JPH0355541A - Development processing method for silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To decrease the silver stains generated in a developing tank and/or on a developing rack and roller surface by subjecting the silver halide photosensitive material having >=10g coating amt. of silver per 1m<2> to image exposing, then processing the material by a developing soln. contg. a specific compd. CONSTITUTION:The silver halide photographic sensitive material having >=10g/m<2> in total coating amt. of silver is subjected to the image exposing and is then processed by the developing soln. contg. at least (a) a hydroquinone developing agent, (b) >=0.3mol/l sulfite and (c) the developing soln. contg. formula I or at least one of formula II and formula III. In the formula I, B1 and D1 respectively independently denote an aliphat. group, alicyclic group, etc.; m1 and n1 are respectively 1 to 3 integer; p is 1 or 2; A2 and E2 are respectively independently formulas -CO-O-M, -SO2-O-M, etc.; M is a monovalent cation. In the formula II, R denotes a phenyl group or lower alkyl group. In the formula III, R' denotes a phenyl group or lower alkyl group; M denotes a hydrogen atom or alkaline metal. The silver stains generated on the walls in the developing tank and on the roller surface 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,
More specifically, it relates to a method for reducing the amount of silver stain (also referred to as silver sludge) that adheres to developing tanks, developing racks, and rollers during the processing of photographic materials, thereby facilitating the daily maintenance of tools and equipment. .

Conventional technology> Generally, when silver halide photographic light-sensitive materials are developed, depending on the amount of processing, the development tank, vat, automatic developing machine (
It has been known for a long time that silver adheres and accumulates on the walls, developing tanks, and developing rollers of developing machines (hereinafter referred to as automatic processors). This is also called silver stain or silver sludge, and it adheres to the photosensitive material being processed and stains the image, so it is necessary to regularly clean and maintain the equipment.

In addition, especially for industrial X-ray sensitive materials, high sensitivity and fine grains are ensured by increasing the amount of silver coated without extremely increasing the grain size. It requires a long time. In processing such sensitive materials, ■
The silver halide grains are fine grains. ■Large amount of silver coated
■Developing time is long. All of these characteristics are factors that increase the amount of silver halide dissolved during development, making silver stains extremely likely to occur.

Furthermore, the image of the defect to be detected in the industrial X-ray sensitive material often shows only a slight change in density, and even the change in density caused by this silver stain is a huge hindrance in terms of image identification. becomes.

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 is known, as in No. 6-2 4 3 4 7. 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 from using it all at once. In addition, a decrease in sensitivity is a serious drawback for a photosensitive material/development processing system that is intended to be used with as high a sensitivity as possible.

OBJECTS TO BE SOLVED BY THE INVENTION Therefore, the purpose of the present invention is, first, to reduce the silver stains that occur in the developing tank and/or the developing rack and rollers when developing silver halide photographic materials. to do,
Second, it facilitates the maintenance of automatic processors and developing equipment; third, it reduces silver contamination without affecting photographic properties; and fourth, it does not compromise 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, fine grain, and no silver stain when processing a photosensitive material such as an industrial X-ray photosensitive material using an automatic processor. be.

Means for Solving Problems> The object of the present invention is to apply at least the following (a), (b), This could be achieved by developing with a developer containing component (c).

It is characterized by processing with a developer containing (a) a hydroquinone-based developing agent, (b) a sulfite of 0.1 mole or more and (C) at least one of the following (X) or the following (Y): A method for developing silver halide photosensitive materials.

(X) Compound (I) (S) represented by the following general formula (I)
, D. (-Et), S-B. (
-At)ゎ(Y) The following (y1) and (y2) (yl) Compounds represented by the following general formula (I!) SH R-CHCH. -COOH [In the formula, R represents a phenyl group or a lower alkyl group. ] (y2) At least one of the compound represented by the following general formula (III), amino(lower)alkanethiosulfonic acid, or an alkali metal salt thereof.

s-sow M R'-CHCH. -COOH [In the formula, R' is a phenyl group or a lower alkyl group, M
represents a hydrogen atom or an alkali metal. ]General formula (I)
Preferred compounds among the compounds represented by the general formula (I'
/), (V).

