EP0315952A2

EP0315952A2 - Photographic processing agents and a method for processing light-sensitive photographic materials

Info

Publication number: EP0315952A2
Application number: EP88118579A
Authority: EP
Inventors: Shinsaku Nagaoka; Tomomichi Kasamatsu; Masayuki Kurematsu; Shigeharu Koboshi
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1987-11-12
Filing date: 1988-11-08
Publication date: 1989-05-17
Also published as: EP0315952A3; JPH01128066A; JPH07117708B2

Abstract

A photographic processing agent and a processing method for photographic material using the processing agent are disclosed. The processing agent is an inclusion compound comprised of a host enclosing an effective component for processing of a photographic material as its guest and used in a processing solution for pfocessing the photographic material. Various kinds of effective components for photographic processing can be used in the form of the inclusion compound of the invention. The photographic processing solution containing the effective component in the form of inclusion compound is improved in its stability in the course of running the processing. As a result of that, good properties of the photographic material can be stably obtained by using the processing solution.

Description

FIELD OF THE INVENTION

The present invention relates to photographic processing agents for use in forming a photographic - processing liquid having a long-term processing stability and a method for processing light-sensitive photographic materials, and more particularly to photographic processing agents for light-sensitive photographic material processing use for the formation of a photographic processing liquid which is for use in processing light-sensitive photographic materials such as silver halide light-sensitive photographic materials of which the processing stability is retained over a long period of time and which enables the high- concentration-with-low-replenishment processing, and a method for processing light-sensitive photographic materials with use of such photographic processing agents.

BACKGROUND OF THE INVENTION

The processing of light-sensitive photographic materials, in the case of, e.g., silver halide light-sensitive color photographic materials, is comprised basically of two processes: color developing process and desilvering process. The desilvering process consists of bleaching and fixing processes or of a bleach-fix process. Additional processes included in the processing are rinsing, washing, and stabilizing or stabilization treatment substituting for washing, and the like.
In the color developing, the exposed silver halide is reduced to become silver, and at the same time, the oxidized aromatic primary amine developing agent reacts with couplers to form dyes. During this process, the halogen ion that has been produced by the reduction of the silver halide becomes dissolved out into and deposited in the developer solution. Separately, the components of the light-sensitive material, such as the development inhibitor and others contained in the material, are also dissolved out into and deposited in the developer solution. In the desilvering process, the silver that has been formed by development is bleached by the oxidizing agent, and all the silver salts are them removed in the form of soluble salts from the light-sensitive material by a fixing agent. In addition, the monobath bleach-fix process which performs both bleaching and fixing simultaneously is also known.
In the above color developer solution, whereas the development inhibitor becomes accumulated as the developing of the light-sensitive material makes progress as stated above, the color developing agent and development accelerator such as benzyl alcohol are consumed or carried out of the developer solution by impregnating into the light-sensitive material, thus resulting in the decline of the concentration of the effective component for photographic processing. So are the bleaching solution and fixing solution or bleach-fix bath; the concentration of the effective component for photographic processing depends on the processing quantity of light-sensitive materials and changes according to the passage of time. Accordingly, in a method of continuously processing a large quantity of light-sensitive materials by an automatic processor, a means to keep the effective component for photographic processing in certain constant concentration ranges is required for avoiding changes in the processed image characteristics due to the changes in the concentration of the effective component for photographic processing. As such the means a • method of replenishing the developer solution with a replenisher liquid is usually used to make up for the shortage of necessary effective components as well as diluting the increased undesirable components.
It is the present state, however, that even in the case where the photographic processing is made, being replenished with a replenisher solution, if the processing is continued over a long period, its processing stability cannot be secured.
This will now be described further by taking a color developer solution as an example:
In the field of photography, incorporation of a sulfite into a color developer solution containing an aromatic primary amine color developing agent is prevailing. The sulfite to be used is generally in the form of a sulfite or bisulfite of an alkali metal. This is used for the purpose of restraining the air oxidation of the aromatic primary amine-type developing agent contained in the color developer solution; it is very useful for this purpose (reference can be made to, e.g., the 'Photography, its Material and Processes', C.B. Neblette, 6th Edition, D. Van Nostrand Co., Inc., p.234). However, the allowable sulfite content of the developer solution is restricted since the sulfite competes with the coupler to the developing agent that has been oxidized in the color developer solution or in the photographic light-sensitive material. This competion adversely affects the color formation. To give a typical example, a yellow dye-forming coupler is slower in the reaction with the oxidized developing agent than cyan dye- and magenta dye-forming couplers, so that the above-mentioned competion between the couplers and the sulfite has a seriously bad influence upon the yellow dye image formation.
The latest tendency in the photographic processing technology is to use a less replenishment volume to the developer solution, which raises questions in connection with lowering the replenishing rate and increasing the concentration of replenisher components. The lowering of the replenishing rate means prolonging the residence time of the developer situation in a processor, whereby the air oxidation rate of the developing agent is increased. This tendency can be prevented by increasing the sulfite concentration in the developer solution, but in that case, the sulfite then competes with the coupler to the oxidized developing agent, thus exerting a bad influence upon the dye image, particularly in the form of lowering the yellow D max. That is, the sulfite, when its amount is kept low enough to little lower the yellow dye density, shows no adequate effect of protecting the developer solution from air oxidation, while on the contrary when its amount is increased in order to satisfy the protection of the developer solution from air oxidation, the aforementioned bad influence upon the dye density increases up to an untolerable level. Therefore, it has until now been difficult to form a color developer solution excellent in the long-term processing stability.
On the other hand, when the processing solution is a bleaching solution or a bleach-fix bath, its bleaching agent, e.g., a ferric complex salt, if a sulfite is present, has its oxidation-reduction potential lowered to tend to produce Fe (11). The bleaching bath or bleach-fix bath, besides bleaching silver, has a function to convert a colorless dye into a chromatic dye; particularly in the case of a cyan dye, it is not color-developed sufficiently in a color developer solution but becomes a complete cyan dye in the bleaching bath or bleach-fix bath. However, if Fe(II) is present to excess in the bath, a leuco compound is formed to cause the D max of the cyan dye to be lowered, and therefore the bleaching or bleach-fix bath becomes one lacking in the long-term processing stability.
Thus, the fact that an effective component for processing has its concentration changed by its reaction with other constituent or by its air oxidation to thus make the processing solution unable to retain its long-term processing stability applies not only to the above-mentioned color developer solution, bleaching solution or bleach-fix solution but also to all photographic processing solutions for use in processing photographic light-sensitive materials whatever the type of the light-sensitive material to be processed may be.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide photographic processing agents capable of forming a photographic processing solution having a long-term processing stability and a method for processing light-sensitive photo graphic materials.
The photographic processing agent of this invention which accomplishes the above object is one for use in a photographic processing solution for processing an imagewise exposed light-sensitive photographic material, in which said photographic processing agent is an inclusion compound comprised of a host enclosing therein an effective component for photographic processing as its guest.
The method for processing light-sensitive photographic materials of this invention which accomplishes the above object is a method for processing an imagewise exposed light-sensitive photographic material, said processing taking place by having a photographic processing agent being an inclusion compound comprised of a host enclosing therein an effective component for photographic processing as its guest present in at least one processing solution.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, the construction of the inclusion compound (host) which encloses an effective component for photographic processing - hereinafter may be called an effective component, although not particularly restricted, is desirable to be made by adopting any of the following conditions so that the concentration fluctuation width of the effective component in a photographic processing solution due to the release of the constituent is less than 1/2 of that in the case of an effective component which does not have the construction of this invention. A preferred embodiment of this invention is an inclusion compound wherein the time required until 90 % by weight of the effective component is released from the compound into a photographic processing solution is not less than three hours, particularly not less than 6 hours, and most preferably not less than 12 hours.
The construction of the host compound is a cavity structure (internal hole) whose cavity may be in any of the cylindrical, basket-type or stratified-type form, and the host compound may be either water-soluble or hydrophobic, but is preferably water-soluble.
Examples of the host (clathrate component) include urea, thiourea, deoxycholic acid, dinitrodiphenyl _ hydroquinone, o-tritimotide, oxyflavan, nickel dicyanoammine, dioxytriphenylmethane, triphenylmethane, methylnaphthalene, spirochroman, perhydrotriphenylene, cyclodextrins including branched cyclodextrin, cyclodextrin polymers (the same shall apply hereinafter), crown ether, water-soluble cyclophane, clay mineral, graphite, zeolite, cellulose, amylose, protein, and the like.
Regarding the above zeolite, examples of natural zeolite include hojasite, chabazite, mordenite, levinite, and the like. On the other hand, examples of synthesized zeolite include montmorillonite, halloysite, and the like.
The host should be selected according to the kind of the effective component for photographic processing on the basis of the size and form of the cavity (internal hole) which the host produces, and the selection should be made in view of the interaction between the host structure and the guest molecule (there exist various interactions ranging from a very weak Van der Waals force to a highly oriented inter- dipole force, and also by one hydrogen bonding).
As the host whose cavitation (internal hole) is in the cylindrical form, urea, thiourea, deoxycholic acid, dinitrodiphenyl, dioxytriphenylmethane, triphenylmethane, methylnaphthalene, spirochroman, perhydrotriphenylene, cyclodextrin, crown ether, water-soluble cyclophane, cellulose, amylose, and the like are known. As the basket-type host, hydroquinone, o-tritimotide, oxyflavan, nickel dicyanoammine, cyclodextrin, crown ether, water-soluble cyclophane, zeolite, and the like are known. And as the stratified host, clay mineral, graphite, and the like are known.
As the host for the guest which is, e.g., methanol, acetonitrile, formic acid, C0₂, 0₂, HCI, HBr, H₂S or S0₂, ,8-hydroquinone is suitably usable, and as the host for the guest which is, e.g., an imidazole derivative (fungicide), cyclodextrin is suitably usable. In addition, those as the host in the case where the effective component for photographic processing is an n-paraffin derivative include urea and zeolite; those as the host in the case of branched or cyclic hydrocarbons include thiourea; those as the host in the case where the effective component is a fatty acid include deoxycholic acid and amylose; those as the host in the case where the effective component is an aromatic compound include deoxycholic acid, cyclodextrin and water-soluble cyclophane; those as the host in the case where the effective component is a diphenyl derivative include dinitrophenyl; those as the host in the case where the effective component is cyclohexane, benzene, chloroform or phenol include o-tritimotide, nickel dicyanoammine and perhydrotriphenylene; those as the host in the case where the effective component is an n-alkane include dioxytriphenylmethane; those as the host in the case where the effective component is a dye include cyclodextrin, cellulose and protein; those as the host in the case where the effective component is a hydrophilic material or polar compound include clay mineral and zeolite; and those as the host in the case where the effective component is an alkali metal include graphite and crown ether.
Subsequently, branched cyclodextrin as an example of the host to be suitably usable in this invention will now be explained.
The branched cyclodextrin to be used in this invention is one that is obtained by adding in the branched form to or combining with the known cyclodextrin a water-soluble material such as a monosac- charide or disaccharide: e.g., glucose, maltose, cellobiose, lactose, cane sugar, galactose, glucosamine, or the like; preferably maltosylcyclodextrin obtained by combining maltose with the cyclodextrin (the number of the combined molecules of the maltose may be any of one molecule or two or three molecules) or glucosylcyclodextrin obtained by combining glucose with the cyclodextrin (the number of the comgined molecules of the glucose may be any of one molecule or two or three molecules).
Synthesis of such cyclodextrins can be made according to those synthesis methods of the prior art as described in, for example, the 'Dempun Kagaku' (Starch Science) Vol. 33, No.2, pp.119 to 126 (1986), pp.127 to 132 (1986), and 'Dempun Kagaku' Vol. 30, No.2 pp.231 to 239 (1983), and the like. For example, the maltosylcyclodextrin can be synthesized from cyclodextrin and multose and by combining the maltose with the cyclodextrin, utilizing an enzyme such as isoamylase, pullulanase or the like. The glucosylcyclodextrin can also be synthesized in like manner.
Useful examples of the branched cyclodextrin in this invention include the following compounds: [Exemplified Compounds]

