mole of silver. /mg～j00m
g is preferable, and 7 mg to 100 mg is more preferable.

Further, when the present compound is added to a non-photosensitive layer other than an emulsion layer, it is preferable that the ratio of compound/silver in a unit area is set within the range of the above-mentioned addition amount upon completion of coating.

The compound of the present invention is Tokukosho! 2-≠jj♂! , Tokuko Sho tλ
-2141! It is disclosed as a silver stain preventive agent to be contained in a processing solution. However, this method is different from the present invention in that the compound is added to the developer, and furthermore, compared to the case where the compound of the present invention is added to the developer,
It was also found that the effect of preventing silver staining is greater when it is included in a photosensitive material, and therefore the amount added can be reduced, which has the advantage that problems such as low sensitivity due to addition of a large amount do not occur.

Also, in the example of Special Publick Showa J6-≠411j.

This patent only cites the use of the compound of the present invention in monobath development fixing agents and processing of photographic materials for silver dye bleaching, and this patent also differs from the previous patent.

The developing agent used in the developer of the present invention is mainly composed of hydroquinones because it is easy to obtain good performance. Good combination with aminophenols.

Hydroquinone-based developing agents used in the present invention include hydroquinone, chloronohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, co-! -dichlorono-hydroquinone, co,3-dibromohydroquinone, λ,j-dimethylhydroquinone, hydroquinone monosulfonate and the like, with no-hydroquinone being particularly preferred.

Examples of the p-aminephenol developing agent used in the present invention include N-methyl-p-aminophenol 5p-7 minophenol, N-(β-hydroxyethyl)-p-aminoneenol, and N-(≠-hydroxyphenyl). There are glycine, cornyl-p-aminephenol, p-benzylaminophenol, among others, N-methyl-p-
Aminphenols are preferred.

The 3-pyrazolidone developing agent used in the present invention is l
-phenyl-3-pyrazolidone, l-phenyl-≠, ≠
-dimethyl-j-pyrazolidone, l-phenyl-μmmethyl-≠-hydroxymethyl-j-pyrazolidone, /-
Phenyl-Hiro, ≠-dihydroxymethyl-3-pyrazolidone% / -phenyA/ -j-methyl-3-pyrazolidone, /-p-aminophenyluda, ≠-dimethyl-3-bilanelidone, /-p-tolyl- Examples include Hiroshi, 4t-dimethyl-3-pyrazolidone, /-p-)lilugoomethyl-goohydroxymethyl-3-pyrazolidone, and the like.

Hydroquinone type developing agent is usually 0.01 mol/l-/
, j mol/l, preferably 0.0! Mol/11-/, 2
It is used in an amount of mol/l.

In addition to this, the p-amine phenolic developing agent or 3-pyrazolidone developing agent is usually 0゜oooz mol/
l-0, comol/II, preferably 0.001 mol/l
It is used in an amount of ~0.1 mol/l.

Sulfites used in the developer of the present invention include sodium sulfite, potassium sulfite, and lithium sulfite.

These include ammonium sulfite, sodium bisulfite, potassium metabisulfite, etc. The sulfite is preferably O03 mol/1 or more, particularly O0 himol/1 or more. Also, the upper limit is 2. jmol/! It is preferable to set it to 1.

For photographic processing of the light-sensitive material of the present invention, JP-A-Sho! 7-711
It is also possible to process with a developer containing imidazoles as a silver halide solvent as described in No. 36. Also, Tokukai Akira! It can be processed with a developer containing a silver halide solvent and an additive such as indazole or triazole as described in Japanese Patent No. 1-374413. The developing solution generally contains other known preservatives, alkaline agents, pH buffering agents, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants, antifoaming agents, etc. Water softener, hardener (
For example, it may contain glutaraldehyde (°), a viscosity-imparting agent, and the like.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The developing method using an automatic processor according to the present invention is described in US Patent No. 3,0! , No. 772, same No. J, j/j,
jjt number, same number J, 673, ril section number, same number J
, 4!7, μj number, British Patent No. 1゜26ri, 2t
It is preferable to use a roller conveyance type automatic developing machine such as that described in No. 1.

The developing temperature is ir'c-jo'c, especially -o 0c.
It is preferable that it is 30°C, and the developing time is in the evening seconds! minutes, especially 10 seconds to Hiro minutes.

