JPS6139659B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for processing silver halide photographic materials to obtain stabilized photographic performance.
More specifically, by developing a silver halide photographic material that has been imagewise exposed in the presence of a specific macrocyclic compound, stable photographic performance can be obtained. This invention relates to a method for processing silver oxide photographic materials. In recent silver halide photographic materials,
It is common to add a sensitizer during the ripening of the main silver halide emulsion, and also add a ripening inhibitor for the purpose of suppressing fog that occurs as the ripening progresses. In addition, changes due to storage of the raw photosensitive material after applying this emulsion to a support such as a transparent film or paper and drying it (mainly fog due to an increase in the fogging tendency of the emulsion due to changes over time and its appearance) Emulsion stabilizers are added to prevent sensitization or desensitization. In this case, the ripening inhibitor and the emulsion stabilizer are not completely separate substances, but the same substance is often used, so they are collectively called an antifoggant. Some of these antifoggants are added to the developer to mainly prevent the occurrence of fog during development, and some of these are added to the emulsion and serve as ripening inhibitors and stabilizers. but,
Many antifoggants have strong effects and can be added sufficiently to the developer, but when added to the emulsion, they strongly adsorb to the silver halide, significantly interfering with development.
In addition, they have adverse effects such as destroying photosensitive nuclei, resulting in significant desensitization, so they are often not added to emulsions in sufficient quantities.In this sense, they are sometimes called development inhibitors to distinguish them from ripening inhibitors. At the early stage of the development of such ripening inhibitors or development inhibitors, silver halide photographic materials were limited to black and white, and additives were either natural products such as quinine, cystine, or a formalin condensate of cystine.
Many of its processed products were used, but increasingly synthetic heterocyclic compounds such as benzimidazole, benzotriazole, and thiodiazole were used. In addition, silver iodobromide emulsions for high-speed negatives have inherently slow developability, and sensitivity is important and even the slightest desensitization cannot be tolerated. Heterocyclic compounds containing only nitrogen, such as less sensitive pyrimidine or azaindolizines (azaindene, diazaindene, triazaindene, and tetraindene), as well as alkyl groups, phenyl groups, -OH groups, - Those substituted with NH ₂ groups, etc., and which were active and did not contain sulfur, were generally used. In this case, active sulfur is used, in particular 2-mercaptobenzoxazole containing a mercapto group, 2-mercapto-benzothiazole, 2-
Mercaptobenzimidazole, 1-phenyl-
Although strong development inhibitors such as 5-mercapto-tetrazole or 6-nitrobenzimidazole, which does not contain sulfur, are sometimes added to the developer solution, they are rarely added to the emulsion. However, in the case of silver chlorobromide emulsions or silver chloride emulsions, where sensitivity loss is not so much of a problem and development speed is fast, development fog is likely to occur.
The strong antifoggant containing sulfur is usually added in an appropriate amount not only to the developer but also to the emulsion along with the relatively weak antifoggant such as benzotriazole or benzimidazole.
Particularly in recent years, it has become essential to add the above-mentioned strong antifoggant to emulsions for photographic paper which have excellent sensitivity and developability. However, the above-mentioned relatively weak or strong antifoggants tend to strongly adsorb to the surface of silver halide particles, so they cannot be sensitized even in emulsions for photographic paper, especially in color emulsions. It is difficult to use because it tends to interfere with the adsorption of sensitive dyes, and it is generally nearly impossible to add it directly to the emulsion layer except in special cases. For this reason, methods are taken to prevent this effect on the emulsion as much as possible by placing it in an intermediate layer, undercoat layer, protective layer, etc., but in this case as well, it will diffuse into the emulsion layer during the coating and drying process, and the degree of diffusion will vary. Since it is easy to change depending on the conditions, it is difficult to obtain a constant fog prevention effect. Therefore, a small amount of benzotriazole or benzimidazole, which has relatively little influence, can be added directly to the emulsion, or recently, sulfonic acid or carboxylic acid groups have been introduced into strong additive molecules containing these mercapto groups to make them anionic. Development inhibitors are now added to the emulsion in small amounts.
The introduction of anionic groups weakens adsorption to silver halogens, and it has the property of creating electrical complexes with cationic substances such as typical sensitizing dyes such as cyanines and merocyanines. There is a theory that these sensitizing dyes are not expelled from the surface of the silver particles, but rather that they form a complex with the sensitizing dyes and are well adsorbed to halogen silver, acting as supersensitizers [O.Riester: Phot.Sci&Eng. .
13 13 (1969)] This is not effective for all sensitizing dyes. In other words, it is generally good for red-sensitive emulsions, but green-sensitive emulsions, blue-sensitive emulsions, or emulsions that are not color-sensitized have a significant desensitizing effect, so they cannot be used freely. Although it can be used conveniently for paper, it is completely difficult to use for high-sensitivity color films and the like. Therefore, recently, a so-called development inhibitor precursor (precnrsor), in which a substance with a masked development inhibitory group is added to the emulsion, separates the free inhibitor and converts it into the original development inhibitor. There are also proposals to bring out the functions of For example, the DIR (development inhibitor releasing) coupler shown in Japanese Patent Publication No. 43-21778 and the development inhibitor releasing compound shown in Japanese Patent Publication No. 46-25214 are used for color development, and the color developing agent When an oxidation intermediate is generated, the former couples with this to produce a dye and releases a development inhibitor, while the latter forms a colorless compound with the oxidation intermediate and releases a development inhibitor. It is. However, with this technology, development is suppressed more strongly in areas where development is more active, so although it has a great effect of softening the gradation, at the foot of the characteristic curve, where little development occurs, in the case of photographic paper, it is difficult to suppress development in white areas. The drawback is that fog is hardly suppressed. Further, the antifoggant precursor shown in US Pat. No. 3,575,699 is a substance in which the active group of a benzimidazole, benzotriazole, or 4-aza-benzimidazole antifoggant is substituted with a benzoyl group. Although it is stable in acidic or neutral conditions, it hydrolyzes in a strongly alkaline developer to release a development inhibitor.
It is effective regardless of the amount of exposure and the amount of developed silver, so it has little effect in softening the gradation, but it has the property of suppressing fog in areas with low exposure and unexposed areas, which are at the foot of the characteristic curve. However, in this way, developing in alkaline for a short period of time (recently, development is
It is important to select a compound that decomposes sufficiently in a short period of time (from 30 seconds to 1 minute) and is stable at the pH of the emulsion (especially in the presence of a large amount of moisture, temperature, and time during coating). It is extremely limited and difficult to freely inactivate the desired inhibitor. As mentioned above, a variety of antifoggants and antifoggants have been devised to date, but all of them have drawbacks and are stable regardless of development processing conditions, storage conditions, etc. The reality is that there are no known compounds that exhibit such anti-fogging effects or methods for processing silver halide photographic materials that exhibit such anti-fogging effects. Therefore, the first object of the present invention is to provide a method for processing silver halide photographic materials that can solve the above-mentioned drawbacks of conventional fog suppressants or antifoggants and can provide a stable fog prevention effect. It is. The second object of the present invention is to provide a novel antifogging agent that effectively prevents fogging even when incorporated into a processing solution, especially a developer, and even when incorporated into a silver halide photographic light-sensitive material, especially an emulsion layer. An object of the present invention is to provide a method for processing a silver halide photographic material using a photosensitive agent. A third object of the present invention is a method for processing a silver halide photographic light-sensitive material capable of suppressing the occurrence of fog without reducing the sensitivity and/or softening the tonality without reducing the excellent photographic performance. The goal is to provide the following. A fourth object of the present invention is to provide a silver halide photographic material capable of suppressing the occurrence of fog while maintaining excellent photographic performance even in the case of a high-sensitivity silver halide photographic material that is rapidly processed at high temperatures. It is an object of the present invention to provide a method for processing materials. The above object of the present invention and other objects of the present invention shown below are to provide a macrocyclic compound represented by the following general formula [], [] or [] (hereinafter referred to as the macrocyclic compound of the present invention). This is achieved by developing a silver halide photographic material that has been imagewise exposed in the presence of at least one species. (In the general formula [], [] or [], A represents an ethylene group or an ethene group which may be substituted with an alkyl group, D represents an oxygen atom or a sulfur atom, and X
represents nitrogen atom, phosphorus atom (same atom),
m ₃ represents 1 or 2, m ₄ represents 1 or 2, m ₅ represents 0 or 1, n ₃ represents 1 or 2, n ₄ represents 1 or 2, n ₅ represents 0 or 1, p ₂ represents 0 , represents 1 or 2, R ₃ and R ₄
each represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an alkoxycarbonyl group. ) In order to clarify the macrocyclic compounds of the present invention, compounds that are a general concept thereof (general formula [] ~
[]) will be explained first. [In general formulas [] and [], R ₁ and R ₂
each represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an alkoxycarbonyl group, or R ₁ and R ₂ may combine with each other to form a divalent group represented by the following general formula [] ; (In the general formula [], A and D are respectively the same as A and D defined below, and p ₁ is 0 to
Represents an integer of 5. ) A is a hydrocarbon group, X is a nitrogen atom or a phosphorus atom; D is an oxygen atom, a sulfur atom,