D-1 a-cyclodextrin combined with one molecule of maltose.
D-2 β-cyclodextrin combined with one molecule of maltose.
D-3 y-cyclodextrin combined with one molecule of maltose.
D-4 a-cyclodextrin combined with two molecules of maltose.
D-5 β-cyclodextrin combined with two molecules of maltose.
D-6 y-cyclodextrin combined with two molecules of maltose.
D-7 α-cyclodextrin combined with three molecules of maltose.
D-8 β-cyclodextrin combined with three molecules of maltose.
D-9 γ-cyclodextrin combined with three molecules of maltose.
D-10 a-cyclodextrin combined with one molecule of glucose.
D-11 β-cyciodextrin combined with one molecule of glucose.
D-12 γ-cyclodextrin combined with one molecule of glucose.
D-13 α-cyclodextrin combined with two molecules of glucose.
D-14 β-cyclodextrin combined with two molecules of glucose.
D-15 -y-cyclodextrin combined with two molecules of glucose.
D-16 a-cyclodextrin combined with three molecules of glucose.
D-17 β-cyclodextrin combined with three molecules of glucose.
D-18 -y-cyclodextrin combined with three molecules of glucose.

The structure of such branched cyclodextrins has long been variously investigated by using measuring methods such as HPLC, NMR, TLC (Thin Layer Chromatography), INEPT (Insensitive Nuclei Enhanced by Polarization Transfer) and the like, but is still not established even by the present-day science and technology, and now in the stage of an assumed structure. However, it is a doubtless fact according to the above-mentioned measuring methods that a monosaccharide or disaccharide is linked to the cyclodextrin. Accordingly, in the present invention, in the case where a number of molecules of a monosaccharide or disaccharide are linked to the cyclo dextrin, it includes, for example, as shown in the following figures, both the case where the molecules are linked separately one by one to some of the glucose members of the cyclodextrin and the case where the molecules are linked in the straight-chain form to one of the glucose members of the cyclodextrin.
(Linked in the straight-chain form) (Linked separately)

―: a-1,4 linkage →: a-1,6 linkage
The branched cyclodextrin, because it has the existing cyclodextrin's cyclic structure kept intact, has a similar enclusure function to that of the existing cyclodextrin, and, also because it has additional highly- water-soluble maltose or glucose, is significantly improved in the solubility in water.
And, the cyclodextrins in the above exemplified compounds can be represented by the following Formula A:
[n' is an integer of 4 to 101
Of these, particularly useful ones for this invention are a-cyclodextrin with n = 4, β-cyclodextrin with n = 5, and γ-cyclodextrin with n = 6. Also, of these branched cyclodextrins, especially useful one in this invention is branched S-cyclodextrin.
The above cyclodextrin group exerts its enclosure function to form an inclusion compound of this invention.
The inclusion compound of the cyclodextrin means a compound which, as described in, e.g., F. Cramer, the 'Einschluβverbindungen', Soringer (1954) or M.Hagan, the 'Clathrate Inclusion Compound', Reinhold (1962), has a specific crystal structure formed in the manner that a three-dimensional struc ture comprised of bonded atoms or combined molecules has thereinside an appropriate-size cavity, into which other atoms or molecules penetrate in a certain composition ratio.
The following are publications to which reference can be made for the preparation of inclusion compounds of such cyclodextrins, but these are only limited examples; the preparation is of course not limited thereto:

o Journal of the American Chemical Society
Vo. 71, p.354, 1949
o Chemische Berichte
Vol.90, p.2572, 1957
o Chemische Berichte
Vo1.90, p.2561, 1957.

