JPS59228644A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain stable photographic characteristics by incorporating a specified compd. to a hydrophilic colloidal layer. CONSTITUTION:At least one of compds. ( I ) or (II) is incorporated in a hydrophilic colloidal layer contg. at least one layer of photosensitive silver halide emulsion layer for photographic material coated on a substrate. By this method, fluctuation of contrast of picture image and increase of fog which are caused frequently in a continuous and large quantity treatment are prevented. In the foumulas, R1-R3, R5 and R6 are H, halogen, OH group, alkyl group, or amino group having eventually substituent; R4 and R7 are H, phosphate group, or OH group; n and m are integers 1-8.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic material, more specifically a silver halide photographic material capable of stably obtaining photographic images with high contrast and low fog. Regarding.

(Conventional wave Wt) In general, high-contrast silver halide photographic materials are used in the photolithography process to form characters and halftone-resolved photographic images, and in the ultra-precision photolithography process to form fine line images. There is. For example, silver halide photographic materials used for such purposes have an average particle diameter of 0.2.
A photosensitive material consisting of a silver chlorobromide emulsion having a narrow grain distribution in μ, a uniform grain shape, and a high silver chloride content (for example, at least a mol% content) is used. A method has been used in which a material is treated with an alkaline hydroquinone developer having a low sulfite ion concentration to obtain an image with high contrast, high sharpness, and high resolution, such as a halftone dot image or a fine line image. This type of photosensitive material is widely known as an Hlith type photosensitive material. The above photolithography process includes the process of converting a continuous tone original into a halftone image;
In other words, it includes the process of converting the continuous gradation density changes of the original into a set of halftone dots having an area proportional to the density.1 Such conversion methods include 1. Alternatively, a common method is to photograph an original through a contact screen and then perform special development processing to form a halftone dot image.

The developer used in the above-mentioned special development process has conventionally been called an infectious developer or a squirrel type developer. For this contagious developer or lith type developer, for example, J.
N.C. Yale, 'Journal Φ Off'e The Book of Franklin Instegoteate Volume 1, Vol. 239, p. 221 (1945). Refers to a developer with a low ion concentration.

In a normal photolithography process, a large amount of developer is required to carry out continuous photolithography using an automatic processor using the above-mentioned Lith developer. Therefore, a control method for maintaining the quality of the developer during continuous processing has become extremely important, and a great deal of effort has been made to develop this control method.

One such method of improvement is that, depending on the rate at which the activity of the developer solution changes and the rate at which it is fatigued due to oxidation that occurs during the processing process, the amount necessary to restore the original activity to compensate for this. A method of correcting using a replenisher is widely and generally adopted.

However, the above method involves controlling the amount of developer replenishment, and has the disadvantage that the developing device and processing operations become complicated.

On the other hand, high-contrast images can be obtained by processing with a non-Lith type developer with a high concentration of sulfite ions, so-called Hounidon, hydroquinone type developer, or methol-hydroquinone type developer, without using the special Naris developer. In other words, a silver halide photographic light-sensitive material exposed by a halftone dot generator, which is a device that forms a halftone image using a laser beam having a coherent output wavelength, is processed using the above-mentioned two types of developer. Methods of processing to obtain high contrast images are also known.

As is clear from the above, there are two known methods for obtaining high-contrast images: processing with a lithium developer and processing with a non-lithium developer. There is a demand for silver halide photographic materials that can produce high-contrast images, and there is also a demand for silver halide photographic materials that can provide stable photographic properties even after continuous processing over long periods of time. Particularly during long-term continuous processing, various additives from the silver halide photographic light-sensitive material are eluted into the developer, resulting in a decrease in image contrast and an increase in capri, making it impossible to obtain the initial photographic properties. As a method to improve this, an inhibitor or activator is added to the release layer of a silver halide photographic light-sensitive material, and the above components are eluted into the developer during the development process, thereby reducing the activity. There are also known ways to control this.