[Formula] (wherein, R' represents a hydrogen atom or a hydrocarbon group. The same applies hereinafter) or a hydrocarbon group; L represents an oxygen atom or a hydrocarbon group;

[Formula] is represented; m ₁ , n ₁ , m ₂ and n ₂ each represent an integer from 0 to 5. However, in the general formula [], at least two atoms or groups represented by D are an oxygen atom, a sulfur atom and

[Formula], and when R ₁ and R ₂ are a group selected from a hydrogen atom, a hydrocarbon group, or an alkoxycarbonyl group, and X is a nitrogen atom,
One of these at least two atoms or groups represented by D is an oxygen atom or a sulfur atom, and the other or group is an oxygen atom or a sulfur atom.

[Formula], and in the general formulas [] and [], m ₁ and n ₁ and m ₂ and n ₂ are never 0 at the same time. ] The macrocyclic compound of the present invention includes its phosphonium and/or ammonium salt and its nitrogen and/or
Alternatively, it may be a phosphoric oxide. Furthermore, in the above general formulas [] to [],
The hydrocarbon group represented by A is preferably 2
Has ~12 carbon atoms. Preference is given to straight-chain and branched alkylene and alkenylene groups having 2 to 8 carbon atoms such as ethylene, propylene, butylene and hexylene and unsaturated congeners thereof; cyclopropylene, cyclobutylene, cyclohexylene and Cycloalkylene and cycloalkenylene groups such as cyclohebutylene and their unsaturated congeners; the corresponding cycloalkylene-di-alkyl groups such as cyclohexylene-dimethyl and phenylene and phenylene-di-alkyl, preferably phenylene-di-methyl. It is an aromatic group such as The group A adjacent to X preferably has an aliphatic moiety attached to X. In addition, the hydrocarbon group represented by R ₁ is 1 to
12 carbon atoms, preferably 1 to 8
straight-chain and branched alkyl radicals having 2 to 8 carbon atoms and straight-chain and branched alkenyl radicals having 2 to 8 carbon atoms. Other representative groups are cycloalkyl, aralkyl and aryl groups. Preferred alkoxycarbonyl groups represented by R ₁ are also groups having up to 10 carbon atoms. Among the macrocyclic compounds of the present invention represented by the above general formula [] or [], preferred compounds are:
m ₁ , n ₁ and p ₁ are integers from 0 to 2, and 2
A compound in which two X's are the same atom. A representative structural formula is shown below (however, in the structural formulas shown in (1) to (16) below, both X's are nitrogen atoms or both X's are oxygen atoms). Representative specific examples of the macrocyclic compounds of the present invention include the above-mentioned
This is exemplified by substituting, for example, various groups shown below for A and R ₁ in formulas (1) to (18). (i) A=-CH ₂ -CHR- (ii) A=-CH ₂ -CHR-CH ₂ - or -CH ₂ -
CH ₂ −CH ₂ − (iii)

【formula】 (iv)

【formula】 (v) A = unsaturated congener of groups (i) to (iv); (vi)

【formula】 (vii)

[Formula] (viii) R ₁ = −CH ₃ ; −CH ₂ −CH ₂ R; −CH ₂ −CH ₂ R
−CH ₃ ; and unsaturated congeners (ix)

【formula】 (x)

[Formula] () R ₁ =H ()

[Exemplary compounds]