General formula (N) General formula (V) S S-C-COOM HaR. R, in the general formula (■), R+ and R- are a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkenyl group, an aralkyl group, a cycloalkyl group, an optionally substituted phenyl group, Represents a 5- or 6-membered heterocycle containing 1 to 3 nitrogen atoms, 1 oxygen atom or 1 sulfur atom, or a carboxyl group, and R2 represents a direct bond or an optionally substituted alkylene group , an alkylidene group, a phenylene group, an aralkylene group, or one CONHCH.
- represents A. is -COOM or -SO. M(M
is synonymous with general formula (1)) ms is 1 or 2.

In general formula (V), R. , R. represents a hydrogen atom or a methyl group.

M is preferably a hydrogen cation or an alkali metal cation (such as Na@ or KΦ).

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

General formula (VI) In general formula (Vl), R. , Rt is a hydrogen atom, an optionally substituted alkyl group (e.g. -CH., -C.Hl,
-CH! OH, 1CH. COOH, etc.), cycloalkyl groups (e.g., cyclopentyl group, cyclohexyl group, etc.), optionally substituted phenyl groups (e.g., phenyl group, tolyl group, p-chlorophenyl group, p-aminophenyl group, p-sulfophenyl group, p-sulfophenyl group, - sulfonamidophenyl group, etc.), or a 5- or 6-membered heterocycle containing 1 to 3 nitrogen atoms, 1 oxygen atom or 1 sulfur atom (such as furyl group, chenyl group, etc.), or carpon It represents an acid group, and Ra and Re may be the same or different.

1 is 1, 2, 3, or 4.

Next, in general formulas (I) and (■), the lower alkyl group represented by RSR' includes methyl group, ethyl group, probyl group, etc., and amino(lower)alkanethiosulfonic acid includes aminoethylthiosulfonic acid. etc.

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

HOOC-H. C-S-S-CH. -COOHH. C-
HC-S-S-CH-CH. HOOC COOH H. C-HC-S-S-CH-CH. HOOC-HC-S-S-CH-COOH1 HOOC-H. C CH. -COOH thiolactic acid α-mercabutoisobutyric acid HOOC (CH^1S S (CH*)g CO
OHHOOC (CHI) $ S S- (CH!
)3 COOHCH. CH. KODC-CH. -NH-Co-CH-S-S-CH-
CO-NH-CH2-(3)KCHs CH. HOOC-CH. -S-S-S-CH. Specific examples of compounds represented by the -COOH general formula (n) or (II[) are listed below.

S.H. CH* -CHCH. -COOH SSO. K l CH. -CHCH. -COOH General formula (I) (n) (I[) represented by The method for synthesizing the compound was published in Japanese Patent Publication No. 56-46, No. 585, same No. 62-28,459, etc.

The amounts of the compounds X and Y added are preferably 0.01 to 50 g, more preferably 0.01 to 50 g, respectively, per liter of developer.
05-20g. For Y, (yl): (y2
) molar ratio of 100:1 to I:100, especially 5:1 to 1
:20 is preferable.

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 other types.

Hydroquinone-based developing agents used in the present invention include hydroquinone, chlorohydroquinone, promhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromhydroquinone, 2,5 -Dimethylhydroquinone, hydroquinone monosulfonate, etc., and hydroquinone is particularly preferred.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl). There are glycine, 2-methyl-p-aminophenol, p-pendylaminophenol, among others, N-methyl-p
-Aminophenol is preferred.

The 3-virazolidone developing agent and shite used in the present invention are l
-phenyl-3-virazolidone, l-phenyl-3-virazolidone, l-phenyl-3-virazolidone, 4.4
-dimethyl-3-virazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-virazolidone, 1-
Phenyl-4,4-dihydroxymethyl-3-virazolidone, l-phenyl-5-methyl-3-virazolidone,
1-p-aminophenyl-4.4-dimethyl-3-virazolidone, 1-p-tolyl-4.4-dimethyl-3-virazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-virazolidone, and so on.