However, in this method, the above-mentioned active ingredients are added to the photosensitive material in advance, and the purpose is to dissolve them. Therefore, this method is applied to both lithium-type and non-lithium-type developers at the same time. This is considered extremely difficult.

The reason for this is that even if the desired effect is achieved with one developer, the opposite effect or no effect may occur with the other developer. be.

(Objective of the Invention) Therefore, the first object of the present invention is to provide a silver halide photographic light-sensitive material that can obtain stable photographic properties for long-term continuous processing when using a lithium developer or a non-lithium developer. It is a second object of the present invention to provide a solution which, when using a lithographic developer or a non-lithium developing solution, has a small increase in fog when a light-sensitive material is continuously processed in large quantities over a long period of time, and The object of the present invention is to provide a silver halide photographic material that can provide a certain level of film stability.

(Structure of the Invention) The present inventors have proposed a silver halide photographic light-sensitive material in which the above object is achieved by coating a photosensitive silver halide emulsion layer on a support with a hydrophilic comoid layer including one layer. It has been found that this can be achieved using a silver halide photographic material containing at least one compound represented by the following general formula (1) or (I) in the hydrophilic colloid layer.

General formula ■ R1 In the formula, R1 and RaFi represent a hydrogen atom, a halogen atom, a human 12-hydroxy group, an alkyl group, or an optionally substituted amino group, and R4 represents a hydrogen atom, a phosphate group, or a hydroxy group. and n represents an integer of 1 to 8.

General Formula I In the formula, R5 and R8 represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, or an optionally substituted amino group, and R? represents a hydrogen atom, a phosphoric acid group, or a hydroxyl group, and m represents an integer from 1 to B.

That is, the present invention is characterized in that a hydrophilic colloid layer constituting a silver halide photographic light-sensitive material contains a small amount (in both cases, one kind) of nitrogen-containing heterocyclic compounds as shown by the above general formulas, thereby reducing the risk of deterioration. The present invention has been found to be able to improve image contrast fluctuations and capri increases that tend to occur during large-volume continuous processing when either a developer or a non-Lith type developer is used. The present invention will be described in further detail below. To describe more specifically the compounds represented by each of the above general formulas that are effectively used in the present invention, R, e R, and R in the above general formula CI).

The halogen atom represented by F'i, jj is preferably an elemental atom or a fluorine atom, and the alkyl group is an alkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. These alkyl groups may be linear or branched (and may be substituted with a hydroxy group. Examples of substituents for the optionally substituted amino group include, for example, those having a carbon number of 1 ~8 linear or branched alkyl groups (e.g. methyl group, ethyl group, n-propyl group, t-butyl group), aryl groups (e.g. phenyl group, tolyl group), alkoxy groups (e.g. methoxy group, ethoxy group, Examples of the phosphoric acid group represented by The halogen atom represented by R11 and R6 in the general formula (2) is preferably a chlorine atom or a fluorine atom, and alkyl As a group, 1 carbon atom number 1 ~
8 alkyl groups, such as methyl group, ethyl group, propyl group, butyl group, octyl group, etc., and these alkyl groups may be linear, monobranched, or substituted with a hydroxy group.