[1] 1,4,7,10,13,16-hexaoxacyclooctadecane [2] 2,5,8,15,18,21-hexaoxatricyclo[20,4,0,0]hexacosane [3] 2,5,8,11,18,21,24,27-octaoxatricyclo[26,4,0,0,12,17]
dotoria contin [4] (2,3)(14,15)-dibenzo-1,
4,7,10,13,16,19,22-octaoxacyclotetracosate-2,14-diene [5] 1,4,7,10,13-pentaoxer-16-
Azacycloocdadecane [6] 1,4,10,13-tetraoxer-7,16-
Diazacyclooctadecane [7] 2,3-benzo-1,4,10,13-tetraoxa-7,16-diazacyclooctadeca-2
-En [8] 4,7,13,16,21-pentaoxer-1,
10-diazabicyclo[8,8,5]tricosane [9] 4,7,13,16,21,24-hexaoxer-
1,10-diazabicyclo[8,8,8]hexacosane [10] 16-dimethyl-13,16,21,24-tetraoxa-1,4,7,10-tetrazabicyclo[8,8,8]hexacosane [11] 1,4,10,13-Tetrathia-7,16-
Diazacyclooctadecane [12] 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane [13] 13,16-dioxa-4,7,21,24-tetrathia-1,10-diazabicyclo[8,8,
8] Hexacosane [14] 1,4-Dioxer-10,13-Dithia-
7,16-diazacyclooctadecane [15] 4,13-dibenzyl-1,7,10,16-
Tetraoxa-4,13-diphosphacyclooctadecane [16] 4, 7, 13, 16, 21, 24-Hexachia-
1,10-diazabicyclo[8,8,8]hexacosane [17] 4,7,13,16,21,24-hexaoxa-1,10-diphosphabicyclo [8,8,8]
Hexacosane The macrocyclic compound of the present invention is, for example, a journal compound.
Journal of the American Chemical Society
Volume 89, pages 7017 and 2495, 1967, same document no.
Volume 92, pages 391, 3500 and 7072, 1970, Volume 86, page 3651, 1964, Volume 91 of the same literature,
4690 pages, 1969; Tetrahedron Letters 2885 pages, 1969; and Chemical Communications.
Communication), p. 1055, 1970, etc., or can be easily synthesized according to the method. Among the above-mentioned exemplary compounds of the macrocyclic compound of the present invention, compounds particularly preferably used in the present invention include 1,4,7,10,13,16-hexaoxacyclooctadecane, 2,5,8,15 ，
18,21-hexaoxatricyclo[20,4,0,
0] Hexacosane, (2,3)(14,15)-dibenzo-1,4,7,10,13,16,19,22-octaoxacyclotetracosate-2,14-diene, 4,
7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8,8,8]hexacosane, 1,
4,10,13-tetrathia-7,16-diazacyclooctadecane or 4,7,13,16,21,24-hexathia-1,10-diazabicyclo[8,8,
8] Hexacosane and the like. At least one type of the macrocyclic compound of the present invention may be used, or two or more types may be used in combination. The above objects of the present invention can be achieved by developing a silver halide photographic material that has been imagewise exposed to light in the presence of at least one type of macrocyclic compound of the present invention. For example, the macrocyclic compound of the present invention is contained in a silver halide photographic light-sensitive material and/or a processing bath (for example, a developer). More specifically, typically, after imagewise exposure of a silver halide photographic light-sensitive material containing the macrocyclic compound of the present invention, the material contains at least one of hydroquinone, metol, and phenidone as a developing agent. or processing a silver halide photographic light-sensitive material containing the macrocyclic compound of the present invention with a developer containing an aromatic primary amine color developing agent after imagewise exposure; or processing an imagewise exposed silver halide photographic light-sensitive material with a developer containing the macrocyclic compound of the present invention and at least one of hydroquinone, metol, and phenidone as a developing agent;
Alternatively, a typical processing method of the present invention includes processing an imagewise exposed silver halide photographic light-sensitive material with a developer containing the macrocyclic compound of the present invention and an aromatic primary amine color developing agent. included in. In one preferred embodiment of the invention,
The macrocyclic compound of the present invention is added to a silver halide emulsion layer or a layer containing a silver halide emulsion and subjected to development processing. In another preferred embodiment of the present invention, the macrocyclic compound of the present invention is present in a layer directly adjacent to a silver halide emulsion layer or a layer containing a silver halide emulsion or a layer adjacent via an intermediate layer; It is added to other constituent layers of the photographic element (eg, protective layer, subbing layer, etc.) and subjected to development processing. When adding the macrocyclic compound of the present invention to a silver halide emulsion layer, it is preferable to add it between chemical ripening and coating processing, but it is preferable to add it by spray method or adhesive method before the development process. It may be incorporated into a silver halide photographic material by adjusting the method or the like. In this case, the macrocyclic compound of the present invention may be dissolved in water or a solvent compatible with water, such as lower alcohols, esters, ketones, or a mixed solvent thereof, and then added to the solution. , Oil Protect may be added in a dispersed form. Furthermore, the macrocyclic compound of the present invention can form a complex with cupric chloride, nickel chloride, ferric chloride, etc., and can be added in the form of a complex, or can form a complex. By doing so, compounds that lose their water solubility can be added after being dispersed in oil protection. In another preferred embodiment of the present invention, the macrocyclic compound of the present invention is added to a processing bath for processing a silver halide photographic light-sensitive material, such as a developing bath or a bath before the developing bath. Developing the photosensitive material. When the macrocyclic compound of the present invention is added to a silver halide emulsion layer or a layer containing a silver halide emulsion and subjected to development processing, the amount of the macrocyclic compound of the present invention added is not limited to the halogen per mole of silveride
The amount added is preferably in the range of 0.01 g to 50 g, and particularly good results can be obtained with the amount added in the range of 0.1 g to 30 g. When the macrocyclic compound of the present invention is added to a layer that does not contain silver halide, such as an intermediate layer, a protective layer, or an undercoat layer, it may be added by a conventional method, and the amount of addition is not limited. No, but 0.01g per 1g of gelatin
A good effect can be obtained by applying an aqueous gelatin solution containing the macrocyclic compound of the present invention in an amount of 10 g to 10 g. When the macrocyclic compound of the present invention is incorporated into a silver halide photographic light-sensitive material for development using a spray method or pre-bath treatment before the development process, and the macrocyclic compound of the present invention is added to the developing bath, etc. When developing processing is performed by adding a compound of the formula, the macrocyclic compound of the present invention is preferably contained in a range of 0.01 g to 100 g per processing bath, particularly 0.1 g.
Good results are obtained between 50 g and 50 g. The amount of the above-described macrocyclic compound of the present invention to be added is desirably selected depending on the type of silver halide in the photosensitive material to be processed, the type of the macrocyclic compound of the present invention, etc. In recent years, there have been several attempts to improve various photographic properties by incorporating macrocyclic compounds into silver halide photographic materials. Techniques related to these include, for example, Japanese Patent Publication No. 38-6447, Japanese Patent Application Laid-Open No. 49-111622, West German Publication No. 2461919, US Patent No. 3901714, US Patent No. 3062646, US Patent No. 3883350.
No. 38983855, etc. However, the present invention has different effects and technical ideas from these conventional techniques. For example, the inventions described in Japanese Patent Publication No. 38-6447 and US Pat. No. 3,062,646 relate to methods for sensitizing silver halide emulsions. According to the description in the specification, in the present invention, the cyclic thioether compound added to the silver halide photographic light-sensitive material also sensitizes in black-and-white development and color development, but fog also increases. On the other hand, in the case of the macrocyclic compound of the present invention, fog hardly increased even during long-term development at high temperatures, and it was found that the development stability was extremely high. Also, Japanese Patent Application Publication No. 49-111622, U.S. Patent No.
No. 388350 and No. 3893855 describe silver halide photographic materials containing a tuna cyclic ligand having four electron donor atoms.
This invention is a method for sensitizing Ag ⁺⁺ ions by disproportionating them, and its action and effect are clearly different from the method of the present invention. Furthermore, the application of this technique is for use in a diffusion transfer method, which is different from the technique of the present invention. The silver halide used in the silver halide photographic material processed according to the present invention includes conventional silver halide photographic emulsions such as silver bromide, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any used is included. These silver halides may be coarse-grained or fine-grained, and can be prepared by any known method, such as U.S. Pat.
No. 3317322, No. 2222264, No. 2222264, No. 3317322, No. 2222264, No.
No. 3320069, No. 3206313 or Journal of Photographic Science (J.
Phot.Sci) Volume 12, No. 5 (September, October issue), 1964
It can be adjusted by the method described in 2010, pp. 242-251. It is also possible to mix and use silver halides prepared by different methods. Note that it is preferable to remove soluble salts from the silver halide emulsion used in the present invention, but
Unremoved ones are also used. Further, the silver halide emulsion used in the photographic light-sensitive material processed according to the present invention can be sensitized with various chemical sensitizers. Examples of sensitizers include activated gelatin, sulfur sensitizers (sodium thiosulfate, allylthiocarbamide, thiourea, allyl isothiacyanate, etc.), selenium sensitizers (N,
N-dimethylselenurea, selenurea, etc.), reduction sensitizers (triethylenetetramine, stannic chloride, etc.), such as potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, 2-ourosulfobenzothiazole methyl chloride , ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadide, and the like can be used alone or in combination of two or more. When using a metal sensitizer, rhodanammonium can also be used as an auxiliary agent.
Furthermore, the silver halide emulsion used in the present invention is
In order to impart photosensitivity to a desired wavelength range, each material is optically sensitized using one or more sensitizing dyes. Various sensitizing dyes can be used, but optical sensitizers that can be advantageously used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, and trinuclear or tetranuclear cyanines. These optical sensitizers include thiazoline, thiazole, etc. as a nitrogen-containing heterocyclic nucleus in their structure. or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, parbituric acid, thioparbituric acid, pyrazolone, etc., and such a nucleus can be substituted with alkyl, hydroxyalkyl, halogen, phenyl, cyano, or alkoxy. , may also be fused with a carbocycle or a heterocycle. Further, the silver halide emulsion used in the present invention is disclosed in, for example, US Pat. No. 2,444,607,
No. 2716062, No. 3512982, West German Application Publication No. 1189380, No. 2058626, No. 2118411,
Compounds described in Japanese Patent Publication No. 43-4133, US Pat. 5,6-trimethylene-7-hydroxy-s-triazolo(1,5
-a) Pyrimidine, 5,6-tetramethylene-7
-Hydroxy-s-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-s-triazolo(1,5-a)pyrimidine, 7-hydroxy-s-triazolo(1,5-a)pyrimidine , 5-methyl-6bromo-7-hydroxy-s
- triazolo(1,5-a)pyrimidine, gallic acid esters (e.g. isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole) ), benztriazoles (5-bromobenztriazole, 4-methylbenztriazole), benzimidazoles (6-nitrobenzimidazole), etc. can be used for stabilization. In addition, silver halide emulsions used in the present invention include, for example, West German Application Publication No. 2,217153;
A latent image stabilizer such as a sulfur-containing amino acid compound described in No. 2217895 can also be used. When the silver halide photographic light-sensitive material used in the present invention is subjected to color development processing, the light-sensitive material contains a coupler for forming a color image, and useful couplers include, for example, an open-chain methylene yellow coupler, Examples include 5-pyrazolone-based magenta couplers, phenol-based or naphthol-based cyan couplers, and these couplers may be so-called 2-equivalent type or 4-equivalent type couplers. It is also possible to use azo-type colored couplers, osazone-type compounds, development-diffusible dye-releasing couplers, etc. for this purpose.
Further, at this time, it is desirable to use a so-called colorless coupler, which is colorless before color development, in combination with the above-mentioned masking coupler. Furthermore, in order to improve the photographic characteristics, so-called competing couplers, DIR couplers, etc. are used in combination with various couplers.
It can also contain couplers called BAR couplers. Open-chain ketomethylene compounds have traditionally been used as yellow couplers; for example, a pivalyl acetanilide type yellow coupler is described in French Patent No. 1291110, and a benzoylacetanilide type yellow coupler is described in Japanese Patent Publication No. 1983-19031. No. Publication,
The one described in U.S. Pat. No. 2,875,051 is effective, and the U.S. Pat.
3408194 specification, US Patent No. 3447928 for active point -o-acyl substitution, JP-A-48-29432 for active-point hydantoin compound substitution, JP-A-48-66834 for active point urazole compound substitution ,
Special Publication of Active Point Substitution with Succinimide Compounds in 1977-
No. 13576, JP-A-50-28834 for active point substitution with a monooxoimide compound, JP-A-49-10736 for active point substitution with a pyritazone compound, British Patent No. 94490 for active point fluorine substitution, British Patent No. 780507 for active point chlorine or bromine substitution, British Patent No. 780507 for active point -o-sulfonyl substitution