Hydroquinone-based developing agents are usually 0.01 mol/1 to 1
．． 5 mol/1, preferably 0.05 mol/1 to 1.
It is used in an amount of 2 mol/1.

In addition to this, the p-aminophenol developing agent or 3-virazolidone developing agent is usually 0.0005 mol/
l~0.2 mol/l, preferably 0.001 mol/l~
0. It is used in an amount of 1 mol/l.

Sulfites used in the developer of the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
and so on. Sulfite is 0.3 mol/1 or more, especially 0.3 mol/1 or more.
It is preferably 4 mol/l or more. Further, it is preferable that the upper limit is 2.5 mol/'l in the developer concentration section.

The pH of the developer used in the development process of the present invention is preferably in the range of 9 to 13. More preferably, the pH range is from 10 to 12.

Alkaline agents used to set pH include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, and potassium triphosphate.
Contains H regulator.

JP-A-62-186259 (Borate), JP-A-62-186259 (Borate)
Buffers such as No. 0-9 3 4 3 3 (eg, sutucarose, acetoxime, 5-sulfosalicylic acid), phosphates, carbonates, etc. may be used.

In the present invention, the developer preferably contains a chelating agent having a chelate stability constant of 8 or more with respect to iron ions.

Here, the chelate stability constant is defined as L. G. Stlls
Sn●A. E. by Martell, H. “Sta.
billttyConstants of Metal
-ion Coaiplexes, TheChe
mical Society, London (
1 9 6 4). S, Chaberek●A.
E. by Martell, 'OrganicS
Equestering Agents, Will
ey (1 9 5 9).

etc. means a commonly known constant.

In the present invention, examples of the chelating agent having a chelate stability constant of 8 or more for iron ions include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Note that the above-mentioned iron ion means ferric ion (Fe'").

In the present invention, specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include the following compounds, but are not limited thereto. Namely, ethylenediamine diorthohydroxyphenylacetic acid, triethylenetetraminehexaacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, Hydroxyethyliminodiacetic acid, l,3-diamino-2-
Probanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamine-N,N,N',
N'tetrakis methylene phosphonic acid, nitrilo N. N
．． N-}rimethylenephosphonic acid, l-hydroxyethylidene-1. 1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2
．． 4-1 ricarponic acid, 1-hydroxy-1-phosphonopropane-1. 2,'3-tricarboxylic acid, catechol-3,5-disulfonic acid, sodium birophosphate,
Examples include sodium tetrapolyphosphate and sodium hexametaphosphate.

Further, a dialdehyde hardening agent or its bisulfite adduct is used in the developer, and specific examples thereof include glutaraldehyde and its bisulfite adduct.

Additives used in addition to the above components include development inhibitors such as sodium bromide, potassium bromide, and potassium iodide:
Organic solvents such as ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol; l-phenyl-5-mercaptotetrazole, 2-mercabutobenzimidazole-5-sulfonic acid sodium salt, etc. It may contain antifoggants such as mercapto compounds, indazole compounds such as 5-ditroindazole, and penzotriazole compounds such as 5-methylbenzotriazole.
Disclosure Volume 176, No. l 7 6
43, Section XXI (December issue, 1978), as well as color toners, surfactants,
It may also contain an antifoaming agent, a water softener, an amino compound described in JP-A-56-106244, and the like.

In the development process of the present invention, a silver stain preventive agent other than the silver stain preventive agent of the present invention is added to the developing solution, such as JP-A-56-2434.
Compounds described in No. 7 can be used.

The developer of the present invention includes European Patent Publication No. 136582
No. 958,678, U.S. Patent Register No. 32327
Amino compounds such as alkanolamines described in No. 61 and JP-A-56-106244 can be used for the purpose of accelerating development, increasing contrast, and other purposes.

Besides this, L. F. “Photographic Processing Chemistry” by A. Mason, published by Focal Press (
1966), pp. 226-229, U.S. Patent No. 2,19
No. 3,015, No. 2,592,364, Japanese Unexamined Patent Publication No. 1973-
64933 and the like may be used.