Examples of the substituent for the amino group which may be further substituted include, for example, a straight-chain or branched alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, n-butabyl group, t-
butyl group), aryl group (e.g. phenyl group, tolyl group), alkoxy group (e.g. methoxy group, ethoxy group, propoxy group), aryloxy group (e.g. phenoxy group), acyl group (e.g. acetyl group, benzoyl group) The phosphoric acid group represented by R7 includes, for example, a monophosphoric acid group, a syric acid group, or a polyphosphoric acid group such as a triline group. Specific exemplary compounds of the compounds of the present invention represented by the above general formulas will be described, but the compounds of the present invention are not limited thereto [Examples of compounds] (1) 2-oxy-4-amino Pyrimidine-5'-methylriboside phosphate (2) 2-oxy-4-ethylamino-5-chloropyrimidine-57-methylriboside syphosphate (3) 2-oxy-4-methoxyaminol 5-hydroxypyrimidine-
5'-(β-ethyl phosphate) riboside (4) 2-oxy-4-amino-5-methylpyrimidine-5'-hydroxymethyl riboside (5) 2-oxy-4-amino-5- and droxyethyl- 5'-Methylriboside phosphate (6) 2-hydroxyamino-5,6-dihydromethylriboside 5'-triphosphate (7)
2.4-Dioxy-pyrimidine-5'-phosphate methyl riboside (8) 2.4-dioxy-5-methylpyrimidine-57-hyde t2 bovine dimethyl riboside (9) 2,4-dioxy-6-hydro p oxymethyl-
5'-Methyl silinate riboside (10) 2,4-dioxy-5,6-dichloro-5
'-Methyl phosphate riboside (11) 2.4-dioxy-5-hydroxypyrimidine-5'-(β-ethyl phosphate) riboside (12) 2.4-dioxy-5-aminopyrimidine-5'-triphosphoric acid Methylriboside (13) Diaminopyrimizidine-5'-hydroxymethylriboside (14) in 2.4-dioxy-5-hydro
) 2.4-dioxy-enthylamino-5'-phosphate methylriboside (15) 2.4-dioxy-5-acetylamino-
6-Hydroxypyrimidine-5'-methylriboside phosphate As the compound represented by the above general formula used in the present invention, a reagent for genetic engineering research available from Wako Pure Chemical Industries, Ltd. can be used.

At least one of the above compounds of the present invention is contained in a hydrophilic colloid layer including a silver halide emulsion layer on the same side as the silver halide emulsion layer on the support constituting the silver halide photographic light-sensitive material. However, in the present invention, it is specifically preferable to include it in the silver halide emulsion layer.
Further, the effects of the present invention can also be obtained by containing it in other hydrophilic colloid layers directly adjacent to the emulsion layer, such as protective layers, interlayers, and other auxiliary layers.

In order to add and contain the compound of the present invention in the above-mentioned hydrophilic colloid layer, it may be dissolved in an appropriate organic solvent such as alcohols such as methanol and ethanol, ethers, esters, etc. , or may be added after being dispersed in a hydrophilic colloid.Furthermore, p
It can be added and contained in the hydrophilic colloid layer after being dissolved in a solution in which the pH is lowered with a high concentration of I(I) or with an acid such as sulfuric acid, citric acid, or oxalic acid.

Furthermore, as an alternative method according to the present invention, gelatin whose nucleic acid content is adjusted in the process of decomposing collagen to form a gelatinous layer can be used as a hydrophilic colloid, and similarly gelatin expressed by the above general formulas can be used. The present invention also includes a method of incorporating gelatin with an adjusted content of the compound of the present invention into a hydrophilic colloid layer.

According to the above, the amount of the compound of the present invention contained in the hydrophilic colloid layer is lXl0-' per mole of silver halide.
% mol to 10 mol, preferably 2X10-'
mole to 2XIO-'' mole, and preferably 0.2XIO-'' mole to hydrophilic colloid lII in the hydrophilic colloid layer.
The compound of the present invention is in the range of 1 to 200 da. The effects of the present invention can be further enhanced by using the compound of the present invention in combination with a heterofused ring compound represented by the following general formula: .

1 General formula [Machi R1 In the formula, R8 represents a hydrogen atom, a halogen atom, a hydroxyl group, or an amine group, and Rg represents a hydrogen atom, a hydroxyl group, or an amine group, but -8 and R9 are simultaneously a hydroxyl group or an amino group. 0 or RIG represents a hydrogen atom - hydroxyl group, amino group or methyl group 〇General formula (5) In the formula, R and aSS represent the same group as Rto of the above general formula [In the formula] I R11 and R14 represent a hydrogen atom, a hydroxyl group, or an amino group, but they cannot be a hydroxyl group or an amino group at the same time.
represents a group of the same type as .