Those described in the specification of No. 1092506 etc. can be used as effective yellow couplers. Among these yellow couplers, particularly effective ones are described in U.S. Patent No. 3408194, Japanese Patent Application Laid-open No. 1982-29432, Japanese Patent Application Laid-Open No. 1972-28834, Japanese Patent Application Laid-open No. 1972-66834, and Japanese Patent Application Laid-open No. 1972-66834. No. 87650, Japanese Patent Application Publication No. 1973-123342
No., JP-A-48-66835, JP-A-49-17371, same.
No. 49-13576, Japanese Patent Publication No. 50-158329, No. 49-1229
No. 48-94432. Examples of magenta couplers used in the present invention include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indazolone compounds. U.S. Patent No. for pyrazolone magenta coupler
Specification No. 3127269, Specification No. 2600788, Specification No.
Specification No. 5519429, Specification No. 3419391, Specification No.
Specification No. 3062653, Specification British Patent No. 1342553,
Those described in West German Patent No. 2162778, Japanese Unexamined Patent Publication No. 1972-29639, and Japanese Patent Application No. 1984-8433, pyrazolone triazole magenta couplers include West German Patent No. 1810464 and Belgian patent. What is described in specification No. 792525,
Pyrazolinobenzimidazole magenta couplers are disclosed in U.S. Patent No. 3061432 and Japanese Pat.
46-60479 and West German Patent No. 2156111, and as the indazolone magenta coupler, those described in Belgian Patent No. 769116 are used. Particularly preferred magenta couplers in the present invention include 3-anilinopyrazolone magenta couplers described in US Pat. No. 3,127,269. Others: JP-A-49-53436, JP-A-49-
No. 16057, Special Publication No. 49-24080, U.S. Patent No.
Those described in each specification or publication of No. 3725067 are also preferably used. Furthermore, useful cyan couplers used in the present invention include, for example, the phenol compounds described in U.S. Pat. No. 2,423,730, U.S. Pat. Active point-o-aryl-substituted naphthol compounds described in Patent No. 2474293 and British Patent No. 1084480, JP-A-47-37425
Publication No. 10135, Japanese Patent Publication No. 1983-10135, Japanese Patent Publication No. 1973-
Publication No. 25288, Japanese Patent Application Publication No. 112038, Japanese Patent Publication No.
Phenols described in JP-A-50-120334, JP-A-50-117422, JP-A-50-130441,
Examples include naphthol compounds. Others: JP-A-50-134644, JP-A-47-21139, JP-A-49-114424, U.S. Patent No. 3737316, U.S. Pat.
Those described in the specifications or publications of No. 3839044 and No. 3758308 are also preferably used. As the colored magenta coupler, a compound in which the active site of a colorless magenta coupler is arylazo-substituted or heteroarylazo-substituted is used; for example, as described in U.S. Pat.
Examples thereof include compounds described in Specification No. 2983608, Specification No. 2801171, British Patent No. 937621, and Japanese Patent Application Laid-open No. 131448/1983. As a colored cyan coupler, active point arylazo-substituted U.S. Pat. No. 3,034,892 and U.S. Pat.
Specification No. 2521908, British Patent No. 1255111,
Compounds described in JP-A-48-22028, as well as JP-A-50-10135, JP-A-50-25228, JP-A-50-117422, JP-A-50-120334
Publication No. 50-130441, British Patent No.
Masking couplers of the type described in JP-A-1084480 and JP-A-50-123341, in which the dye flows out into the processing bath by reacting with the oxidized developer, can also be used. U.S. Patent No. 1 for a computing coupler
Those described in the specification of No. 2742832, such as citradinic acid, can be used, and as the Weis coupler, those described in West German Patent No. 1155676 can be used. Hydrophilic colloids that are advantageously used to prepare the silver halide emulsion used in the present invention include gelatin, colloidal albumin,
Agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, imidized polyamide, polyvinyl alcohol, hydrolyzed polyvinyl acetate, such as British Patent No. 523661, West German Publication No. 2255711,
Water-soluble polymers and gelatin derivatives such as those described in U.S. Pat. No. 2046682 and U.S. Pat. gelatin, or polymerizable monomers having an ethylene group such as styrene acrylate, acrylic ester, methacrylic acid, and methacrylic ester as described in U.S. Pat. Nos. 2,548,520 and 2,831,767. These hydrophilic colloids can also be used in layers that do not contain silver halide, such as antihalation layers, protective layers, and intermediate layers. The hydrophilic colloid used in the present invention may include various photographic additives, such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, antistain agents, PH adjusters, as needed. Antioxidants, antistatic agents, thickeners, graininess improvers, dyes,
Mordants, brighteners, development speed regulators, matting agents, and the like 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, for example, thickeners and plasticizers such as those disclosed in U.S. Pat.
No. 4939, West German Application Publication No. 1904604, Japanese Unexamined Patent Publication No. 1973
-63715, Japanese Patent Publication No. 45-15462, Belgian Patent No. 762833, U.S. Patent No. 3767410, Belgian Patent No. 558143, such as styrene-sodium maleate, etc. There are polymers, dextran sulfate, etc. As the hardening agent, use various hardening agents such as aldehyde type, epoxy type, ethyleneimine type, active halogen type, vinyl sulfone type, isocyanate type, sulfonic acid ester type, carbodiimide type, mucochloric acid type, acyloyl type, etc. I can do it. As an image stabilizer, 6,6'-butylidene bis(2-t-butyl-4-methylphenol),
4,4'-methylenebis(2,6-di-t-butylphenol) and the like can be used. In addition, examples of ultraviolet absorbers include, for example, Special Publication No. 48-736, Special Publication No. 5496, Special Publication No. 48-41572, Special Publication No. 48-41572, Special Publication No. 48-41572, Special Publication No.
-30492, Special Publication No. 31255, U.S. Patent No.
Compounds described in the specifications or publications of No. 3253921 and British Patent No. 1309349, especially 2-
(2′-hydroxy-5′-tertiary butylphenyl)benzotriazole, 2-(2′-hydroxy-3′,
5'-di-tert-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-
5'-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tertiary butylphenyl)-5-chloropenzetriazole, and the like can be used. British Patent Nos. 548532 and 1216389 as coating aids, emulsifiers, permeability improvers for processing liquids, antifoaming agents, and surfactants used to control various physical properties of photosensitive materials. US Patent No.
No. 3026202, No. 3514293, Special Publication Showa 44-26580
No. 43-17922, No. 43-17926, No. 43-
No. 13166, No. 48-20785, French Patent No. 202588,
Anionic, cationic, nonionic, or amphoteric compounds described in Belgian Patent No. 773459 and Japanese Patent Application Laid-open No. 101118/1984 can be used. As the mordant, for example, compounds described in the specifications of US Pat. No. 2,113,381 and US Pat. No. 2,548,564 can be used. As anti-stain agents, for example, US Pat. No. 2,361,210, US Pat.
Compounds described in the specifications of No. 2732300 and No. 3700453, especially 2-methyl-5-hexadecyl-hydroquinone, 2-methyl-5-sec-
Octadecyl-hydroquinone, 2,5-di-t
-Octylhydroquinone etc. can be used. As antistatic agents, Japanese Patent Publication No. 46-24159,
JP-A-48-89979, U.S. Patent No. 2882157, U.S. Patent No.
No. 2972535, Japanese Patent Publication No. 48-20785, No. 48-43130
No. 48-90391, Special Publication No. 46-24159, No. 46-
No. 39312, No. 48-43809, No. 49-4853, No. 49-
Compounds described in the specifications or publications of No. 64, No. 47-8742, and JP-A No. 47-33627 can be used. In addition, as a matte agent, for example, British Patent No. 1221980, US Patent No. 2992101,
No. 2956884, French Patent No. 1395544, Special Publication No. 1977-
Compounds described in the specifications or publications of No. 43125, particularly silica gel having a particle size of 0.5 to 20μ, and polymers of polymethyl methacrylate having a particle size of 0.5 to 20μ can be mentioned. Furthermore, benzyl alcohol, polyoxyethylene compounds, etc. can be used as development accelerators, and these compounds are effective even when added to the processing bath. The silver halide photographic light-sensitive material used in the present invention is formed by coating a silver halide emulsion containing the various photographic additives and other constituent layers on a suitable photographic support. Examples of the support used include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate,
For example, polyester film such as polyethylene terephthalate, polyamide film, polypropylene film, polycarbonate film,
Typical examples include polystyrene film and the like, and these supports are selected as appropriate depending on the intended use of the photographic material. The silver halide photographic material used in the present invention is preferably applied to various uses. For example, silver halide photographic materials for black and white include general negative and positive light-sensitive materials, X-ray light-sensitive materials, light-sensitive materials for printing, light-sensitive materials for microphotography, light-sensitive materials for infrared photography, and the like. Furthermore, color silver halide photographic materials include general negative and positive photosensitive materials, general reversal photosensitive materials, direct positive photosensitive materials, and special photosensitive materials (for example, printing, X-ray, high resolution, infrared, etc.) ) Photosensitive materials, etc.
Furthermore, it can also be applied to various photosensitive materials for silver salt diffusion transfer, dye diffusion transfer, silver dye bleaching, heat development, and printing. After exposure, the silver halide photographic material used in the present invention is developed with a developer containing a black and white developing agent or a color developing agent as a main component. As a developing agent preferably used in the present invention, for example, hydroquinone, metol, phenidone, etc. are used as a developing agent for black and white.
These developing agents may be used alone or in combination of two or more. Especially MQ or PQ
The developer is advantageously applied to the present invention because of its excellent liquid adjustment and storage stability, but in addition,
"The Theory of Photographic Process"
Developers or development aids such as those described in "Process", 3rd edition, pages 374-378 (1966) can be advantageously used. In addition, as a color developing agent,
Typical examples include p-phenylenediamine-based products, such as diethyl-p-phenylenediamine hydrochloride,
Monomethyl-p-phenylenediamine hydrochloride, dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-diethylaminotoluene hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-methane Sulfonamidoethyl-4-aminoaniline, 4-N
-Ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline hydrochloride, 4-amino-3
-Methyl-N-ethyl-N-β-hydroxyethylaniline sulfate, 4-amino-3-β-
(Methanesulfonamido)ethyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-m-toluidine, etc. are used. These color developing agents may be used alone or in combination of two or more, and if desired, in combination with a black and white developing agent such as hydroquinone. Furthermore, the developing solution used in the present invention generally has pH adjustment and buffer functions using caustic alkali, alkali carbonate, or amines, the addition of preservatives such as sodium sulfite, and the addition of inorganic agents such as brompotali. It is optional to add an organic development inhibitor such as a development inhibitor and benztriazole, a development regulator such as citradinic acid, or a development accelerator such as benzyl alcohol. In the present invention, "at least one of the macrocyclic compounds"
"Developing in the presence of seeds" means incorporating the macrocyclic compound of the present invention into a silver halide photographic light-sensitive material by various methods, and developing the light-sensitive material in a developer; This means dissolving the macrocyclic compound of the present invention in a developing solution and processing a conventional silver halide photographic material containing the macrocyclic compound of the present invention, and various embodiments are included. be done. Generally, the macrocyclic compound of the present invention may be contained in either the photographic material or the developer. For example, the development temperature is 50
The temperature is preferably below 0.degree. C., particularly preferably around 30.degree. C., and the development time is generally completed within 30 minutes, particularly preferably within 5 minutes, which often brings about good results. That is, due to the development stabilization effect, the occurrence of fog is suppressed, resulting in a sensitizing effect, and the occurrence of fog during storage is also suppressed, resulting in a so-called thermostability effect.
Further, post-development processing steps such as stopping, fixing, bleaching, bleach-fixing, and further steps such as pre-hardening and neutralization may be optionally employed, and these may be omitted as appropriate. Furthermore, the macrocyclic compound of the present invention may be dissolved in these treatment baths as necessary. For example, if added to a bleach bath,
It can be expected to have a bleaching accelerating effect. 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 typical examples, but the technical scope of the present invention is not limited in any way by the following examples.
A wide variety of implementations are possible. Example 1 A gold sensitizer and a sulfur sensitizer were added to a silver iodobromide emulsion for X-rays containing 2 mol% of silver iodide, and after second ripening to the highest sensitivity, 4-hydroxy-6 -Methyl-1,3,3a,7-tetrazaindene was added as a stabilizer in an amount of 4.0 g per mole of silver halide, and predetermined amounts of a coating aid and a hardening agent were added. The silver halide emulsion thus obtained was divided into seven parts, one part of which was coated simultaneously with a protective layer formed using a 2.5% aqueous gelatin solution on a polyethylene terephthalate film base, and a comparison sample (sample number 1) was coated on a polyethylene terephthalate film base. )It was created. On the other hand, in the remaining 6 parts of the silver halide emulsion divided above, exemplified compounds of the macrocyclic compound of the present invention [6],