The fixer is an aqueous solution containing thiosulfate and has a pH of 3.8 or higher, preferably 4.2 to 7.0.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0. 1 to about 6 mol/l.

The fixer may also contain water-soluble aluminum salts that act as hardeners, such as aluminum chloride, aluminum sulfate, potassium alum, and the like.

In the fixing solution, tartaric acid, citric acid, gluconic acid, or their derivatives can be used alone or in combination of two or more. These compounds contain 0.0 per liter of fixer.
Those containing 0.05 mol or more are effective, especially 0.01 mol/i
~0.03 mol/1 is particularly effective.

The fixing solution may optionally contain preservatives (e.g., sulfites, bisulfites), pH buffers (e.g., acetic acid, boric acid), pH adjusters (e.g., sulfuric acid), chelating agents with water softening ability, and The compound described in No. 62-78551 may be included.

In the present invention, "developing process time" or "developing time" refers to the time from when the leading edge of the photosensitive material to be processed is immersed in the developing tank solution of the automatic processing machine until it is immersed in the next fixing solution. The period from immersion in the fixing tank solution to the next immersion in the washing tank solution (stabilizing solution) "Washing time" refers to the time spent soaking in the washing tank solution.

In addition, "drying time" is usually 35℃ to 10℃ for automatic processors.
A drying zone is installed in which hot air of 0°C, preferably 40°C to 80°C is blown, and refers to the time spent in the drying zone.

In the development process of the present invention, the development time is 10 seconds to 8 minutes, preferably 30 seconds to 5 minutes, and the development temperature is preferably 17°C to 40°C, more preferably 20°C to 35°C.

The fixing temperature and time are preferably about 17° C. to 40° C. and 10 seconds to 5 minutes, more preferably 18° C. to 30° C. and 30 seconds to 3 minutes.

Water washing or stable dissolution temperature and time are 00-50℃ for 10'
-8 minutes is preferable, and 15 degreeC - 30 degreeC, 30 seconds - 3 minutes are more preferable.

According to the method of the invention, the developed, fixed and washed (or stabilized) photographic material is dried by squeezing out the washing water, ie passing through a squeeze roller. Drying is carried out at about 30°C to about 100°C, and the drying time can be changed appropriately depending on the surrounding conditions, but it is usually about 10 seconds to 3 minutes, particularly preferably about 30 seconds to 80°C. It is 3 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 preferable. used. The content of silver iodide is preferably 30 mol% or less, particularly 1O mol% 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 4 μm or less, where the grain size is defined as the diameter of a sphere having the same volume as the grain. In particular, 2.0 μm to 0.1 μm is preferable. The particle size distribution may be narrow or wide. In particular, 50% or more and 100% or less of all the grains in the emulsion are 0. It is highly preferred that the particles consist of particles with a size of less than 5 .mu.m to 0.1 .mu.m.

The silver halide grains in the emulsion may have regular crystal shapes such as cubic, octahedral, tetradecahedral, and rhombic dodecahedral, or may have irregular crystal shapes such as spherical, plate-like, potato-like, etc. It may have an irregular crystal form 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 5 times or more the grain thickness are preferably used for the present invention (in detail, R
ESEARCH DISCLOSURE Volume 225 It
em 22534 P. 20 ~P. 58, January issue, 1983, and JP-A-58-127921, same 5
8-113926).

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. Substantially non-light sensitive emulsion (
(The surface or interior may or may not be covered) may be mixed and used, or may be separated into separate layers (for details, see U.S. Pat. No. 2,996,382, No. 3, 3
No. 97,987, etc.). For example, a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 5 times or more than the grain thickness may be placed in the same layer or in a different layer as described in JP-A-58-127921. May be used for. 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.