The entire development process from the start of development to the end of fixing, water washing, and drying is preferably 30 seconds to 10 minutes, particularly ≠0 seconds to 7 minutes.

As the silver halide in the photosensitive silver halide emulsion used in the present invention, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide can be used, but silver iodobromide is preferably used. It will be done. Here, the content of silver iodide is preferably 30 molt or less,
In particular, it is preferably in a range of 10 molti or less. The distribution of iodine in the silver iodobromide grains may be uniform or may be different between the inside and the surface.

The grain size of the silver halide grains is preferably .mu.m or less, where the diameter of a sphere having the same volume as the grain is defined as the grain size diameter. Particularly preferred is λ, Opm~0.12m. The particle size distribution may be narrow or wide. In particular, JrO% or more of 1oo out of all the grains in the emulsion.
It is very preferred that the particles have a size of 0.3 μm or less and r4 or less and 0.07 μm or more.

The silver halide grains in the emulsion are cubic and tessellated.

/prohedron, rhombus/, regular like dihedron
r) may have a crystal shape, and may be spherical, plate-like,
irregular, such as potato-shaped
) or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms. Further, tabular grains having a particle diameter of three times or more the grain thickness are preferably used in the present invention (for details, refer to RESEARCH DISCLO8URE J 2r
Volume ItemJ2jJ! P, 20-P, 11. /
Monthly issue, /913, and Japanese Patent Application Publication No. Sho TR-IS7YXI, JR-//392).

The photographic emulsion used in the present invention is P, Glafkide.
Written by Chimie et Physique Photo
ographique (published by Paul Monte1,
/ri 67) %G, F'.

Photographic Emuls by Duffin
ionChemistry (The Focal P
ress, 196), V. L. Zelikman
Makingand Coating P by et al.
Photographic Emulsion (The
Published by Focal Press, 1986), Tokukai Sho 3
It can be adjusted using the methods described in 1-/27F21 and 31-//3926. That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

A method in which silver halide grains are formed in an excess of silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion consisting of silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

Even if the crystal structure of silver halide grains is similar to the inside, there are also grains with a layered structure with different inside and outside, and those described in British Patent &3j, t≠/No., US Patent J, 622.
It may also be of a so-called conversion type as described in No. 311. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver rhodan and silver oxide may be bonded, for example. Further, either a surface latent image type or an internal latent image type may be used. In addition to the iridium compounds, cadmium salts, zinc salts, lead salts,
A thallium salt, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Further, during grain formation, grain growth may be controlled by adding so-called silver halide solvents such as ammonia, thioether compounds, thiazolidine-corchion, tetrasubstituted thiourea, rhodanpotash, rhodanammonium, and amine compounds.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. As a method for chemical sensitization, known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used, and these may be used alone or in combination.

Among the noble metal sensitization methods, the gold sensitization method is a typical method and uses a gold compound, mainly a total complex salt. There is no problem in containing complex salts of noble metals other than pure metals, such as platinum and palladium. A specific example is the US Patent Co.

AAT, OTO, British Patent TAR, No. 06.1, etc.

As the sulfur sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used. Specific examples include US Patent/, j74t, tag number j,
Same, core 1. Tag No. 7, same 2. ll10. lrr No., No. 927♂, No. JAF, No. J, jO/, 3/J
No., J, Aj & ? j! This is what is written in the issue.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silano compounds, etc. can be used, and specific examples thereof are described in U.S. Pat. III, No. 471, Ibid. 13, 1,0
No. ri, same co, yr3. tio issue, same, 2, 694A
, I, No. 37.

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more types of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen/composition, sensitivity, etc. A light-sensitive emulsion may be mixed with a substantially non-light-sensitive emulsion (which may or may not be covered on the surface or inside), or may be separated into separate layers (see details for details). are described in U.S. Pat. No. 6,312, U.S. Pat. For example, in the same layer as a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of at least 1 times the grain thickness, or as described in JP-A No. 1986/072/2003. It may be used in different layers such as. When used in different layers, the photosensitive silver halide emulsion consisting of tabular grains may be located on the side closer to the support or, conversely, on the side farther away.