Samples of the present invention (sample numbers 2, 3,
4, 5, 6 and 7) were prepared. A medical fluorescent X-ray screen (KYOKKO, FS, emission spectrum maximum 4250
A continuous roller conveyance type automatic system that can consistently perform development, fixing, washing, and drying after irradiating X-rays for 0.5 seconds through a light wedge made of aluminum (made by Dainippon Toyo Co., Ltd.) and aluminum with two steps. A high-temperature rapid development process was performed using a developing machine at 40° C. for 30 seconds and 45 seconds using the following developer formulation. [Developer formulation] Anhydrous sodium sulfite 70g Hydroquinone 10g Boric anhydride 1g Sodium carbon monohydrate 20g 1-phenyl-1,3-pyrazolidone 0.35g Sodium hydroxide 5g 5-methylbenzotriazole 0.05g Potassium bromide 5g Glacial acetic acid 8g Add water and make up to 1. PH=10.20 Sensitometry was performed on the samples of the present invention and comparative samples thus obtained, and the photographic performance obtained is shown in Table 1. Note that the sensitivity shown in the table is a relative value with respect to the sensitivity when the comparative sample (sample number 1) was developed for 30 seconds as 100.

[Table] As is clear from Table 1, the macrocyclic compounds of the present invention (exemplary compounds [6],