The photographic emulsion used in the present invention is P. Glafkid
Chimie et Phisique Pho by es
tographique (Paul Nontel, 1967), G.F. Written by Duffin Ph.
otographic Emulslon Che
mistry (The Focal Press
(Published, 1966), V. L. Zeltk+san
Written by etat? Iakia (and C
oting Photographic Emuls
ion (The Focal Press, 19
1964), JP-A-58-127921 and JP-A No. 58-1
It can be adjusted using the method described in Japanese Patent No. 13926 and the like. 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. ．． It is also possible to use a method in which halogenated linear particles are formed in an excess of silver ions (the so-called back-mixing method). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase is kept constant under the control of halogenated radiation, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion consisting of silver halide grains with a regular crystal shape and a nearly uniform grain size can be obtained. Even if the crystal structure of silver halide grains is uniform inside, there are also those with a layered structure with different inside and outside, British Patent No. 635.841, US Patent No. 3,622.3
It may also be of the so-called conversion type as described in No. 18. Further, halogenated resins having different combinations may be joined by epitaxial joining, and compounds other than Rodin's daughter and silver oxide may be joined, for example. Also, either surface H& type or internal latent image type is acceptable. Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or their complex salts, rhodium salts or their complex salts, iron salts or iron complex salts, etc. may coexist. Further, when controlling particle size, so-called halogenated SFAm agents such as ammonia, thioether compounds, thiazolidine-2-thione, tetrasubstituted thiourea, rhodanpotash, rhodanammonium, and amine compounds may be present to control particle size. The halogenated emulsion used in the present invention may or may not be chemically sensitized. Known methods such as sulfur sensitization, reduction sensitization, and gold sensitization can be used as methods for chemical sensitization, 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 gold compounds, mainly gold complex salts. There is no problem in containing complex salts of noble metals other than gold, such as platinum, palladium, and iridium. A specific example is U.S. Patent 2,448.06
No. 0, British Patent No. 618.061, etc. As the sulfur field sensitizer, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thioM salts, thioureas, thiazoles, and rhodanine compounds can be used. As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used. The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. That is, azoles {e.g., penzothiazolium salts, nitroimidazoles, nitrobenzydazoles, chlorobenzicamedazoles, promobenzidazoles, nitroindazoles, penzotriazoles, aξnotriazoles}: merkabut Compounds [e.g. merkabutothiazoles,
Mercabutobenzothiazoles, merkabutobenzimidazoles, merkabutothiadiazole, merkabutotetrazole (particularly 1-phenyl-5-mercaptotetrazole), merkabutopyrimidines, merkabuttriazines, etc.; For example, oxadrinthione Thioketo compounds such as; azaindenes (e.g. triazaindenes, tetraazaindene B (especially 4-hydroxy substituted (1.3,3a.7) tetraazaindene), pentaazaindene, etc.); benzenethiosulfonic acid A number of compounds known as antifoggants or stabilizers can be added, such as benzenesulfuric acid, benzenesulfonic acid, penzenesulfonic acid amide, etc. Specifically, RESERCH DISCLOSURE
Item 7 6 43 ■ (1978 12
Monthly issue P. 24~P. 25) or in the literature cited. In particular, JP-A No. 60-76743,
Nitrones and their mK derivatives described in JP-A No. 60-87322, mercabuto compounds described in JP-A-60-80839, heterocyclic compounds and heterocyclic compounds described in JP-A-57-164735. Complex salts of compounds and silver (e.g. l-phenyl-5-mercaptotetrazole 1!)
etc. 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, holophoric cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used. Useful sensitizing dyes for use in the present invention include, for example, RESERCH DISCL