Next, specific representative examples of compounds represented by the above general formulas [eaves to [■] will be listed, but the present invention is not limited thereto◎ [Example of compounds] (A) 6-chloro-purine (B) 6-Methylaminopurine (C) 6-oxy-purine (D) 2-amino-6-oxy-purine ■6-amino-
Purine (3) Pyrazolo (a, 4-d) Pyrimidine ((334-
Amino-6-hydroxyvirazolo[3゜4-d]pyrimidine 4-hydroxy-pyrazolobirimicin According to the present invention, it can be effectively used in combination with the compound of the present invention represented by the general formula CI) or (II). Preferably, the hetero-fused metal ring compound represented by the above general formula [[l to ■]] is added together with the compound of the present invention in an amount approximately the same as the amount of the compound of the present invention described above. It can be contained in the hydrophilic colloid layer of the contact layer. and addition,
The addition can be carried out using the same method of addition as in the case of the compound of the present invention.

Examples of the silver halide used in the silver halide emulsion layer constituting the silver halide photographic light-sensitive material of the present invention include silver bromide-silver chlorobromide, silver iodobromide monochloroiodobromide, silver chloride, etc. Any of those used in conventional silver halide photographic emulsions are included.

In particular, when used as a sensitive material for a scanner that is exposed using a halftone dot generator used for a light source such as an argon laser or a helium neon laser, a silver chlorobromide emulsion with a high silver chloride content is preferable as the silver halide composition. be.

These silver halides may be coarse-grained or fine-grained and may be prepared by any known method, such as U.S. Pat.
No. 592,250, No. 3,276.877, No. 3
．． No. 317,322, No. 2.222,264, No. 3.320.069, Mg No. 3,206,313, or "Journal of Photographic Science (J-Photo.

Sai, ) J Volume 12, No. 5 (September, October issue), 1
964, pp. 242-251. It is also possible to mix and use silver halides prepared by different methods.

In the present invention, the silver halide contained in the silver halide emulsion layer has an average grain size of 0.05 to 1.5 μm, preferably 0.1 to 0.0, s.
microns, and at least 75%, preferably at least 75% of the total number of particles are 0.5 to 1.5% of the average particle size.
It is desirable to include silver halide having a grain size of 5 times, preferably 0.6 to 1.4 times.

According to a most preferred embodiment of the present invention, the silver halide used in the present invention has an average grain size of 0.10 μm to 0.3 μm, and more than 80% of the total grains have an average grain size of 0.3 μm. It is silver chlorobromide or silver chloride having a grain size of .6 to 1.4 times.

In addition, iridium,
Atoms such as rhodium, osmium, bismuth, cobalt, nickel, palladium, ruthenium, iron, copper, zinc, lead, and cadmium may be contained. When these atoms are contained, 1O-! per mole of silver halide! ~1
It is preferably contained per 0-" mole, especially 10-6
It is suitable to contain 4 moles of ~10''. Further, it may be a surface latent image type or an internal latent image type. Additionally, silver halides prepared by a variety of different methods may be mixed. The crystal shape may be cubic, octahedral, tetradecahedral, or spherical without any limitations.

The compound of the present invention is added to the hydrophilic colloid layer alone or preferably in combination as described in 5 above, and the hydrophilic colloid of the colloid layer particularly advantageously used in the present invention is gelatin. Examples of hydrophilic colloids other than gelatin include colloidal albumin, agar, gum arabic-alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives, e.g. Phenylcarbamyl gelatin, acylated gelatin N phthalated gelatin, as described in each specification of U.S. Pat. No. 2,614,923, U.S. Pat.
No. 520 to No. 2,831,767, polymerizable monomers having an ethylene group such as styrene acrylate/acrylic ester 1 methacrylic acid and methacrylic ester are added to gelatin. These hydrophilic colloids can also be used in layers containing no silver halide, such as antihalation layers, protective layers, intermediate layers, etc.