By adding [9] or [10], even in high-sensitivity silver halide photographic materials that undergo high-temperature rapid development processing, it is possible to achieve photographic performance with excellent gradation without lowering sensitivity and without fogging. I understand what is shown. Example 2 A gold sensitizer and a sulfur sensitizer were added to a microfilm silver iodobromide emulsion containing 98 mol% of silver bromide and 2 mol% of silver iodide with developed [100] planes in the form of fine grains.
After a second ripening to the highest sensitivity, 4.0 per mole of silver halide using 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene as a stabilizer.
g, and further added predetermined amounts of a coating aid and a hardening agent. A sample was obtained by simultaneously coating the silver halide emulsion thus obtained on a polyethylene terephthalate film base together with a protective layer formed using a 2.5% gelatin aqueous solution. This sample was divided into 5 parts, and each sample was exposed to white light using a KS-1 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) based on the JIS method, and then processed in the same manner as in Example 1 for comparison. The photographic performance results of the sample (sample number 8) were obtained (however, the development time was 30 seconds). On the other hand, for the remaining four samples, the above-mentioned exemplified compounds [15] and [17] of the macrocyclic compounds of the present invention were added to the developer in the amounts shown in Table 2, and the same treatment was carried out. type of sample (sample number 9,
10, 11 and 12) photographic performance results were obtained. These results are summarized in Table 2.