In addition to the above-mentioned compounds, the photographic emulsion used in the present invention may contain various other compounds for the purpose of preventing fogging during the manufacturing process of the light-sensitive material or during storage, or for stabilizing the photographic performance. namely, azoles (e.g. be/dithiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, immetriazoles, aminotriazoles, etc.); mercapto compounds (e.g. mercapto (tetrazoles, mercaptothiazoles, mercaptobenzothianols, mercaptobenzimidazols, mercaptothiadiazoles, mercaptopyrimidines, mercaptotriazines, etc.); thioketo compounds such as oxadorinthione: azaindenes [For example, triazaindenes, tetraazaindenes (especially ≠-hydroxy-substituted (/ + j + J a + 7 ) tetraazaindenes), pentaazaindenes, etc.): benzenethiosulfonic acid, benzenesulfinic acid, benzene Known as antifoggants or stabilizers such as sulfonic acid amides. Many compounds can be added.

Be specific RESERCHDISCLO8ERItem
/7J! Section 7 (/y7e July issue P, 24'P
, 2j) Described in K or cited literature.

In particular, JP-A No. 7 O-7' t3, JP-A-7 O-J' 7
Nitrones and their derivatives described in 32.2, mercapto compounds described in JP-A No. 013-013,
Tokukai Showa J7-/J≠73! The heterocyclic compound and the complex salt of a tetracyclic compound and silver (for example, silver /-phenyl-!-mercaptotetrazole) described in the above publication can be preferably used.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holoholadianine color L styryl dyes, hemicyanine dyes, oxonol dyes, hemioquinol dyes, etc. can be used.

Useful sensitizing dyes for use in the present invention include, for example, RESER
CHDISCLO8URE Item / 76t
A! ■-A section (/ri7 to 2015/February P, 2J), same item
m/1113/ X term (/ri 7 r month P, ≠ 37)
It is described in or cited in the literature.

The sensitizing dye can be used at any stage of the photographic emulsion manufacturing process, or at any stage after manufacturing until immediately before coating. Examples of the former include a silver halide grain formation process, a physical ripening process, and a chemical ripening process.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic agents, etc. Improved compatibility, emulsification and dispersion, prevention of adhesion and improvement of photographic properties (e.g.
One of various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/fuglycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Nonionic materials such as polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of li-acyl, alkyl esters of sugars, etc. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbensene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyltaurifs, sulfosuccinic acid Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkylpolyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl phosphates. / Surfactants; Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic tertiary ammonium salts Cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

As an antistatic agent, especially Tokkai Sho! Turf≠! jF issue,
The fluorine-containing surfactant described in JP-A No. 1.0-1'0rllY, JP-A No. 2-10, JP-A No. 62-λ/J Core No. 2 is due to the polymer, JP-A No. 6-O -7t7μ2, same t
o-rot<6, same 60-r o r<4, same 6
No. 0-40132, No. 60-74711/No. jI-
No. 2017413, No. 2 Co. 7723≠3, JJ-
/73g! Nonionic surfactants described in Japanese Patent Publication No. 15272, T2-CO No. 15272, etc., or JP-A-Sho! 7-20≠! Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in ILtO No. and A2-2/jλ7 No. ILtO can be preferably used. Examples of inorganic antistatic agents include ammonium, alkali metal, and alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, acetates, phosphates, and thiocyanates. Conductive tin oxide, zinc oxide, or a composite oxide obtained by doping antimony or the like with these metal oxides, described in .

In the present invention, US Patent No. λ is used as a matting agent.

Tata λ, No. 10/, Same λ, 70/, Kohiro! No., same It,
/112. l'F4' issue, same! , j5'A, 7 (a homopolymer of polymethyl methacrylate or a polymer of methyl methacrylate and methacrylic acid as described in No. 7j, an organic compound such as starch, silica, titanium dioxide,
Fine particles of inorganic compounds such as sulfuric acid, strontium, barium, etc. can be used. The particle size is /, 0-
It is preferably 10 μm, especially 2 to 3 μm.

The surface layer of the photographic light-sensitive material of the present invention contains a slip agent as described in US Patent No. 3. Hiroturi, j76, room clerk, O≠7, ri! In addition to the silicone compounds described in No. R and the colloidal silica described in Japanese Patent Publication No. 2313, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used.

Polyols such as trimethylolpronone, tantanediol, butanediol, ethylene glycol, and glycerin can be used as plasticizers in the hydrophilic colloid layer of the photographic material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. Polymers include homopolymers of alkyl esters of acrylic acid or copolymers with acrylic acid, styrene-
Butadiene copolymers, polymers or copolymers consisting of monomers having active methylene groups can be preferably used.