The photosensitive material according to the present invention has a hydrophilic colloid layer including one silver halide emulsion layer on the support as described in 5 above, and the photosensitive material according to the present invention is present in at least one of the hydrophilic colloid layers. It contains a heterofused ring compound according to
A protective layer having an appropriate thickness on the layer side, that is, preferably 0
．． It is desirable that a gelatin protective layer of 1 to 10 .mu.m, particularly preferably 0.8 to 2 .mu.m, is applied.

The hydrophilic colloid used in the present invention may contain various photographic additives, such as gelatin plasticizers, hardeners,
Surfactant, image stabilizer, ultraviolet absorber 1 antistain agent/pH adjuster 1 antioxidant, antistatic agent, thickener,
Graininess improvers - dyes, mordants, brighteners, development speed regulators, matting agents, etc. can be used within the range that does not impair the effects of the present invention.

Among the above-mentioned various additives, those that can be particularly preferably used in the present invention include those described in U.S. Pat.
Publication No. 939, West German Application Publication No. 1,904,604, Japanese Unexamined Patent Publication No. 48-63715, Japanese Patent Publication No. 45-i5
Publication No. 462, Belgian Patent No. 762,833,
U.S. Patent No. 3,767.410, Belgian Patent No. 5
58,143, such as styrene-sodium maleate copolymer, dextran sulfate, etc. Hardeners include aldehyde-based, epoxy-based, ethyleneimine-based, active halogen-based, vinyl Sulfone type, incyanate type, sulfonic acid ester type,
Various hardening agents and ultraviolet absorbers such as carbodiimide-based, mucochloric acid-based, and acylinyl-based agents include, for example, U.S. Patent No. 3,253,921 and British Patent No. 1,309,349.
Compound 1, especially 2-(2
-hydroxy-5-t@rt-butylphenyl)benzotriazole, 2-(2'-hydroxy-3,5-di-tert-butylphenyl)benzotriazole, 2-
(2-Hydroxy-3-t@rt-butyl-5'-butylphenyl)-5-ri! Lorbenzotriazole, 2-(2-hydroxy-3/
, S/-di-tart-butylphenyl)-5-chlorobenzotriazole, etc., and examples of dyes include U.S. Pat. 3,048,487
Compounds described in various specifications such as No. 1 and U.S. Patent No. 515,998 can be used, and these compounds may be included in a protective layer, an emulsion layer, an intermediate layer, etc. ◎Additionally, coating aids and emulsifiers. British Patent Nos. 548,532 and 1,216 as permeability improvers for processing solutions, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials.゜389, U.S. Patent No. 3,026,202, U.S. Patent No. 3,514,293
Specifications of each issue, Special Publication No. 44-26580＼No. 43-1
No. 7922, No. 43-17926, No. 43-1316
No. 6, No. 48-20785, Buddhist Temple Patent No. 20
It is possible to use anionic, cationic, nonionic or amphoteric compounds described in the specifications of No. 2,588, Belgian Patent No. 773,459, JP-A-48-101118, etc. Yes, but these 5-
Particularly preferred are anionic surfactants having a sulfonic group, such as succinic acid ester sulfonated compounds, alkylbenzene sulfonated compounds, and alkylbenzene sulfonated compounds. Antistatic agents include Japanese Patent Publication No. 46-24159, Japanese Patent Application Laid-Open No. 48-89979, and U.S. Patent No. 2.
882,157, 2,972,535, JP 48-20785, JP 48-43130, JP 48-90391, JP 46-24159,
There are compounds described in JP-A-46-39312, JP-A-48-43809, and JP-A-47-33627, and as matting agents, for example, British Patent No. 1.
No. 221,980, U.S. Patent No. 2,992,101;
Same No. 2,956゜884, Buddhist Temple Patent No. 1,395,5
Compounds described in the specifications of No. 44, Japanese Patent Publication No. 48-43125, etc., especially silica gel with a particle size of 0.5 to 20μ, polymethyl methacrylate with a particle size of 0.5 to 20μ Examples include merging.