[Processing process]

Color development (4 minutes) - bleach fixing (1 minute 30 seconds) - washing with water (2 minutes) - stabilization (1 minute) - rinsing - drying The composition of the processing bath used is as follows. The processing temperature is 30°C for all processes except for washing and rinsing.
I did it at ℃. [Color developer] Benzyl alcohol 5.0ml Sodium hexametaphosphate 2.5g Anhydrous sodium sulfite 1.85g Potassium bromide 0.5g Sodium bromide 1.4g Borax 39.1g N-ethyl-N-β-methanesulfonamide
Ethyl-4-amino-3-methylaniline sulfate 5.0g Dilute to 1 with water and adjust the pH to 10.3. [Bleach-fix solution] Ethylenediaminetetraacetate iron ammonium
61.0g Ammonium thiosulfate 124.5g Sodium metabisulfite 13.3g Anhydrous sodium sulfite 2.7g Ethylenediaminetetraacetic acid-2-ammonium 5.0g Bring to 1 with water and adjust the pH to 6.5. [Stabilizer] Add 2.0ml of glacial acetic acid and 800ml of water, then adjust the pH to 3.5-4.0 with sodium acetate.
Adjust to 1 and finish with water. Sensitometry was performed on the samples of the present invention and comparative samples thus obtained, and the photographic performance obtained is shown in Table 3.

[Color developer]

Anhydrous potassium carbonate 26.0g Anhydrous sodium bicarbonate 3.5g Potassium sulfite dihydrate 1.8g Potassium bromide 1.3g Sodium chloride 0.2g Sodium nitrilotriacetate monohydrate 2.0g Potassium hydroxide 0.4g Hydroxylamine sulfate 2.0g 4- Amino-3-methyl-N-ethyl-(β-
Hydroxyethyl)aniline sulfate 5.0g Make up to 1 with water. PH=10.5 [Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt
100g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150g Glacial acetic acid 10.0ml Make 1 with water. PH=6.0 [Fixer] Ammonium thiosulfate (70% aqueous solution) 175.0ml Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Adjust to 1 with water. PH=6.0 [Stabilizer] Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Adjust to 1 with 7.5ml water. Sensitometry was performed on the samples of the present invention and comparative samples thus obtained, and the photographic performance obtained is shown in Table 4. Note that the sensitivity is expressed as a relative sensitivity with the sensitivity of sample number 18 as 100.