Also in this invention, in accordance with those methods as described in these publications, inclusion compounds of the cyclodextrin with avaiable photographic constituents as the guest can be prepared.
The branched cyclodextrin to be used in this invention is commercially available: for example, maltosylcyclodextrin is available in a product called 'Isoelite' (registered trade name) by Ensuiko Sugar Refining Co., Ltd.
The branched cyclodextrin for use in this invention may be in the either powdery form or liquid form (e.g., 70% solution).
Subsequently, the cyclodextrin polymer suitably usable in this invention will be explained.
As the cyclodextrin polymer those represented by the following Formula B are particularly suitable.
The cyclodextrin polymer usable in this invention may be prepared by the closs-linking polymerization of a cyclodextrin by using, e.g., epichlorohydrin.
The solubility in water of the aforesaid cyclodextrin polymer is desirable to be not less than 20 grams in 100 ml of water at 25 C, and for that, the polymerization degree n in the above Formula B should be 3 or 4; the smaller the value, the higher the solubilizing effect of and the water-solubility of the cyclodextrin polymer.
Such the cyclodextrin polymer may be synthesized in accordance with those ordinary methods as described in, e.g., Japanese Patent O.P.I. Publication No. 97025/1986, German Patent No. 3,544,842, and the like.
This cyclodextrin polymer also may be used as the inclusion compound of the cyclodextrin polymer for enclosing an effective component as its guest.
Next, the water-soluble cyclophane suitably usable in this invention will now be explained.
The water-soluble cyclophane has a hydrophobic internal hole that is formed by its aromatic ring and methylene chain, so that it is capable of taking therein an organic compound as its guest in its aqueous solution. Furthermore, since it is a purely artificial synthetic host, the hydrophobic internal hole can be freely deisgned according to the structure of one to be its guest. In a cyclophane CP 44.4HCI (1, n = 4) of the type of having a diphenylmethane framework, its internal hole's structure can be changed easily by changing the frame-work or cross-linked portion. The following Hosts 1 and 5, as amine salts, are soluble in water under an acidic condition, while Hosts 2 through 4, where nitrogen is made quaternary, are soluble in water at every pH region. In cyclophanes of these types, since a hydrophobic internal hole of a structure determined according to the diphenylmethane workframe is formed, the take-in of a guest in an aqueous solution thereof selectively takes place chiefly according to the host-guest identification of the three-dimensional structure of the hydrophobic portion. For example, hosts of the 1 and 2 types (n = 4-7), in an aqueous solution, take in significantly selectively aromatic effective components. The host of the type 3 is one that a part of the diphenyl methane framework is replaced by a naphthalene ring, and by the introduction of the naphthalene ring, the width of the internal hole is extended to thus exhibit a capability of taking in aliphatic components suitable for photographic processing. The biscyclophane of the host type 4, which is formed by two hydrophobic internal holes of QCP 44(2, n=4) having aromatic selectivity which are connected by a spacer, where its guest is an appropriate one, forms a complex comprised of two aromatic rings 1:1 simultaneously taken in. This is take-in of a guest according to common identification in a plurality of linking positions, and further such the double host enables also simultaneous take-in of two guest molecules - i.e., guest collection. The optical active cyclophane (Host 5) having asymmetric hydrophobic internal holes is one that is formed by cross-linking two diphenylmethane frameworks with an asymmetric unit derived from L-tartaric acid. In an acid aqueous solution, Host 5 forms a host-guest complex comprised of a chiral aromatic guest and a diastereomeric host. The host of the inclusion compound to be used in this invention is selected from among existing or newly synthesized hosts on. the basis of accumu lated basic data on their take-in effect to or their reaction with effective components, or is designed on its molecule to the structure of an objective guest, i.e., an effective component, or to the progress of an objective reaction condition. These things apply not only to the case where a water-soluble cyclophane is a host but also to the case where other compound is selected as a host.
In addition to the above, details about the host applicable to this invention are described in the 'Host-Guest no Kagaku', compiled by Tetsuro Osa, Kyoritsu Shuppan K.K. (1979), 'Host-Guest Chemistry' compiled by Michio Hiraoka, Kodansha K.K. (1984), and 'Hosetsu Kagobutsu no Kagaku' (Chemistry of Inclusion Compounds), 1st ed., in Gendai Kagaku series 40, Tokyo Kagaku Dojin K.K. (1969), and the like.
The present invention can be applied to every effective component for use in processing all kinds of light-sensitive photographic materials, and thus may be used for photographic processing agents in this invention. Above all, it is desirable to be applied to effective components that are liable to cause changes in concentration in its reaction or oxidation with other components. For example, the invention can be applied to any of those effective components to be used in known methods and known processing solutions as disclosed in Research Disclosure No.176, pp. 28_-30. The photographic processing may, according to purposes, be any of a developing process for the formation of silver images (black-and-white development) or a dye image-forming developing process (color development). The invention can also be applied to those effective components for use in the process wherein black-and-white development (first development) is followed by color development (second development) as in the processing of color reversal light-sensitive materials and to those effective components for use in the process wherein fogging exposure takes place prior to or during development as in the processing of direct-positive-type light-sensitive materials.
The processing may take place in any manner: bath processing is prevalent, but various other methods may also be used which include, for example, the spray method wherein a processing solution is sprayed; the web method wherein processing is carried out by contacting a light-sensitive material with a processing solution-impregnated carrier; the developing method which uses viscous processing solutions; and the like. The present invention, however, is most desirable to be applied to those effective components for use in bath processing. The photographic processing agent of this invention is allowed to be put in a processing bath, but is preferably in the liquid circulation system or stirring system for each bath.
The processing method is not particularly restricted; this invention is applicable to any effective components for use in every processing method. For example, where the light-sensitive material to be processed is a color photographic light-sensitive material, typical methods therefor include the method of color developing followed by bleach-fix and, if necessary, washing and/or stabilizing; the method of color developing followed by bleaching and fixing separately, and, if necessary, further washing and/or stabilizing; the method of making in order prehardening, neutralizing, color develop ing, stop-fix, washing, bleaching, fixing, washing, post-hardening and then washing; the method of making in order color developing, washing, supplementary color developing, stopping, bleaching, fixing, washing and then stabilizing; the method wherein the developed silver produced by color developing is subjected to halogenation-bleaching and then color-developed again to increase the amount of the formed dye; and the like. Thus, the invention may be applied to those effective components to be used in any of these methods.
Now, examples of those effective components which are desirable to be the photographic processing agent of this invention will be given below in the order of being added to a developer solution, but the present invention is not limited thereto:
As a preferred embodiment of this invention, the effective component to which this invention is.to be applied includes those compounds having the following Formula I.
The application of this invention to these compounds having Formula I exhibits not only the objective effect of this invention satisfactorily but also another effect to restrain the occurrence of fog at the time of processing at a low replenishing rate. Formula I
wherein R is an alkyl group which may have a straight-chain or branched-chain substituent having from 4 to 25 carbon atoms or
wherein R₁ and R₂ each is a hydrogen atom or an alkyl group having from 1 to 20 carbon atoms which may have a substituent, and t is an integer of zero to 4; A and B each is --
and they may be either the same or different, provided that ni, mi and 1₁ each is 0, 1, 2 or 3; D is a hydrogen atom or -SO₃M, wherein M is a hydrogen atom, sodium, potassium, ammonium or lithium; and n and m each is an integer of zero or from 1 to 25.
Further, another preferred embodiment of this invention is to use as the photographic processing agent of this invention those compounds having the following Formulas II through VI, which are to be added to a developer solution.
The application of this invention to those compounds having Formulas II through VI exhibitis not only the objective effect of this invention satisfactorily but also another effect of significantly improving the preservability of the developer solution in an automatic processor having a large air-contact surface area.
wherein A₁ is a carboxyl group, phosphoric acid group or a salt of any one of these groups; X is a hydroxyl group or a salt thereof; B₁ is a halogen atom, a hydroxyl group, an alkyl group, a carboxyl group, a phosphonic acid group, or a salt of any one of hydroxyl, carboxylic acid or phosphonic acid group; r and 1₂ each is 0, 1 or 2; n₂ is an integer of from 1 to 4; and m₂ is an integer of up to 3.
wherein R₃ is an alkyl group which may have a substituent having from 1 to 5 carbon atoms or an amino group.

wherein R₄, Rs, Rs, R₇ and R₈ each is a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having from 1 to 7 carbon atoms, a -OR₉ group, a -COOR₁₀ group a
group or a substituted or unsubstituted phenyl group; and R_s, Rio, R₁₁ and R₁₂ each is a hydrogen atom or an alkyl group having from 1 to 18 carbon atoms. Formula VI
wherein n, m, A and B are as defined in the foregoing Formula I.
Preferred typical examples of the compound of this inven tion represented by Formula I are found in Japanese Patent Application No. 112044/1987, pp. 24-1 to 24-26.
These compounds may be synthesized in accordance with those general synthesis methods as described in British Patent No. 1,022,878, U.S. Patent Nos. 3,723,341 and 3,437,598. Also, these compounds are commercially available (from, e.g., Olin Mathieson Chemical Corp., etc.}.
The photographic processing agent according to this invention containing the compound having Formula I, when the compound is used in the amount range of from 0.001 gram to 10 grams per liter of a developer solution, accomplishes the object of this invention particularly satisfactorily and, when the compound is used in the amount range of from 0.01 gram to 3 grams, exhibits the effect of this invention more particularly satisfactorily.
Preferred typical examples of the compound having Formula II are found in Japanese Patent Application No. 112044/1987, pp.28 to 30.
These compounds may be synthesized in accordance with those general synthesis methods as described in U.S. Patent No. 3,632,637 and Journal of the American Chemical Society, Vol.89 (1967); p.837.
Subsequently, typical examples of the compound having Formula III will be given below:

III-1: 1-Hydroxyethylidene-1,1-diphosphonic acid
111-2: 1-Hydroxypropylidene-1,1-diphosphonic acid
III-3: 1,2-Dihydroxyethane-1,1-diphosphonic acid
III-4: 1-Hydroxybutane-1,1-diphosphonic acid
III-5: 1-Hydroxy-2-carboxy-ethane-1,1-diphosphonic acid
III-6: 1-Amino-ethylidene-1,1-diphosphonic acid

Examples of the compounds having Formulas IV and V include 1,2-dihydroxybenzene, 4-isopropyl-1,2-dihydroxybenzene, 1,2-dihydroxybenzene-3,5-disulfonic acid, 1,2-dihydroxybenzene-3,4,5-trisulfonic acid, 1,2-dihydroxybenzene-3,4,6-trisulfonic acid, 1,2,3-trihydroxybenzene, 1,2,3-trihydroxybenzene-5-carboxylic acid, methyl 1,2,3-trihydroxybenzene-5-carboxylate, n-propyl 1,2,3-trihydroxybenzene-5-carboxylate, 5-t-butyl-1,2,3-trihydroxybenzene, 2,3-dihydroxynaphthalene-6-sulfonic acid, 2,3,8-trihydroxynaphthalene-6-sulfonic acid, and the like, but are not limited to these described compounds. Of the above compounds, particularly suitably usable as the effective component for photographic processing in this invention are the 1,2-dihydroxybenzene-3,5-disulfonic acid and its sodium and potassium salts, the 1,2-dihydroxybenzene-3,4,6-trisulfonic and its sodium and potassium salts, and above all, the most preferred are the 1,2-dihydroxybenzene-3,5-disulfonic acid and its sodium and potassium salts.
The photographic processing agent of this invention containing any of the compounds having Formulas II through V is desirable to be used so that the compound is in the amount range of from 0.01 gram to 10 grams per liter of a developer solution, and more preferably from 0.03 gram to 3 grams.
The following are typical examples of the compound having Formula VI:

VI-1: N=(CH₂CH₂0H)₃
VI-2: Nm[(CH_2CH₂0H)₂H]₃
VI-3: N≡[(CH₂
CH₂O)₂H]₃
VI-4: N≡(CH₂
CH₂0H)₃
VI-5: N≡(CH₂CH₂CH₂OH)₃
VI-6: N≡(CH₂CH₂CH₂CH₂OH)₃

Of the above compounds having Formula VI, particularly suitably usable as the effective component for photographic processing in this invention are VI-1 and VI-2.
The photographic processing agent of this invention containing any of these compounds having Formula VI is desirable to be used so that the compound is in the amount range of from 0.3 gram to 50 grams per liter of a developer solution, and, when used in the amount range of from 1 gram to 20 grams, this invention displays its effect most significantly.
In the case where an aminocarboxylic acid-type or aminophosphonic acid-type compound is used in a developer solution, by using these compounds as the inclusion compound of this invention, not only can the object of this invention be carried out more effectively but also another effect of preventing the deposition of a developing agent that tends to occur in a low-temperature storage is exhibited at the same time. Therefore, in this invention, it is desirable to use an aminocarboxylic acid-type or aminophosphonic acid-type compound as the photographic processing agent of this invention. The aminocarboxylic acid-type compound and aminophosphonic acid-type compound represent amino compounds having at least two or more carboxylic acid groups and amino compounds having at least two or more phosphonic acid groups, respectively, and these are preferably those compounds having the following Formulas VII and VIII:

wherein E is a substituted or unsubstituted alkylene group, cycloalkylene group, phenylene group, -R₁₃OR₁₃OR₁₃- group or -R₁₃ZR₁₃- group, wherein Z is a N-R₁₃-A₆ or N-A₆ group; R₉ through R, ₃ each is a substituted or unsubstituted alkylene group; A₂ through As is a hydrogen atom, a -OH, -COOM or -PO₃M₂ group; and M is a hydrogen atom or an alkali metal atom.
Preferred examples of the compounds having Formulas VII and VIII will now be given below:

VII-1: Ethylenediaminetetraacetic acid
VII-2: Diethylenetriaminepentaacetic acid
VII-3: Ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triactic acid
VII-4: 1,3-propylenediaminetetraacetic acid
VII-5: Triethylenetetraminehexaacetic acid
VII-6: Cyclohexanediaminetetraacetic acid
VII-7: 1,2-Diaminopropanetetraacetic acid
VII-8: 1,3-diaminopropane-2-ol-tetraacetic acid
VII-9: Ethyl ether-diaminetetraacetic acid
VII-10: Glycol ether-diaminetetraacetic acid
VII-11: Ethylenediaminetetrapropionic acid
VII-12: Phenylenediaminetetraacetic acid
VII-13: Disodium ethylenediaminetetraacetate
VII-14: Tetra(trimethyl ammonium) ethylenediaminetetraacetate
VII-15: Tetrasodium ethylenediaminetetraacetate
VII-16: Pentasodium diethylenetriaminepentaacetate
VII-17: Sodium ethylenediamine-N-(β-hydroxyethyl)-N,N',N'-triacetate
VII-18: Sodium propylenediaminetetraacetate
VII-19: Ethylenediaminetetramethylenephosphonic acid
VII-20: Sodium cyclohexanediaminetetraacetate
VII-21: Diethylenetriaminepentamethylenephosphonic acid
VII-22: Cyclohexanediaminetetramethylenephosphonic acid
VII-1: Nitrilotriacetic acid
VIII-2: Iminodiacetic acid
VIII-3: Hydroxyethyliminodiacetic acid
VIII-4: Nitrilotripropionic acid
VIII-5: Nitrilotrimethylenephosphonic acid
VIII-6: Iminodimethylenephosphonic acid
VIII-7: Hydroxyethyliminodimethylenephosphonic acid
VIII-8: Trisodium nitrilotriacetate