The photographic emulsion layer and/or other hydrophilic colloid layer of the present invention is disclosed in Japanese Patent Application No. 42-33! It may contain the composite latex described in J70.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, chromium salts (chromium alum, etc.), dehydes (
formaldehyde, etc.), N-methylol compounds, dioxane derivatives, active vinyl compounds (/, J, J-triacryloyl-hexahydro-8-triazine, bis(vinylsulfonyl) methyl ether, N, N'-methylenebis-[β- (vinylsulfonyl)propionamide]
etc.), active halogen compounds (x, p-dichloro-t-
Hydroxy-5-) riazine), mucohalogen acids (such as mucochloric acid), and the like can be used alone or in combination. Among them, Tokukai Akira! 3-'AI2.20
No. 3-17217, same! Active vinyl compounds described in U.S. Pat.

The active halides described in No. 217 are preferred.

When the photosensitive material of the present invention is used as an X-ray photosensitive material,
The hydrophilic colloid layer must be hardened using these hardening agents so that the swelling ratio in water, defined as (total film thickness in water/dry film thickness), is 300% or less, especially 230% or less. is preferred.

The binder or capture colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention includes:

Although gelatin is advantageously used, other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, calxoxymethyl cellulose, and cellulose sulfate esters; sugar derivatives such as sodium alginate, dextran, and starch derivatives. ; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin may be used, and hydrolysates of gelatin may also be used.

Among these, it is preferable to use dextran and polyacrylamide together with gelatin.

In addition to the light-sensitive silver halide emulsion layer, the silver halide photographic material of the present invention may have non-light-sensitive layers such as a surface acquisition layer, an intermediate layer, and an antihalation layer.

There may be two or more silver halide emulsion layers, and the two or more silver halide emulsion layers may have different sensitivities, gradations, etc.

Further, the support may have seven or more silver halide emulsion layers or non-photosensitive layers on both sides.

Cellulose triacetate films are preferred as supports for general photosensitive materials, and may be colored or uncolored for antihalation purposes.

The support for the X-ray photographic material is preferably a polyethylene terephthalate film or a 7'Cn triacetate e-cellulose film, and is particularly preferably colored blue.

In order to improve the adhesive force with the hydrophilic colloid layer, the support is preferably treated with a corona discharge treatment, a claw discharge treatment, or an ultraviolet irradiation treatment on its surface, or is made of styrene-butadiene latex, vinylidene chloride latex, etc. An undercoat layer may be provided, and a gelatin layer may be further provided on top of the undercoat layer. Further, an undercoat layer using an organic solvent containing a polyester swelling agent and gelatin may be provided. These undercoat layers can be surface-treated to further improve their adhesion to the hydrophilic colloid layer.

The present invention can be used with any photographic material that undergoes normal development processing.

For example, it is used in X-ray photographic materials, lithographic photographic materials, black and white negative photographic materials, color negative photographic materials, color reversal photographic materials, color paper photographic materials, and black and white -par photographic materials.

Here, when used as an X-ray photographic material, R
ESEARCHDISCLO8URE Item
/ruj/(/97F r month P, 1A33~P, 41/
) Techniques related to stabilizers, antifoggants and anti-nick agents (P, ≠ 33 to P, 4 < J 4) Techniques related to protective layers (P, #3t, item ■), Crossover control technology ( P, ≠361V term), etc. are preferably used.

To obtain an X-ray photographic image, exposure may be carried out using conventional methods. That is, the method involves directly irradiating X-rays or sandwiching a photosensitive material having photosensitive layers on both sides between two fluorescent intensifying screens or lead foil intensifying screens to expose the material to X-rays.

Alternatively, in the case of a photosensitive material with a photosensitive layer on one side, a method is used in which a fluorescent intensifying screen is irradiated with X-rays and the emitted light is recorded on the photosensitive material. Of course, the X-rays may be irradiated by bringing the photosensitive material into contact with the fluorescent intensifying screen. Here, as the phosphor, a blue-emitting phosphor such as calcium toughgestate or barium sulfate, or a green-emitting rare earth phosphor is used. In addition, after accumulating the X-rays exposed in the phosphor, various light sources including infrared light such as cathode ray tube flying spot, light emitting diode, laser light (e.g. gas laser, YAG laser, dye laser, semiconductor laser, etc.) can be used. It can also be exposed to light.