OSURE Ite+g 1 7 6 4 3 [V
- Section A (December 1978, P.23), same r.
ts+sl 8 4 31X (August 1979, P. 437) or in the literature cited. 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 the silver halide particle formation process, the physical P process, and the chemical process. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention contains a coating aid, antistatic agent, slippery improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes such as nonionic surfactants such as sabonin (steroid type) and alkyl esters of sugars; alkyl sulfonates, alkylbenzene sulfonates, alkyl Naphthalene sulfonate, alkyl sulfate, N-
Anionic surfactants such as acyl-N-alkylcurins, sulfosuccinates, and sulfoalkylborioxyethylene alkylphenyl ethers; amphoteric surfactants such as alkylbetaines and alkylsulfobetaines; aliphatic or aromatic surfactants; Cationic surfactants such as quaternary ammonium salts, viridinium salts, and imidazolium salts can be used. Among these, sabonin, dodecylbenzenesulfone 9Na salt, di-2-ethylhexyl α-sulfosuccinic acid Na salt, p-octylphenoxethoxyethoxyethanesulfonic acid Na salt, dodecyl iaNa salt, }liinpropylnaphthalene sulfonate 7
Anions such as JNa salt, N-methyl-oleoyl curine Na salt, dodecyltrimethylammonium chloride, N-oleoyl-N'N',N'-}limethylammoniodiaminopropane bromide, dodecylpyridium chloride, etc. cation, N-dodecyl-N. N-
Dimethylcarboxybetaine, N-oleoyl-N,
Betaines such as N-dimethylsulfobutylbetaine can be particularly preferably used. As the antistatic agent, perfluorooctanesulfonic acid KI, N-probyl-N-perfluorooctanesulfonylglycine Na salt, N-probyl-N-berfluorooctanesulfonyl aξnoethyloxyboly(n=3)
Oxyethylenebutanesulfonic acid Na salt, N-perfluorooctanesulfonyl-N',N',N'-}limethylammoniodiatonopropane chloride, N-perfluorodecanoyla ξnobrovir N',N' Preferably used are fluorine-containing surfactants such as dimethyl-N'-carboxybetaine, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides doped with antimony or the like. In the present invention, as matting agents, homoponomers of polymethyl methacrylate or polymers of methyl methacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, strontium, and barium can be used. ．． The particle size is preferably 1.0 to 10 μm, particularly 2 to 5 μm. In addition to the slip agent silicone compound and colloidal silica described in Japanese Patent Publication No. 56-23139, paraffin wax, higher fatty acid esters, starch derivatives, etc. can be used in the surface layer of the photographic material of the present invention. Polyols such as trimethylolpropane, pentanediol, 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 contains polymer latex for the purpose of improving pressure resistance. It is preferable to contain. As the polymer, a homopolymer or a copolymer of an alkyl ester of acrylic acid or a copolymer with acrylic acid, a styrene-butadiene copolymer, and a polymer or copolymer consisting of a monomer having an active methylene group can be preferably used. The photographic emulsion layer and/or other wood-philic colloid layer of the present invention may contain the composite latex described in Japanese Patent Application No. 62-335570. The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners. For example, chromium salts (chromium alum), aldehydes (formaldehyde, glitaraldehyde, etc.)N
- methylol compounds (dimethylol urea, etc.) dioxane derivatives (2,3-dihydroxydioxane, etc.),
Active vinyl compound (1.3.5-}reacryloyl hexahydride-$1 triazine, bis(vinylsulfonyl) methyl ether, N.N'-methylenebis-(β-(
vinylsulfonyl) propionamide], active halogen compounds (2,4-dichloro-6-hydroxy-s
-} riazine, etc.), mucohalogen acids (mucochloric acid, etc.), isoxazoles, dialdehyde starch, 2
-Chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them,
Unexamined Japanese Patent Publication No. 53-53-5725
7, active vinyl compounds described in 59-162546 and 60-80846 and U.S. Pat. No. 3,325,287
The active halides described in this issue are preferred.