Particularly suitably usable in respect of the objective effect of this invention among these aminocarboxylic acid-type and aminophosphonic acid-type compounds are the Compounds VII-1, VII-2, VII-5, VII-8, VIII-1, VIII-3 and VIII-5.
It is discretional whether these aminocarboxylic acid-type and aminophosphonic acid-type compounds are to be used in the form of sodium salts, potassium salts or lithium salts.
The photographic processing agent of this invention containing such the aminocarboxylic acid-type compound or aminophosphonic acid-type compound is desirable to be used so that the compound is in the amount range of from 0.1 gram to 20 grams per liter of a developer solution, and particularly preferably from 0.3 gram to 5 grams.
Where as the developer solution a color developer solution is used, in this color developer solution, a p-phenylene diamine-type color developing agent is suitably used, and these agents of this type, to be more stable than the free state, are used generally in the salt form, e.g., hydrochloride or sulfate. When the p-phenylenediamine-type color developing agent is used as the effective component for photographic processing in this invention, it is usually used so that its component concentration is from about 0.5 gram to about 30 grams per liter of a color developer solution.
In this invention, a p-phenylenediamine-type color developing agent that is particularly useful from the point of view of making the object of this invention even more effective is an aromatic primary amine-type color developing agent having at least one water-soluble amino group, and particularly preferably a compound having the following Formula IX:
wherein R₁₄ is a hydrogen atom, a halogen atom or a straight-chain or branched-chain, substituted or unsubstituted alkyl group having from 1 to 5 carbon atoms; and R₁₅ and R₁₆ each is a hydrogen atom, an alkyl or aryl group each being allowed to have a substituent; provided that at least one of the R₁₄, R₁₅ and R16 _sis an alkyl group substituted by a water-soluble group such as a hydroxyl group, carboxyl group, sulfo group, amino group, sulfonamido group or the like, or (̵(̵CH₂)̵_tO(̵_rR₁₇, wherein R₁₇ is a hydrogen atom or an alkyl group, said alkyl group being a straight-chain or branched-chain alkyl group having from 1 to 5 carbon atoms, and t and r each is an integer of from 1 to 5.
Typical examples of the compound having Formula IX are found in Japanese Patent Application No.112044/1987, pp.40-43.
Further, the p-phenylenediamine derivative having Formula IX may be used in the form of an organic or inorganic salt such as hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, oxalate, benzyldisul- fonate, or the like.
The effect of this invention is exhibited satisfactorily particularly where, in these p-phenylenediamine derivatives having Formula IX, the R15 and/or R₁₆ is (̵(̵CH₂)̵_tO)̵_rR₁₇ (wherein t, r and R₁₇ are as defined in above).
When a triazylstilbene-type brightening agent is used as the photographic processing agent of this invention in a color developer solution, the effect of this invention is exhibited more satisfactorily, and because it also provides another effect to improve the tarring characteristic of the developer replenisher solution in storage, it can be more suitably used in this invention.
Preferred as the triazylstilbene-type brightening agent usable in this invention are those having the following Formula X:
wherein Xi, X₂, Y₁ and Y₂ each is a hydroxyl group, a halogen atom such as chlorine, bromine, etc., morpholino group, alkoxy group such as methoxy, ethoxy, methoxy-ethoxy; aryloxy group such as phenoxy, p-sulfophenoxy; alkyl group such as methyl, ethyl; aryl group such as phenyl, methoxyphenyl; amino group; alkylamino group such as methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di(β-hydroxyethyl)amino, β-sulfoethylamino, N-(β-sulfoethyl)-N -methylamino, N-(_j8-hydroxyethyl-N -methylamino), etc.; arylamino group such as anilino, o-, m-, p-sulfoanilino, o-, m-, p-chloroanilino, o-, m-, p-toluidino, o-, m-, p-carboxyanilino, o-, m-,p-hydroxyanilino, sulfonaphthylamino, o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.; and M is the same as the M defined in the foregoing Formula I.
Examples of such the brightening agent include those compounds disclosed in the forementioned Japanese Patent Application No. 112044/1987, pp.47-51, but are not limited to the compounds.
These triazylstilbene-type brightening agents may be synthesized in accordance with those general synthesis methods as described in, e.g., the 'Keikozohakuzai (Brightening Agents)' compiled by Kaseihin Kogyo Kyokai (published in Aug. 1976), p. 8.
The photographic processing agent of this invention containing any of these triazylstilbene-type brightening agents is suitably used when the brightening agent is in the amount range of from 0.2 gram to 3 grams per liter of a color developer solution, and particularly preferably from 0.4 gram to 3 grams.
The color developer solution is allowed to contain any of those alkali agents as usually used in developer solutions, such as, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, borax, or the like, and further various other additives including benzyl alcohol, halogenated alkali metals such as potassium bromide, potassium chloride, etc., development control agents such as citrazinic acid, preservatives such as hydroxylamine, its derivatives or sulfite, and the like. It is desirable that these additives be used as the photographic processing agent of this invention.
It is also desirable to select hydroxylamine or those compounds represented by the following Formula C as the effective component for photographic processing in this invention.
wherein Ric and R_2c each is a hydrogen atom or a substitutable alkyl group having from 1 to 5 carbon atoms, provided that the R_ic and R_2c cannot be hydrogen atoms at the same time, and the R_ic and R_2c are allowed to form a ring together.
Examples of such the compound are found in Japanese Patent O.P.I. Publication No. 48549/1988, pp.15-17.
It is known that those oxidizing agents or peroxides for use in the intensification method known to be used in the color developing process are so unstable and so highly reactive with the components being present together that they become fast deteriorated. It is useful for the sake of long-term processing stability to use an inclusion compound (photographic processing agent of this invention) which, according to this invention, encloses as its guest the hydrogen peroxide or hydrogen peroxide-releasing compounds, percarbonates or perborates, out of photographic processing constituents for use in the intensification process.
Also, in a developing-bleach-fix monobath solution, it is useful to use an inclusion compound (photographic processing agent of this invention) which encloses as its guest the sulfite or fixing agent such as thiosulfate, thioglycol or thiocyanate.
In the case of black-and-white development, long-term processing stability can be largely improved by using an inclusion compound (photographic processing agent of this invention) which encloses the sulfite as its guest.
Also, the long-term processing stability can be largely improved by using an inclusion compound (photographic processing agent of this invention) which encloses phenidone and/or phenidone derivatives as its guest.
Further, an inclusion compound (photographic processing agent of this invention) which encloses the precursor of a color developing agent as its guest may be used, and as examples of this, those color developing agents' Schiff's base-type compounds as disclosed in U.S. Patent Nos. 2,507,114, 2,695,234 and 3,342,599; Research Disclosure Voi.151, No.15159, Nov. 1979, and those as described in Research Disclosure Vol.129, No.12924, Oct. 1976, and Vol. 121, No.12146, June 1974, and Vol.139, No.13924, Nov.1973, and the like, may be applied.
The effective component of the photographic processing agent of the present invention also includes those various effective components for photographic processing as used in a bleaching solution or bleach-fix solution in the bleaching process. For example, as the bleaching agent there are generally known those compounds wherein metal ions such as of iron, cobalt, copper, etc. are coordinated with an organic acid such as the aforesaid aminopolycarboxylic acid, oxalic acid, citric acid, or the like.
For the bleaching agent for use in bleaching or bleach-fix processing, particularly organic ferric complex salts are suitable. Suitable organic acids for use in the formation of such organic ferric complex salts are, preferably, aminocarboxylic acid-type compounds and aminophosphonic acid-type compounds both representing at least one carboxyl group-having amino compounds and at least one phosphonic acid group-having amino compounds, respectively, and more preferably being those compounds having the foregoing Formulas VII and VII.
The organic acid ferric complex salt may be used in the free acid form or in the form of an alkali metal salt such as sodium salt, potassium salt, lithium salt, etc., or ammonium salt or a water-soluble amine salt such as triethanolamine salt or the like, but preferably, the potassium salt, sodium salt and ammonium salt are used.
These ferric complex salts may be used alone or in combination of two or more of them.
As the iron(III) complex salt one or more kinds of the existing complex salt may be used, or an iron(III) salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric-ammonium sulfate, ferric phosphate, etc. and a chelating agent such as aminopolycarboxylic acid, aminopolysulfonic acid, phosphonocarboxylic acid, etc. may be made react with each other in a solution thereof to thereby form a ferric ion complex salt. In forming the complex salt in the solution, each of both or either one of the ferric salt and the chelating agent may be in combination of two or more kinds. In either case of the existing complex salt or of the complex salt formation, the chelating agent may be used in excess of the stoichiometric amount. Metal ions such as of cobalt, copper, etc. other than iron, and complex salts of them or hydrogen peroxide may also be mixed in.
Applicable persulfates include alkali metal salts of persulfuric acid such as potassium persulfate, sodium persulfate, and ammonium persulfate.
The amount of a bleaching agent per liter of a bleach-fix ability-having processing solution is normally from 0.2 mole to 2 moles, preferably from 0.25 mole to 1.0 mole, and most preferably from 0.30 mole to 1.0 mole.
As has been described above, in the bleaching bath or bleach-fix bath, as the bleaching agent, ferric ion complexes of aminopolycarboxylic acid, aminopolysulfonic acid, phosphonocarboxylic acid and organic phosphonic acid are suitably usable, and further, in addition to the ferric ion complexes of the above chelating agents, free chelating agents may be used for the stabilization of ferric ion complexes, but as a result of our investigation, it has been found that if the ferric ion complex contains more than 7.5% of the free chelating agent, the recolorability tends to be deteriorated. Accordingly, the free chelating agent content of the ferric ion complex being less than 7.5 mole%, particularly less than 5 mole% is suitable from the point of view of another object of this invention, i.e., the recolorability., and therefore, it is appropriate to consider these effective components for photographic processing as the photographic processing agent of this invention.
If at least one of these compounds having the following Formulas 1 to 9 is selected as the effective component of the photographic processing agent of this invention, and if this is used as the photographic processing agent of this invention, the effect of this invention is exhibited more satisfactorily, and further the trouble arising due to the silver inside a bleaching solution or bleach-fix bath can be prevented.
wherein Q is a group of atoms necessary to form a nitrogen-containing heterocyclic ring, including 5- or 6- member unsaturated ring condensate; R₁ is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic group, including 5- or 6-member unsaturated ring condensate, or amino group.
wherein R₂ and R₃ each is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, hydroxy group, carboxy group, amino group, acyl group having from 1 to 3 carbon atoms, aryl group or alkenyl group; A is