<Example> Next, the effects of the present invention will be specifically explained.

(Example 1) A silver nitrate aqueous solution and a potassium bromide aqueous solution were added to a gelatin aqueous solution to prepare silver bromide particles with an average particle size of 0.27 μm.

To this emulsion were further added an aqueous solution of silver nitrate, potassium bromide, potassium iodide, and an aqueous solution of potassium hexachloroiridate (I[[)].

Silver iodobromide containing silver iodide was formed on the outside of the previous grain. The final particles had a size of 0.3 hiromu.

After desalting this emulsion in the usual manner, /, Kointsinthiazolin-3-one, β-oxyethylphenyl ether and gelatin were added, /phenyl-! -Gold/sulfur sensitization was performed by adding mercaptotetrazole.

Exemplary compounds as shown in Table 1 were added to this emulsion, and 4'-hydroxy-+-methyl-/.

3,ja,7-thitrazaindene and 3-(!-mercaptotetrazolyl)-benzenesulfonic acid l-I
It was stabilized by adding Jum. In addition, polyacrylamide, resorcinol, and even absorbing adult t 2 j nm
A dye with an absorption rate of J/Onm was added, and a hardening agent was added so that the development swelling ratio was 230 inches (total film thickness when swollen/dry film thickness), and the mixture was coated on a polyethylene terephthalate support.

At the same time, matting agents, inorganic salts, fluorine-containing compounds, anionic surfactants, organopolysiloxanes,
DV-7 described in 2-33jj70! Then, a surface protective layer containing a polyethylene oxide nonionic surfactant was applied.

Such coating was carried out on both sides of the support, and the amount of coated silver on each side was 7 g/m2 (on both sides/≠
g/m2). (Samples Aa to C) Next, developer concentrate note A, ξ-t B1. e) Show the formulation of C and starter.

/ξ meat 1
Part B for 01 Part C Diethylene glycol for starter 1OjJ 720g The method for preparing the working solution is to add water to about 61g and note A to 2°jJ,,e-
Add and dissolve 40ml of part B and 20ml of part C with stirring, and finally make 101 with water.
pH 10. Adjusted to μO. This used solution is used as a developer replenisher. Add 20% of the starter to this replenisher/l.
It was added at a ratio of ml.

This liquid is the developer tank liquid and is used at the start of running.

Next, as shown in Table 1, using K and various developing solutions, the following development processing was performed using an A-2 transport type automatic processor.

The automatic developing machine was operated for 3 days for 7 tests, and on each operating day, 100 sheets of half-exposure (so that the optical density was approximately 2.0) and half-cut (Jj, Acmx≠3.2 cm) were processed. Processed.

After 300 sheets were processed by repeating the above-described running process, silver stains were evaluated based on the stains on the wall inside the developer tank, the stains on the roller surface, and the degree of stains attached to the photosensitive material.

At the same time, they were exposed to light using the method shown in Japanese Patent Application No. 6, Coater μr72, and developed at the end of the second month of each working day to determine the relative sensitivity of the light-sensitive materials.

Table 2 shows the results obtained from such experiments.

(Table) Processing process Development fixing 8 Washing temperature 2!0C 23°C Co'C Time 3 minutes 3 minutes 3 minutes Replenishment measurement Occ/(3!, A x !j, 2cm)
300cc/()! , Ax33. 31//min per λcm) Exemplary Compound (1) As can be seen from Table λ, when this compound is added to the emulsion layer, silver stains in the developing tank are extremely reduced.

Also, when comparing this result with the case where the compound was added to the developer, it was found that the same effect could be obtained with the addition amount of about 2/2,
In this case, it can be seen that there is an advantage that the decrease in sensitivity is rather small.

(Example 1) Potassium bromide in 1 liter of emulsion preparation water! g, potassium iodide, org, gelatin 30g, thioether HO(CH2)2S(CH2)2S(CH2)20H! Aqueous solution.

Add t cc to the solution maintained at 73°CK, add 33 g of silver nitrate 1r and potassium bromide with stirring! .

An aqueous solution containing 7 μg and 726 g of iodizing power IJ O was added in 4'J-seconds using a double jet method. Subsequently, after adding 72, j g of bromide power, silver nitrate r
.

An aqueous solution containing 33 g was added over 2 portions so that the flow rate at the end of the addition was double that at the start of the addition.