The present invention can also be applied to direct-positive photographic materials, but the silver halide for direct-positives used in the photographic material of the present invention has been fogged by a conventionally known technique prior to Ii. Ru. Fog may be imparted using a reducing agent alone or in combination with a reducing agent and a gold compound. Representative of advantageous reducing agents include, for example, formalin, hydrazine, polyamines (e.g. triethylenetetramine, tetraethylenepentamine, etc.), thiourea dioxide 1
Tetra(hydroxymethyl)phosphonium chloride, boron compounds (e.g. amine borane, water) are used. Polyamines, thiourea dioxide and boron compounds are particularly preferably used. Representative examples of gold compounds include chloroauric acid. , potassium chloroaurate, gold sulfide, gold selenide, etc., and generally 1.0% per mole of silver halide.
0x10-6 to 1. It is used in the range of OXIO-4 moles.

The degree of fog ripening of the direct positive silver halide emulsion in the present invention can be suitably determined depending on the amount of fog, fog ripening temperature, time conditions, etc. ! It can be played for 1m.

The photosensitive material of the present invention is formed by coating a hydrophilic colloid layer containing the compound of the present invention on a suitable photographic support. Examples of the support used in the present invention include baryta paper, glyethylene-coated paper, etc. ) Polypropylene synthetic paper, glass plate,
Typical examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, polystyrene films, etc., and these supports are each supported by silver halide photographic sensitization. The material is appropriately selected depending on the intended use of the material.

Examples of the developer that can be included in the developer used for developing the photosensitive material of the present invention include the following.

Typical [0-(CH-C)I) rr-()HI type developers include catechol, pyrogallol and its derivatives, and ascorbine m, as well as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, Toluhydroquinone, methylhydroquinone, 2,3-dichlorohydrogynon 12
．． 5-dimethylhydroquinone, 2゜3-dibromohydrobinone, 2.5-dihydroxyacetophuninone,
2.5-diethylhydroginone, 2.5-di-p-7
enethylhydroquinone, 2,5-dibenzoylaminohydroquinone, catechol, 4-tertetracatechol,
3-phenylcatechol, 4-phenylcatechol,
3-methodicatechol, 4-acetyl-pyrogallol, 4-(2-hydroxybenzoyl)pyrogallol,
Sodium ascorbic acid, etc.

Typical no -(CH=CI() n-NH, type developers include ortho and para aminophenols or aminopyrazolones, and 4-aminophenol 1
2-amino-6-phenylphenol, 2-amino/-4
-chloro-6-phenylphenol, 4-amino-2-
Phenylphenol, 3,4-diaminophenol, 3
-Methyl-4,6-diaminophenol, 2.4-cyamylsorcinol, 2.4.6-triaminophenol, N-methyl-p-aminophenol, N-β-human p
xyethyl-p-aminophenol, p-hydrobodiphenylaminoacetic acid, 2-7 minonaphthoyl etc. N-diethylaniline, 2.4-diamino-N, N-diethylaniline, N-(4-amino-3-methylphenyl)-morpholine, p-7 22-diamine, 4-amino-N,
N-dimethyl-3-hydroxyaniline, NNN'N'
Tetotemethylbaraphenylenediamine, 4-amino-N
-ethyl-N-(β-hydroxyethyl)-aniline,
4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline, 4-amino-N-ethyl-
(β-methoxyethyl)-3-methyl-aniline, 4-
Amino-3-methyl-N-ethyl-N-(β-methylsulfonamidoethyl)-aniline, 4-amino-N-butyl-N-r-sulfobutylaniline ~1-(4-'7
minophenyl)-pyrrolidine, 6-amino-1-ethyl, 1,2.3.4-tetrahydroquinoline, 9-aminoylolidine, etc.

Examples of the heterocyclic source developer include 1-phenyl-3-
Pyrazolidone, l-phenyl-4-amino-5-pyrazolone, 1-(p-aminophenyl)-3-amino-2-
Pyrazoline, 1-phenyl-3-methyl-4-amino-
5-pyrazolone, 5-aminouracil, 5-ami/-2
, 4,6-dolihydride, xyphyrimidene, etc.