or a n₁-valent heterocyclic ring residue, including 5- or 6-member unsaturated ring condensate; X represent =S, =0 or =NR", wherein R and R' are the same in definition as the R₂ and R₃, respectively; X is the same in definition as X; Z is a hydrogen atom, an alkali metal atom, an ammonium group, amino group, nitrogen-containing heterocyclic residue, alkyl group, or
group; M is a divalent metal atom; R is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic residue, including 5- or 6-member unsaturated ring condensate, or amino group; n₁ to n₆ and m₁ to ms each is an integer of from 1 to 6; B is an alkylene group having from 1 to 6 carbon atoms; Y is -N= or -CH=; R₄ and Rs are the same in definition as the R₂ and R₃, respectively, provided that the R₄ and Rs each may represent -B-SZ, and each pair of the R₂ and R₃, R and R', and R₄ and R₅ may combine with each other to form a ring.
In addition, those compounds represented by this formula include ethanolated ones and salts thereof.
wherein R_s and R₇ each is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, hydroxy group, carboxy group, amino group, acyl group having from 1 to 3 carbon atoms, aryl group, alkenyl group or -B₁-S-Z₁ group, provided that the R₆ and R₇ are allowed to combine with each other to form a ring; Y₁ is a =N- or =CH- group; B₁ is an alkylene group having from 1 to 6 carbon atoms; Z₁ is a hydrogen atom, alkali metal atom, ammonium group, amino group, nitrogen-containing heterocyclic residue or
and n₇ is an integer of from 1 to 6.
wherein R₈ and R₉ each is
R₁₀ is an alkyl group or -(CH₂)n₈SO₃⊖, provided that when the R₁₀ is -(CH₂)n₈SO₃⊖, 1 is zero, while when the R₁₀ is an alkyl group, t is 1; G⊖is an anion; and ns is an integer of from 1 to 6.
wherein Q₁ is a group of atoms necessary to form a nitrogen-containing heterocyclic ring, including 5- or 6- member unsaturated or saturated ring condensate; R₁₁ is a hydrogen atom,
or an alkyl group, provided that Q' and Q₁ are the same in definition.
wherein D₁, D₂, D₃ and D₄ each is a simple bond or an alkylene or vinylene group having from 1 to 8 carbon atoms; qi, q₂, q₃ and q₄. each is an integer of zero, 1 or 2; and each ring formed along with the sulfur atom may further be condensed with a 5- or 6-member saturated or unsaturated ring.
wherein X₂ represents a -COOM', -OH, -SO₃M', -CONH₂, -SO₂NH₂, -NH₂, -SH, -CO, -CH₂R₁₆, -SO₂R₁₆, -OR₁₆, -NR₁₆R₁₇, -SR₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHSO₂R₁₆, -OCOR₁₆ or -SO₂R₁₆ group; Y₂ represents
or a hydrogen atom; m_s and n₈ each is an integer of from 1 to 10; R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇ and R₁₈ each is a hydrogen atom, a lower alkyl group, acyl group or
R₁₆ is a lower alkyl group; and R₁₉ is a -NR₂₀R₂₁, -OR₂₂ or -SR₂₂ group, wherein R₂₀ and R₂₁ each is a hydrogen atom or a lower alkyl group; R₂₂ is a group of atoms necessary to form a ring together with the R₁₈; and the R₂₀ or R₂₁ is allowed to form a ring together with the R₁₈; and the M' is a hydrogen atom or a cation.
wherein Ar is an arylene group or a divalent organic group formed in combination of an aryl group with an oxygen atom and/or an alkylene group; B₂ and B₃ each is a lower alkylene group; R₂₃, R₂₄, R₂₅ and R₂₆ each is a hydroxy-substituted lower alkylene group; x and y each is an integer of zero or 1; G is an anion; and z is an integer of zero, 1 or 2.
wherein R₂₉ and R₃₀ each is a hydrogen atom, an alkyl group, aryl group or heterocyclic group; R₃₁ is a hydrogen atom or an alkyl group; and R₃₂ is a hydrogen atom or a carboxy group.
Those compounds represented by Formulas 1 through 9 are compounds generally usable as bleach accelerating agents, and examples of them include those compounds as described in Japanese Patent Application No. 160449/1987 pp.26-48. Besides, Exemplified Compounds Nos.l-2, 1-4 to -7, 1-9 to -13, 1-16 to -21, 1-23, I-24, I-26 and -27, I-30 to -36, 1-38, II-2 to -5, II-7 to -10, II-12 to -20, II-22 to -25, II-27, II-29 to -33, 11-35 and -36, II-38 to -41, 11-43, 11-45 to -55, II-57 to -60, 11-62 to -64, 11-67 to -71, 11-73 to -79, 11-81 to -84, II-86 to -99, II-101 and -102, II-104 to -110, II-112 to -119, II-121 to -124, II-126, II-128 to -144, II-146, II-148 to -155, II-157, III-4, III-6 to -8, III-10 and 11, III-13, III-15 to -18, III-20, III-22, III-23, III-25, III-27, 111-29 to -32, III-35 and 36, IV-3, IV-4, V-3 to -6, V-8 to -14, V-16 to -38, V-40 to -42, V-44 to -46, V-48 to -66, V-68 to -70, V-72 to 74, V-76 to -79, V-81 and 82, V-84 to -100, V-102 to -108, V-110, V-112 and 113, V-116 to -119, V-121 to -123, V-125 to -130, V-132 to -144, V-146 to -162, V-164 to -174, V-176 to -184, VI-4, VI-7, VI-10, VI-12, VI-13, VI-16, VI-19, VI-21, VI-22, VI-25, VI-27 to -34, VI-36, 7-3, 7-6, 7-13, 7-19, 7-20, etc. described in pp.51-115 of Japanese Patent O.P.I. Publication No. 123459/1987 may also be used as the effective component for photographic processing in this invention.
Those inclusion compounds, photographic processing agents of this invention, enclosing any of these bleach accelerating agents as their guest may be used alone or in combination of two or more of them, and good results can be obtained when the inclusion compound is used so that the bleach accelerating agent is in the amount range of generally from about 0.01 gram to about 100 grams per liter of a bleaching or bleach-fix solution.
When the bleach accelerating agent is used as the photographic processing agent of this invention, the agent is allowed to be used as it is, but desirable to be in advance dissolved in water, an alkaline solution or organic acid to be formed as a photographic processing agent of this invention, or otherwise may, if necessary, be dissolved in an organic solvent such as methanol, ethanol, acetone, etc. to be made a photographic processing agent of this invention.
As the bleach-fix bath there may be applied a liquid of a composition containing the foregoing organic acid iron(III) complex salt as a bleaching agent, aiso containing a silver halide fixing agent, and, as needed, containing a persulfate. There are also other bleach-fix bath solutions: A bleach-fix solution containing a small amount of a halide compound such as potassium bromide in addition to the organic acid iron(III) complex salt and the above-mentioned silver halide fixing agent; a bleach-fix solution of a composition comprising, by contrast, a large amount of a halide compound such a potassium bromide; and further a specific bleach-fix solution having a composition comprising the combination of the organic acid iron(III) complex salt bleaching agent with a large amount of a halide compound such as potassium bromide. To various effective components for photographic processing usable in these processing solutions the present invention can be applied. As the above-mentioned halide compound, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, ammonium bromide, sodium iodide, potassium iodide, ammonium iodide or the like may also be used besides the potassium bromide.
Typical examples of the silver halide fixing agent to be incorporated into the bleach-fix or fixing solution include those compounds which react with a silver halide to thereby form a water-soluble complex salt and for use in the ordinary fixing process, such as, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate, ammonium thiosulfate, etc.; thiocyanates such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.; thiourea, thioether, and the like. Where any of these fixing agents is regarded as the inclusion compound of this invention, it can be used in a dissolvable amount exceeding 5 grams per liter.
In addition, the bleach-fix solution may contain a single or combined pH buffer comprised of various salts such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, acetic acid, sodium acetate, ammonium hydroxide and the like. Further, it may contain various brightening agents, defoaming agents, or surface active agents. It may also contain arbitrarily preservatives such as hydroxylamine or its derivatives, hydrazine, aldehyde compound's hydrogensulfite addition product, etc.; organic chelating agents such as aminopolycarboxylic acid, etc.; stabilizers such as nitroalcohol, nitrates, etc.; organic solvents such as methanol, dimethylsulfoamide, dimethylsulfoxide etc.; and the like. These effective compounds for photographic processing may also be regarded as the inclusion compound of this invention.
In the processing method of various light-sensitive materials, washing takes place usually after the bleach-fix or fixing process, but there are cases where washing-substitute stabilization treatment and, as needed, ordinary stabilization treatment after that are performed. Further, there are also cases where usual processing steps such as black-and-white developing, fogging, stopping, washing, etc., are made prior to color developing. And at least one of the effective components for use in these photographic processing solutions can be regarded as the inclusion compound of this invention.
The above term 'washing-substitute stabilization treatment' means a process wherein a light-sensitive material is subjected to stabiliaztion treatment, which requires no substantial washing, upon completion of the processing in a fixability-having solution. The processing solution for use in this stabilization treatment is called 'washing-substitute stabilizer solution, and the bath that is used therefor is called the 'washing-substitute stabilizer bath. Those compounds suitably usable in the washing-substitute stabilizer solution include chelating agents whose chelating stability constant to iron ions is not less than 8, and at least one of these compounds may be used as the inclusion compound of this invention.
The term 'chelating stability constant' means such the generally known constant as described in L. G. Stillen and A. E. Martell, the 'Stability Constants of Metal Ion Complexes', The Chemical Society, London (1964); S. Chaberek and A. E. Martell, the 'Organic Sequestering Agents', Wiley (1959), and the like.
Examples of the chelating agent, whose chelating stability constant to the iron ions to be suitably used in the washing-substitute stabilizer solution is not less than 8, include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, polyhydroxy compounds, and the like. The above-mentioned iron ions means ferric ions (Fe3
Particular examples of the chelating agent, whose chelating stability constant to iron ions is not less than 8, include the following compounds, but this invention is not limited to the examples: ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, hydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminedipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diaminopropanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonoethane-2-carboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxy-1-phosphonopropane-1,2,3-tricarboxylic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, sodium tetrapolyphosphate, and sodium hexametaphosphate. Of these, particularly preferred are the diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid and 1-hydroxyethylidene-1,1-diphosphonic acid, etc., and above all the 1-hydroxyethylidene-1,1-diphosphonic acid is most suitably usable.