[Developer prescription]

Potassium hydroxide 75g Cesium hydroxide 47g Titanium hydroxide 500g Carboxymethyl cellulose 35g Benzotriazole 10g 5-Bromo-6-methyl-4-azabenzimidazole 1g 2-Methylimidazole 3.5g N-phenethyl-α-pyronium bromide
17.5 g Adjust to 1 with water After processing, development was stopped by washing the negative with acetic acid. A comparative sample was prepared in this way. Next, 2 g of the above-mentioned exemplified compound [16] of the macrocyclic compound of the present invention was added to the developer solution, and a sample of the present invention was prepared by performing the same treatment. On the other hand, it showed excellent photographic performance with no decrease in sensitivity and no fogging. On the other hand, 2 g of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane (outside the present invention) was added to the developer to obtain the above comparative sample. When the same processing as above was carried out, an increase in sensitivity was observed compared to the above comparative sample, but a product with considerably higher fog was obtained. Example 7 [Composition of A-D] A: 660 ml of distilled water, 40 g of gelatin, potassium bromide
160g, potassium iodide 6g (70℃) B: 2000ml distilled water, 200g silver nitrate (68℃) C: 600ml distilled water, 360g gelatin (70℃) D: 200ml distilled water (70℃) Stir the above A and add to it. 1/3 of B above
was added for 1 minute, then added the above D, and heated at 70℃ for 10 minutes.
Let rise for a minute. Next, add 1/3 of the above B for 1 minute, age at 70℃ for 10 minutes, and then add the remaining 1/3 of the above B.
Add 3 and mature at 70℃ for 30 minutes. Add the above C while stirring, and after 2 minutes, cool and solidify. The electrical conductivity of the emulsion is 1800 in running water below 15℃.
Rinse with water until ×10 ^-6 mho/cm. After washing with water,
Take the total amount to 3Kg and divide it into two. A part of the 4-hydroxy-6-
2.5 g of methyl-1,3,3a,7-tetrazaindene was added as a stabilizer, and predetermined amounts of a coating aid and a hardening agent were added. Then, a comparative sample (sample number 26) was prepared by simultaneously coating a polyethylene terephthalate film base with a protective layer formed using a 2.5% gelatin aqueous solution. Separately, 1.0 g of the above-mentioned exemplary compound [12] of the macrocyclic compound of the present invention was added to the remaining part of the above-mentioned divided portion, and second ripening and coating were carried out in the same manner as the above-mentioned comparative sample. Sample number 27) was prepared. Separately, an emulsion was prepared in the same manner as the comparative sample described above, except that 2.0 g of the exemplified compound [14] of the macrocyclic compound of the present invention was added to D, and this was washed with water. Divide into two and take one part,
A sample of the present invention (sample number 28) was prepared by performing second ripening and coating in the same manner. Furthermore, 1.0% of the above-mentioned exemplary compound [11] of the macrocyclic compound of the present invention is added to the remaining part of the above-mentioned divided portion.
A sample of the present invention (sample number 29) was prepared by performing second ripening and coating in the same manner as the comparative sample except that g was added. The thus obtained samples of the present invention and comparative samples were exposed to white light using a KS-1 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) based on the JIS method, and then used in Example-1. The same process was carried out using the same developer. Sensitometry was performed on the samples of the present invention and comparative samples thus obtained, and the photographic performance obtained is shown in Table 5. Note that the sensitivity is expressed as a relative sensitivity with the sensitivity of sample number 26 as 100.

[Table] As is clear from Table 5, even when the macrocyclic compound of the present invention is used in the production of high-sensitivity black-and-white negative emulsions, there is no decrease in sensitivity and excellent photographic properties without fogging. It can be seen that this shows that

Claims (1)

[Claims] 1. Development processing of an imagewise exposed silver halide photographic light-sensitive material in the presence of at least one macrocyclic compound represented by the following general formula [], [] or []. A method for processing a silver halide photographic material, characterized by: (In the general formula [], [] or [], A represents an ethylene group or an ethene group which may be substituted with an alkyl group, D represents an oxygen atom or a sulfur atom, and X
represents nitrogen atom, phosphorus atom (same atom),
m ₃ represents 1 or 2, m ₄ represents 1 or 2, m ₅ represents 0 or 1, n ₃ represents 1 or 2, n ₄ represents 1 or 2, n ₅ represents 0 or 1, p ₂ represents 0 , represents 1 or 2, R ₃ and R ₄
each represents a hydrogen atom, a hydrocarbon group having 1 to 12 carbon atoms, or an alkoxycarbonyl group. 2. The method for processing a silver halide photographic material according to claim 1, wherein the macrocyclic compound is present in the silver halide photographic material and/or the developer. 3. A method for processing a silver halide photographic light-sensitive material according to claim 1 or 2, wherein the macrocyclic compound is a phosphonium and/or ammonium salt and a nitrogen and/or phosphorus oxide. . 4 The macrocyclic compound is 1,4,7,10,13,16-
hexaoxacyclooctadecane, 2,5,8,
15,18,21-hexaoxatricyclo(20,4,
0,0) hexacosane, (2,3)(14,15)-dibenzo-1,4,7,10,13,16,19,22-octaoxacyclotetracosate-2,14-diene,
4,7,13,16,21,24-hexaoxer-1,10
-Diazabicyclo[8,8,8]hexacosane,
1,4,10,13-tetrathia-7,16-diazacyclooctadecane or 4,7,13,16,21,24
-Hexathia-1,10-diazabicyclo [8,
8,8] The method for processing a silver halide photographic material according to claim 1, 2 or 3, characterized in that hexacosane is used. 5. Claim No. 5, characterized in that, after imagewise exposure, a silver halide photographic light-sensitive material containing a macrocyclic compound is processed with a developer containing at least one of hydroquinone, metol, and phenidone as a developing agent. A method for processing a silver halide photographic material according to any one of items 1 to 4. 6. Claims 1 to 6, characterized in that, after imagewise exposure, a silver halide photographic light-sensitive material containing a macrocyclic compound is processed with a developer containing an aromatic primary amine color developing agent. 5. The method for processing a silver halide photographic material according to any one of Item 5. 7. Claim 1, characterized in that the imagewise exposed silver halide photographic light-sensitive material is processed with a developer containing a macrocyclic compound and at least one of hydroquinone, metol, and phenidone as a developing agent. A method for processing a silver halide photographic material according to any one of items 1 to 5. 8. Claims 1 to 8, characterized in that the imagewise exposed silver halide photographic light-sensitive material is processed with a developer containing a macrocyclic compound and an aromatic primary amine color developing agent. 5. The method for processing a silver halide photographic material according to any one of Item 5.