Others: The Theory of Fist Ops The Association Photographic Process by T. H. James, M 4th edition (Ths
Th・ory ofth@Photographic
Proc@ss e Fourth Editio
n) Ic 2918334 pages and journal
Op the American Chemical SocietyCJou
rnal of the American Ch.
Volume 73, No. 3
Developers such as those described on page 100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination.The developer used in the present invention may also contain preservatives such as sodium sulfite, Even if sulfites such as potassium sulfite to ammonium sulfite are used, the effects of the present invention will not be impaired (this can be mentioned as one of the features of the present invention.Also, hydroxylamine or hydrazide compounds may be used as preservatives). 0Other pH adjustment using K such as caustic alkali, carbonate alkali or amine used in general black and white developer and buff 1
- Inorganic development inhibitors such as brompotali and organic development inhibitors such as penttriazole, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, etc. 1 Alkylarylsulfonic acid It is optional to add surfactants such as sodium, natural saponin monosaccharides or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin 1-glyoxal, ionic strength regulators such as sodium sulfate, etc. .

The photosensitive material of the present invention can be processed under various conditions. Regarding the processing temperature, for example, the development temperature is preferably 1d 50 °C or less, especially around 30 °C, and the development time is generally completed within 3 minutes, but particularly preferably within 2 minutes, which gives good results. There are many things. Furthermore, it is optional to employ processing steps other than development, such as washing with water, stopping/stabilization/fixing, and further steps such as pre-hardening and neutralization if necessary, and these may be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame development, or mechanical development such as roller development or hanger development.

Hereinafter, the present invention will be explained in more detail with reference to Examples. The technical scope of the present invention is not limited in any way by the following examples (although various embodiments are possible).

Example 1 An aqueous solution containing 1 mol of silver nitrate dissolved in 930 + JK water was used as an aqueous solution, and gelatin 6N and potassium A 23.811
Sodium chloride 61.4 II- Potassium chloroiridate 1 da and potassium chlororhodate 1 d to water 9
The aqueous solution in which 30mK was dissolved is called aqueous solution (), and the aqueous solution in which gelatin 241 is dissolved in water 624d is called aqueous solution (C).
◎ The above aqueous solution (C) was kept warm at 67°C, and while stirring vigorously, this aqueous solution (the above aqueous solution (4
) and T) are added simultaneously over 1 minute.

After the addition, the mixture was stirred at 67°C for 6 minutes, and then the temperature was gradually lowered and maintained at 40°C.

The emulsion prepared above was desalted and redispersed to obtain a monodisperse emulsion sample (1) with a grain size of 0.25 μm.

Next, 2-oxy-4 for comparison was added to the aqueous solution (C).
-Add 200 g of aminopyrimidine, add an aqueous solution in the same manner as above, desalt and redisperse, and remove particles with a particle size of 0.
, 25μ for a monodispersed emulsion sample) was obtained, and an emulsion sample (l [)1 Exemplary compound according to the present invention-11, 2009
An emulsion sample (■) prepared by adding .
Emulsion samples (VI) were prepared by adding 14,100 ml of Exemplified Compound of the Invention and 40 ml of Exemplified Compound of the Invention (3).

Each of the emulsion samples (i) to (VI) prepared above was
Keep warm at 3°C, add 0.21.F sodium chloride and 0.18F potassium iodide while stirring, add 2.8μ of sodium 100sulfate after 4 minutes, and chemically ripen for 65 minutes. . After chemical ripening, 0.151 of 4-hydrobix 1,3,3a,7-chitrazaindene was added as a stabilizer.
was added.

This emulsion contains two sensitizing dyes shown below: 0) and (
b) and optically sensitized, 3.6Ii of saponin as a spreading agent and 0.56 g of mucochloric acid as a hardening agent.

Glyoxal 8.41 N-methylol 7.08.9 was added and a thickener was added to bring the viscosity to 150. The emulsion obtained by adjusting the emulsion to P, 1 gi was coated on a polyethylene terephthalate base support with a backing layer and a thickness of 100 μm, and a protective layer was further coated thereon and dried.