Where the above chelating agent is used as the photographic processing agent of this invention, the chelating agent is used in the amount range of preferably from 0.01 gram to 50 grams per liter of a washing-substitute stabilizer solution, and more preferably from 0.05 gram to 20 grams.
Useful additives to the washing-substitute stabilizer solution include ammonium compounds. At least one of these compounds may be regarded as the inclusion compound of this invention.
These may be provided by ammonium salts of various inorganic compounds which include ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, ammonium fluoride, ammonium acid fluoride, ammonium fluoroborate, ammonium arsenate, ammonium hydrogencarbonate, ammonium hydrogenfluoride, ammonium hydrogensulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaphosphate, ammonium acetate, ammonium adipate, ammonium lauryltricarboxylate, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethylthiocarbamate, ammonium formate, ammonium hydrogen- malate, ammonium hydrogenoxalate, ammonium phthalate, ammonium hydrogentartrate, ammonium thiosulfate, ammonium sulfite, ammonium ethylenediaminetetraacetate, ferricammonium ethylenediaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidinedithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate, ammonium tartrate, ammonium thioglycolate, ammonium 2,4,6-trinitrophenol, and the like. Out of these ammonium compounds, ammonium thiosulfate is particularly useful for accomplishing the effect of this invention. The adding amount of the ammonium compound, when used as the inclusion compound of this invention, is in its own amount preferably not less than 1.0x1 0-5, more preferably from 0.001 mole to 5.0 moles per liter of a stabilizer solution, and most preferably from 0.002 mole to 1.0 mole.
The washing-substitute stabilizer solution is desirable to contain a sulfite to an extent not allowing the growth of bacteria.
The sulfite to be contained in the washing-substitute stabilizer solution is allowed to be any organic or inorganic one as long as it releases sulfite ions, but preferably an inorganic sulfite. Preferred particular sulfite compounds include sodium sulfite, potassium sulfite, ammonium sulfite, potassium hydrogensulfite, sodium hydrogensulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, hydrosulfite, sodium glutaraldehyde-bis-hydrogensulfite, sodium succinaldehyde-bis-hydrogensulfite, and the like. And these compounds may be used as the inclusion compound of this invention.
The above sulfite, when used as the inclusion compound of this invention, is added in an amount of preferably at least 1.0x10^-5 mole per liter of the washin-substitute stabilizer solution, and more preferably from 5x10_' ^s mole to 1.0x10-¹ mole per liter. The addition of the sulfite, although allowed to be made directly to the washing-substitute stabilizer solution, is desirable to be made to a washing-substitute stabilizer replenisher solution or to the circulation or stirring system for the stabilizer solution.
The washing-substitute stabilizer solution contains preferably a fungicide, whereby the preservability of processed images as well as its antisulfuration can be improved.
Suitable fungicides include sorbic acid, benzoic acid-type compounds, phenol-type compounds, thiazole-type compounds, pyridine-type compounds, guanidine-type compounds, carbamate-type compounds, triazole-type compounds, morpholine-type compounds, quaternary phosphonium-type compounds, ammonium-type compounds, urea-type compounds, isoxazole-type compounds, propanalamine-type compounds, sulfamide-type compounds, pyronone-type compounds and amino-type compounds. At least one of these effective components for photographic processing may be regarded as the inclusion compound of this invention.
The foregoing benzoic acid-type compounds include salicyclic acid, hydroxybenzoic acid and hydroxybenzoic acid esters such as methyl, ethyl, propyl, butyl, etc. ester compounds. Of these compounds, preferred are hydroxybenzoic acid n-butyl ester, isobutyl ester, propyl ester, and salicyclic acid, and more preferred is a mixture of these three different esters of hydroxybenzoic acid, and these agents may be used as the inclusion compound of this invention. The same may be said of the following exemplified compounds.
The aforementioned phenol-type compounds are ones that are allowed to have a substituent such as a halogen atom, nitro group, hydroxyl group, carboxyl group, amino group, alkyl group, particularly an alkyl group having from 1 to 6 carbon atoms, or phenyl groups, and are preferably orthophenylphenol, orthocyclohexylphenol, nitrophenol, chlorophenol, cresol, guaiacol, aminophenol, and phenol.
The aforesaid thiazole-type compounds are 5-member cyclic compounds having nitrogen and sulfur atoms, and are preferably 1,2-benzoisothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-octyl-4-isothiazolin-3- one, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-(4-thiazolyl)benzimidazole.
The foregoing pyridine-type compounds include 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, sodium 2-pyridinethiol-1-oxide, and the like. Of these compounds, preferred is the sodium 2-pyridinethio-1-oxide.
The foregoing guanidine-type compounds include cyclohexidine, polyhexamethylenebiguanidine hydrochloride, dodecylguanidine hydrochloride, and the like. Of these compounds preferred are the dodecylguanidine and its salts.
The carbamate-type compounds include methyl-1-(butylcarbamoyl)-2-benzimidazole carbamate, methylimidazole carbamate, and the like.
The morpholine-type compounds include 4-(3-nitrobutyl)morpholine, 4-(3-nitropropyl)morpholine, and the like.
The quaternary phosphonium-type compounds include tetra alkylphosphonium salts, tetraalkox- yphosphonium salts and the like. Of these, preferred are the tetraalkylphosphonium salts, and more preferred particular compounds are tri-n-butyl-tetradecylphosphonium chloride and triphenyl-nitrophenyl- phosphonium chloride.
The quaternary ammonium-type compounds include benzalkonium salts, benzethonium salts, tetraalkylammonium salts, alkylpyridium salts, and the like; to be concrete, there are dodecyldimethylbenzylam- monium chloride, dodecyldimethylammonium chloride, laurylpyridinium chloride, and the like.
The urea-type compounds include (N-(3,4-dichlorophenyl)-N -(4-chlorophenyl)urea, N-(3-tolyl- fluoromethyl)-N-(4-chlorophenyl)urea, and the like.
The isoxazole-type compounds include 3-hydroxy-5-methylisoxazole, and the like.
The propanolamino-type compounds include n-propanols and isopropanols; to be concrete, there are DL-2-benzylamino-1-propanol, 3-diethylamino-1-propanol, 2-dimethylamino-2-methyl-1-propanol, 3-amino-1-propanol, isopropanolamine, diisopropanolamine, N,N-dimethyl-isopropanolamine, and the like.
The sulfamide-type compounds include o-nitrobenzenesulfamide, p-aminobenzenesulfamide, fluorinated sulfamide, 4-chloro-3,5-nitrobenzenesulfamide, a-amino-p-toluenesulfamide, sulfanylamide, acetosul- faguanidine, sulfathiazole, sulfadiazine, sulfamerazine, sulfamethazine, sulfaisooxazole, homosulfamine, sul- famidine, sulfaguanidine, sulfamethyzole, sulfapyrazine, phthalisosulfathiazole, succinylsulfathiazole, and the like.
The pyronone-type compounds include dehydroacetic acid and the like.
The amino acid-type compounds include N-lauryl-.8-alanine and the like.
The triazole-type compounds include 2-aminotriazole, benzotriazole, 5-methylbenzotriazole, and the like.
In this invention, suitably usable compounds among the above enumerated fungicides are the thiazole-type, sulfamide-type and pyronone-type compounds.
The adding amount of such the fungicide to the foregoing stabilizer solution is in the range of preferably from 0.001 gram to 30 grams, and more preferably from 0.003 to 5 grams. The fungicide, when used as the inclusion compound of this invention, should be used in the above-mentioned amount.
The stabilizer solution is desirable to contain a metal salt in combination with the chelating agent.
Such the metal salt is a metal salt of Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, AI or Sr, and may be provided as a inorganic salt such as a halide, hydroxide, sulfate, carbonate, phosphate, acetate or the like, or as a water-soluble chelating agent, and at least one of these may be used as the inclusion compound of this invention. The adding amount of it to the stabilizer solution is in the range of from 1x10^-4 to 1x10'' mole per mole of the solution, and preferably from 4x10-⁴ to 2x10-^z mole.
Other compounds which may be added to the washing-substitute stabilizer solution include salts or organic acids such as citric acid, acetic acid, succinic acid, oxalic acid, benzoic acid, etc.; pH buffers such as phosphoric acid, borates, hydrochloric acid, sulfuric acid, etc.; or surface active agents. Regarding these compounds, any of the compounds may be used in any combination as long as they are used within the adding amount range not adversely affecting the stability of color photographic images in storage or precipitation in the .stabilizer solution. At least one of these compounds may be used as the inclusion compound of this invention.
The effective component for photographic processing which can be regarded as the photographic processing agent of this invention is not limited to these compounds which have been described above but applicable also to any of those effective components of processing solutions for use in processing photographic light-sensitive materials for general use such as color or black-and-white photographic papers, color or black-and-white positive films, color or black-and-white reversal films, color or black-and-white reversal papers, and the like.
The silver halide grain crystal of light-sensitive materials to which the processing in this invention is applied may be regular or twin or others, and any silver halide grains whose crystal is of an arbitrary [1.0.0] face-[1.1.1] face proportion may be used. Further, the crystal of these silver halide grains may be of either homogeneous structure from the inside through outside of heterogeneous structure stratified or phases with the inside and the outside (core/shell type). In addition, these silver halides may be of either the type of forming a latent image mainly on the grain surface or the type of forming a latent image inside the grain. Further, planar-type silver halide grains (see Japanese Patent O.P.I. Publication No. 113934/1983 and No. 47959/1986) may also be used. As couplers for use in the light-sensitive material to which the processing according to this invention is to be applied, various yellow couplers, magenta couplers and cyan couplers may be used with no particular restrictions. These couplers may be either the so-called two-equivalent-type or four-equivalent-type couplers.