It is preferable that the hardening layer of the hydrophilic colloid layer is hardened using these hardening agents so that the swelling ratio in water is 280% or less.

The photographic light-sensitive material of the present invention may have two or more silver halide emulsion layers, and in this case, the two or more silver halide emulsion layers may have different sensitivities, gradations, etc.

Further, one or more silver halide emulsion layers or non-photosensitive layers may be provided on both sides of the support.

The coating amount of the silver halide emulsion layer of the present invention is 10.0 g/rrr or more in terms of the coating amount of silver on both sides of the entire emulsion.

This means that the silver halide emulsion layer has a weight of 10.0 g per side.
tri or more, and the other side may be coated with a layer containing no silver halide particles,
Alternatively, 5.0 g or more of silver halide emulsion may be coated on each side.

Cellulose triacetate film is preferred as a support 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 cellulose triacetate film, and is particularly preferably colored blue.

In order to improve the adhesion with the hydrophilic colloid layer, the surface of the support is preferably subjected to corona discharge treatment, claw discharge treatment, or ultraviolet irradiation treatment, or is made of styrene-butadiene-based latex, vinylidene chloride-based 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, X-ray photographic materials, black and white negative photographic materials,
It is used for such things.

Here, when used as an X-ray photographic material, R
ESEARCH DISCLOSURE Item
l 8 4 3 1 (August 1979 P.433-P.
441) Technologies related to stabilizers, antifoggants and antifogging agents (P.433 to P.436), technologies related to protective layers described in (P.436, Section IV), crossover control technologies (P.436, It is preferable to use Section V) or the like.

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 exposing a photosensitive material having photosensitive layers on both sides by sandwiching it between two lead intensifying screens or fluorescent intensifying screens.

Alternatively, in the case of a photosensitive material having 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 screen.

Here, as the phosphor, a blue-emitting phosphor such as calcium tungstate or barium sulfate, or a green-emitting rare earth phosphor is used. In addition, after X-ray exposure is accumulated in a phosphor, a cathode ray tube flying spot, an emitting diode, a laser beam (e.g. gas laser, YAG laser,
Exposure can also be performed with a variety of light sources including infrared light, such as dye lasers (semiconductor lasers, etc.).

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

(Example 1l) Potassium hexachloroiridate(III) having a grain size of 0.35 μm was added by a controlled double jet method to prepare approximately cubic silver iodobromide grains. 1-Phenyl-5-mercabutotetetrazole was added to this emulsion, chemical sensitization was performed using gold/sulfur sensitization, and 4-hydroxy-6-methyl-1. 3.
3a, ? -tetrazaindene, 1,2-benzisothiazolin-3-one and β-oxyethyl phenyl ether are added as preservatives, and 2,4-dichloro-6-hydroxy-s-4 lyazine is added as a hardening agent. and coated on both sides of a polyethylene terephthalate support. Furthermore, using gelatin as a binder, a matting agent, an anionic surfactant, a fluorine-containing compound, an organopolysiloxane polyethylene oxide type nonionic surfactant, and the DV- A surface protective layer containing '759 was applied. The amount of silver coated on this sample was determined by applying the same amount on both sides.
The amount of silver was set as shown in 1. (Sample No.a
-d) Table 1. 2 b 8.0
3 c 10.0 4 d l4.0 5 a 6.0 Add 0.5g of exemplified compound ■ per 1 liter of developer 6 b 8.0 7 C 10.0 8 d l6.0 Exemplary compound ■ Developed at 25° C 3 minutes 90cc/(35.6an x 43.2cm) fixing 1 23°C 3 minutes 300cc/( ) washing with water 20°C 3 minutes 3171 minutes Next developer concentrate part A, part B1 part C and starter formulation shows.

Bart A Bart B Part C For 10J For 10j7 For 1Ol Add water to make starter 2 50 ml To prepare the liquid, add approximately 61 liters of water to Part A 2.5 C Part B 40 0 ml and Part C 250 mj7 in order while stirring. The solution was added and dissolved, and finally the pH was adjusted to 10.40 by adding water. This used solution is used as a developer replenisher. The starter was added at a rate of 20 mA to every liter of this replenisher. This liquid is the developer tank liquid and is used at the start of running.

Next, as shown in Table 1, the following development processing was performed using a roller conveyance type automatic processor using various developing solutions.

The automatic developing machine was operated for 3 days for one test, and on the operating days, 100 sheets of half-exposure (so that the engineering density was approximately 2.0) and cut in half (35.6an x 43.2cm) were processed per day. 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. 62-94-879, and developed at the end of the second day of each working day to determine the relative sensitivity of the light-sensitive materials.

The results obtained from such experiments are shown in the table. Shown in 2.