The sample after drying was baked on a base wedge under the conditions of tungsten base 800C, M, and S, and the following developer (1) was used to develop a developer volume of 401. The material was developed using a roller-conveying automatic developing machine at a temperature of 30°C and 2000 seconds.The material was further blackened by 30% and then cut into quarters for 2,000 sheets.
The sample with the original wedge burned in the same way as above was 38'C1 (fund).
Processed in seconds. However, the replenisher used in the continuous processing step had the same composition as the developer (1) below, and the replenishment amount was 5 per quarter.

[Sensitizing dye]

(stomach) (CH2), OH [Developer (1)] The results obtained are shown in Table 1 below.

[Table 1] From the results in Table 81 above, the emulsion samples using the compounds of the present invention alone or in combination (emulsion numbers m, rv, v and It was revealed that there were few changes, especially changes in contrast, high contrast, and almost no increase in capri ◎Example 2, using emulsion sample (I) prepared separately according to Example 1, the above An emulsion sample (■) was obtained by adding exemplified compound-5, 20■ according to the present invention to an emulsion that had been subjected to chemical ripening in the same manner.
Exemplary compound-8 according to the present invention is prepared in exactly the same manner as 209.
An emulsion sample (■) containing the added emulsion, an emulsion sample (IX) containing the exemplified compound according to the present invention (g), an emulsion sample (IX) containing the exemplified compound according to the present invention (C), and an exemplified compound according to the present invention -9+ 4 m9 was added to the emulsion sample (X
), and an emulsion sample (XI) in which exemplified compound-14, 10■ according to the present invention and exemplified compound (C) according to the present invention, 4 DA were added, and an emulsion sample to which no compound according to the present invention was added. was prepared as (II).

Additives other than the above compounds were added in exactly the same manner as in Example 1, and an emulsion prepared was coated together with a protective layer onto a polyethylene terephthalate base support on which a backing layer had been previously coated, and dried.

The original wedge of the sample obtained above was baked using a xenon flash discharge tube for an exposure time of 10' seconds, and the developing solution (2) shown below was used at 32° C. using a roller conveyance type automatic developing machine with a developing solution capacity of 60 It. Development processing was performed for 1 minute.

After continuously processing 2,000 pieces of 30% blackened quarter-sized sheets, they were exposed for 104 hours using a xenon flash discharge tube.
The replenisher used in the continuous processing step was one with the same composition as the developer (2) below, and the amount of replenisher used was one replenishment amount. The length was 25 m per piece cut into four pieces.

The above results are shown in Table 2 below. 〇 [Developer (2)] In the above developer composition, the @ amount in parentheses indicates the case of a replenisher.

[Table 2] As is clear from the above table, the emulsion samples in which the compounds of the present invention were used alone or in combination (emulsion sample numbers ■, ■, ■, and XI) had a continuous It was found that changes in photographic properties due to processing, especially changes in contrast, high contrast, and almost no increase in capri were observed. ) The silver decagenide photographic material containing the compound represented by formulas (III) to (V) alone or in combination with the compounds represented by formulas (III) to (V) is stable with little change in photographic properties due to continuous processing. Contrast, no fog, O agent Zenimi Kuwahara

Claims (1)

[Scope of Claims] A silver halide photographic material comprising a hydrophilic colloid layer containing at least one photosensitive silver halide emulsion layer coated on a support, wherein the hydrophilic colloid layer contains the following general compounds. A silver halide photographic material containing at least one compound represented by formula (1) or (2). General formula (1) [In the formula, R1I Bg and R3 represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, or an optionally substituted amine group, R4 represents a hydrogen atom, a phosphoric acid group, or a hydroxy group, and n 0 representing an integer from 741 to 8] General 2■ [In the formula, R3 and R4 represent a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, or an optionally substituted amino group; group or a hydroxy group, and m represents an integer of 1 to 8. ]