2 more to come! % ammonia solution 20 cc,!
After adding 0% NH4NO3/Occ and physically ripening for 20 minutes, /N sulfuric acid 2≠Occ was added to neutralize. Next, silver nitrate/! 3.311 g of an aqueous solution and an aqueous solution of potassium bromide were added in ≠θ minutes by a controlled double jet method while maintaining the potential at pAgJ', 2. The flow rate at this time was accelerated so that the flow rate at the end of addition was twice the flow rate at the start of addition.

After the addition is complete, add 2N potassium thiocyanate solution! cc and further 7% potassium iodide aqueous solution 2! cc was added over 30 seconds. After this, the temperature was lowered to 3r'C and soluble salts were removed by the sedimentation method, then the temperature was raised to ≠00C, 30g of gelatin and phenolcog were added, and the pH was adjusted to 6.4LO, pAgf, / with wild soda and potassium bromide.
Adjusted to 0.

After raising the temperature to 6°C, 10mg of a sensitizing dye having the following structure and 0mg of a stabilizer were added. After 10 minutes, μmg of thiosulfuric acid, Omg of potassium thiocyanate, and J/mg of chloroauric acid were added to each emulsion, and after 10 minutes, the mixture was rapidly cooled and solidified to form an emulsion. In the obtained emulsion, 2j% of the total projected area of all grains consists of grains with an asbestos ratio of 3 or more, and the average projected area diameter of all the grains is 7.4.
Lμm% Standard deviation Ko2chi, average thickness FiO, /17
The aspect ratio in μm is 7. It was J'.

ΦWater-soluble polyester Adjust the amount of silica added. Table-/ Types of description and amount ・Polymer latex (Polymer latex) Li(ethyl acrylate) /methacrylic acid)=ri7 /3) ・Hardening agent 2j, Og.

- Phenoxyethanol λ g The following chemicals were added per mole of silver halide to the emulsion to prepare a coating solution.

・Gelatin Table-/Ag/Bin listed
The ratio will be 2.6-bis(hydroxyamino)-≠-diethylamino-/,! ,! - Triazine 10 mg ・Sodium polyacrylate (average molecular weight ≠, 10,000) Hiroshi, Og ・Potassium polystyrene sulfonate (average molecular weight t 0,000) /, Og ・Exemplary compound (2) of the present invention (amount ≠ in the table) ・Exemplary compounds of the present invention (
3) (Amounts shown in Table 1) The above coating solution was coated on a 773 μm thick transparent PET support simultaneously with the surface protective layer coating solution.

The total amount of silver coated on both sides is 3. ．． It was set to 2g7m2.

The surface protective layer was prepared so that each component had the following coating amount.

0.0. 2 0.0Jj o, oi Q, 00I 3H7, C4F17802N+CH2-)(-CH2-9;y
sO3Na0.00/ e gelatin / , / j g/
m2・Polyacrylamide (average molecular weight ≠, 0,000) O, Coj ・Sodium polyacrylate (average molecular weight ≠0,000) O, O2・pt-octylphenoxydi-glycerylbutyl sulfo 0. 003 and Proxel 0,00/・Polymethyl methacrylate (average particle size 3.52 m) 0,02!・Poly(
Methyl methacrylate/methacrylate) (molar ratio 7:3, average particle size).

μm) - Exemplary compound (2) - Exemplary compound (3) Exemplary compound (2)! 0.020 (Amount of surface coating) () (Table-3) Processing process temperature time Replenishment amount Development 3z0c/a second 1Ltjml/1Ox
l coin inch (cutting size) Fixation 3.2°C//sec tOml/10'sC/
2 inches (41, cut size) Exemplary compound (3) The automatic processing machine is operated for t days a week, and on the operating days, it processes ioo sheets of half-exposed cut size (10 inches x / 2 inches) per 7 days. did.

The same developing solution as in Example 1 was used in this automatic processor, and Table 3
The experiment was conducted under the conditions shown below.

Dry zsoc io second meter ≠! Note that Fuji F (manufactured by Fuji Photo Film Co., Ltd.) was used as the fixing solution.

The running experiment as described above continued for a total of one week, and the total number of sheets processed was 1200 sheets.

The results thus obtained are shown in Table-≠.

As can be seen from Hiroshi Omote, the effect of this compound was confirmed in this experiment as well, and it can be seen that it is equally effective not only when added to the emulsion layer but also when added to the surface protective layer.