As can be seen from Tables 2 and 2, it can be seen that when the amount of coated silver is small, the sensitivity is low, and when the amount of coated silver is increased to obtain high sensitivity, the silver stain becomes extremely worse. Also, does silver stain worsen when the applied silver amount is 10g/rr? The above shows that when the compound shown in the present invention is added to such a system, silver staining is greatly improved and its occurrence is prevented.

(Example 2) A silver nitrate aqueous solution and a potassium bromide aqueous solution were added to a gelatin aqueous solution to prepare silver bromide particles having an average particle size of 0.55 μm.

An aqueous silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were further added to this emulsion to form silver iodobromide containing 2 mol % of silver iodide on the outside of the previous grains. The average size of particles is 0.34%, and particles larger than 0.5μ account for 9.5% of the total.
%.

After desilvering this emulsion in a conventional manner, 1,2-penzisothiazolin-3-one, β-oxyethyl phenyl ether and gelatin were added, and 1-phenyl-5-mercaptotetrazole was added. - Sulfur sensitized. (Emulsion A5) An emulsion (emulsion B) with a grain size of 0.65 μm was also prepared in exactly the same manner as in the above emulsion A except that the amount of ammonia was increased.
The proportion of particles smaller than μ was 10% or less.

These emulsions A and B are shown in the table below. 3.4-hydroxy-6-methyl-1,3.3a. 7-
Tetrazaindene and sodium 3-(5-mercaptotetrazolyl)monobenzenesulfonate were added for stabilization. In addition, polyacrylamide, resorcinol, a dye with an absorption of 623 nm, and a dye with an absorption of 510 nm are added.
nm dye was added thereto, and a hardening agent was further added so that the development swelling ratio was 230% (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, organoborisiloxanes,
DV-7 described in No. 2-3 3 5 5 7 0
59. A surface protective layer containing a polyethylene oxide nonionic surfactant was applied. (eA'g to sample N) Each of the samples e-g thus obtained was coated with the same amount of silver on both sides, and the resistance was 12.0 g/distance on both sides.

Table using these samples. Example 1 The experiment as shown in 3.
It was carried out in the same way.

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

The results obtained in this way are shown in the table. Shown in 3.

(Grain: RMS evaluation method) (1) Using the X-rays, lead intensifying screen, and cassette used to determine relative sensitivity, the optical density after development was 2. X-rays are irradiated so that it becomes 0.

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

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

(4) This single-sided sample was measured using a microdensitometer that measures grain size (a circular slit with a diameter of 12 μm was used for the measurement). M. Find S.

As can be seen from this table, when 50% or more of particles with a size of 0.5 μm or less are contained, the RMS improves, but on the other hand, silver stain worsens.

It can be seen that when the compound shown in the present invention is included in the developer, silver staining can be prevented even in such cases without deterioration of RMS.

Claims (1)

[Claims] (1) After imagewise exposure of a silver halide photosensitive material having a coated silver amount of 10 g or more per 1 m^2 (total in the case of both sides), at least (a) a hydroquinone developing agent, (b) 0.3 mol 1. A method for developing a silver halide photosensitive material, comprising processing with a developer containing at least 1/1 sulfite and (c) at least one of the following (X) or the following (Y). (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,
m_1 and n_1 are numbers 1, 2 and 3, respectively, p is 1 or 2, A_2 and E_2 has the formulas -CO-O-M, -SO_2-O-M, ▲mathematical formulas, chemical formulas, tables, etc.▼, -S-Z and ▲mathematical formulas, chemical formulas, tables, etc.▼ (these In the formula, X and Y are each a hydrogen atom or an alkyl group having up to 8 carbon atoms which may be substituted with a hydroxyl group, a carboxylic acid group or a sulfonic acid group, and Y is further a phenylsulfonic acid group, a lower It may be an 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) The following (y1) and (y2) (y1) Compound 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)
50% or more of the silver halide grains in all emulsion layers100
2. The developing method according to item 1, wherein % or less consists of small particles with a particle size of 0.5 μm or less.