(Example 3) Emulsion A prepared in the same manner as in Example 3 had an average grain size of 0.3 μμ and 9j grains of 0.2 μ or less and 0.12 or more.
%. Separately, Emulsion B was prepared in exactly the same manner as Emulsion A except that the amount of ammonia was changed. This emulsion B has an average grain size of 0.1. J-μ
and 0. It contained 70% of particles with jμ or less of 0.12 or more.

List these emulsion A and emulsion B! Mix in the proportions shown in 4! -Hydroxy-6-methyl-7,3゜3a,7-
Citrazaindene and sodium J-(t-mercaftotetrazolyl)-benzenesulfonate were added for stabilization. Furthermore, polyacrylamide, resorcinol, a dye with an absorbing capacity of A 2 J nm, a dye with an absorption dilation of j/Onm, and the compounds shown in Table A hardening agent was added and coated on a polyethylene terephthalate support so that the resultant film had a thickness of /dry film thickness. At this time, a matting agent,
Inorganic salt, fluorine-containing compound, anionic surfactant, organopolysiloxane, patent application Sho AJ-33! ! DV-7 described in issue 70! Then, a surface protective layer containing a polyethylene oxide nonionic surfactant was applied.

Each sample e-gVi thus obtained was coated with the same amount of silver on both sides, and lλ on both sides.

It was made to be 0g7m2.

Using these samples, experiments as shown in Table 3 were carried out in the same manner as in Example.

At this time, graininess was also evaluated using the following method.

The results thus obtained are shown in the table below.

(Grain: RMS evaluation method) (1) To determine the relative sensitivity, an X-ray using a button, a lead intensifying screen, and a cassette were used, and the optical density after development was 2.
X-rays are irradiated so that the temperature becomes O.

(2) This sample is developed after the sample for determining relative sensitivity.

(3) One side of the sample obtained by plating is removed using sodium hypochlorite.

(4) Measure this single-sided sample with a microdensitometer that measures grain size (measurement using a circular slit with a diameter of /-μm). From this, calculate R, M, and S.

From this example, O0! Particles with sizes below μm and above! If it contains 0 or more, the RMS will improve, but on the other hand, silver contamination will worsen. It can be seen that when the emulsion layer contains the compound shown in the present invention, silver staining can be prevented even in such cases without deterioration of RMS.

Claims (2)

[Claims] (1) A silver halide photographic material having at least one silver halide emulsion layer on a support, containing at least (a) a hydroquinone developing agent, and (b) a sulfite of 0.1 mol/l or more. In a method for developing a silver halide photographic material which is processed with a developer, the silver halide photographic material contains at least one of the following (X) or (Y). Development processing method. (X) Compound (I) represented by the following general formula (I) ▲ Numerical formula, chemical formula, table, etc. group group, aromatic group or heterocyclic group 5
membered ring or 6-membered ring (this ring may be further fused,
containing 1 to 3 nitrogen atoms and 1 oxygen atom or 1 sulfur atom), m_1 and n_1
are the numbers 1, 2 and 3, respectively, and p is 1 or 2
, A_2 and E_2 independently have the formulas -CO-O-M, -SO_2-O-M, ▲mathematical formulas, chemical formulas, tables, etc.▼, -S-Z and ▲mathematical formulas, chemical formulas, tables, etc. ▼ (In these formulas, X and Y are each a hydrogen atom or an alkyl group of up to 8 carbon atoms optionally substituted by a hydroxyl group, a carboxylic acid group, or a sulfonic acid group, and Y is further phenyl. It may be a sulfonic acid group, a lower alkylsulfonyl group or a phenylsulfonyl group, M is a monovalent cation, Z is X and Y
(has the same meaning as , except that it is not a hydrogen atom). However, when it is a group represented by -CO-OM, the corresponding B_1 and D_1 mentioned above do not have an α-amino group. ](Y)
(y1) and (y2) (y1) Compounds represented by the following general formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, R represents a phenyl group or a lower alkyl group. ] (y2) At least one compound represented by the following general formula (III), amino(lower)alkanethiosulfonic acid, or an alkali metal salt thereof. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R' represents a phenyl group or a lower alkyl group, and M represents hydrogen or an alkali metal. ] (2) The developing method according to item 1, wherein 50% or more and 100% or less of the silver halide grains in the entire emulsion layer are composed of grains having a grain size of 0.5 μm or more and 0.1 μm or more.