EXAMPLES

The present invention will be illustrated in detail by the following examples, but the embodiment of this invention is not limited to and by the examples.

EXAMPLE-1

On a polyethylene-coated paper support the following layers were coated in order from the support side, whereby a light-sensitive material was prepared.
The polyethylene-coated paper that has been used herein is one obtained by forming on the obverse side of a 170gim^2-weight high-quality paper by the extrusion coating method a 0.035mm-thick coat layer of polyethylene containing titanium oxide prepared by adding 6.8% by weight of anatase-type titanium oxide to a mixture of 200 parts by weight of a polyethylene having an average molecular weight of 100,000 and a density of 0.95 with 20 parts by weight of a polyethylene having an average molecular weight of 2000 and a density of 0.80, and on the reverse side of the paper was formed a 0.040mm-thick polyethylene coat layer comprised of polyethylene alone. The surface of the polyethylene coat layer on the obverse side of the paper support was subjected to corona discharge pretreatment, and after that, the following layers were coated on the support.

Layer 1:

A blue-sensitive silver halide emulsion layer comprised of a silver chlorobromide emulsion containing 0.5 mole % silver bromide: This emulsion contains 350g of gelatin per mole of silver halide, and is sensitized by using 2.5x10-⁴ mole per mole of silver halide of the following structure-having Sensitizing Dye I (isopropyl alcohol is used as a solvent therefor), and also contains 200mg/m² of 2,5-di-t-butylhydroquinone and 2.0x10^-1 mole per mole of silver halide of Yellow Coupler Y-1 having the following structure which both are dissolved in dibutyl phthalate to be dispersed. This emulsion was coated so that its coating weight was 210mg/m².

Layer 2:

A gelatin layer containing 300mg/m² of di-t-octyl-hydroquinone dissolved in dibutyl phthalate to be dispersed and 200mg/m² of a mixture of ultraviolet absorbing agents 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-benzotriazole, 2-(2 -hydroxy-5 -t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chloro-benzotriazole and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole (1:1:1:1). This was coated so that the coating weight of the gelatin was 1900mg/m².

Layer 3:

A green-sensitive silver halide emulsion layer comprised of a silver chlorobromide emulsion containing 0.5 mole % silver bromide: This emulsion contains 450g of gelatin per mole of silver halide, and is sensitized by using 2.5x10^-4 mole per mole of silver halide of the following structure-having Sensitizing Dye II, and also contains Antiirradiation Dye I, 2,5-di-t-butylhydroquinone and 1.5x10-' mole per mole of silver halide of Magenta Coupler M-1 having the following structure which both are dissolved in a mixture solvent of dibutyl phthalate and tricresyl phosphate (2:1). This emulsion was coated so that the coating weight of silver was 160mg/m² and that of AI dye I was 50mg/m^2. In addition, an oxidation inhibitor 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was added in an amount of 0.30 mole per mole of the coupler.

Layer 4:

A gelatin layer containing 30mgim² of di-t-octylhydroquinone dissolved in dioctyl phthalate to be dispersed and 500mg/m² of a mixture of ultraviolet absorbing agents 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-benzotriazole, 2-(2 -hydroxy-5'-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-t-butyl-5'-methylphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-3',5'-di-t-butylphenyl)-5-chlorobenzotriazole (2:1.5:1.5:2). This was coated so that the coating weight of the gelatin was 1900mg/m².

Layer 5:

A red-sensitive silver halide emulsion layer comprised of a silver chlorobromide emulsion containing 0.5 mole % silver bromide: This emulsion contains 500g of gelatin per mole of silver halide, and is sensitized by using 2.5x10^-5 mole per mole of silver halide of the following structure-having Sensitizing Dye III, and also contains Antiirradiation Dye II, 150mg/m² of 2,5-di-t-butylhydroquinone and 3.5x10^-1 mole per mole of silver halide of the following structure-having Cyan Coupler C-1 which both are dissolved in dibutyl phthalate to be dispersed. This emulsion was coated so that the coating weight of silver was 200mg/m² and that of AI dye II was 40mgim².

Layer 6:

A gelatin layer: Coated so that the coating weight of gelatin was 900mg/m².
The silver halide emulsion that was used in Layers 1, 3 and 5 was prepared in accordance with the method described in Japanese Patent Examined Publication No. 7772/1971, then chemically sensitized by using pentahydrated sodium thiosulfate, and then into the emulsion were incorporated a stabilizer 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene (2.5g per mole of silver halide), a hardening agent bis- ; (vinylsulfonylmethyl)ether (10mg per gram of gelatin), and a coating aid saponin.
The color photographic paper that was prepared in the above method was exposed and then processed by the following processing steps and in the following processing solutions in accordance with the following Processing Manners-1 through 5.
Compositions of the Processing Solutions: (Color Developer Bath Solution)
Water to make 1 liter. Adjust the pH to 10.15 by using potassium hydroxide and 20% sulfuric acid.
1) Color Developing Agent:

(Bleach-Fix Bath Replenisher)

Brightening Agent K-1

Processing Manner-1:

The foregoing color photographic paper sample was exposed through a step wedge in usual manner and then subjected to a runing processing test in the manner that the sample was processed in a KONICA Nice Printing System Automatic Processor whose baths are filled with the above-prepared color developer bath solution, bleach-fix bath solution and stabilizer bath solution, respectively, and while the processing was making progress, the above color developer replenisher, bleach- fix bath replenisher and stabilizer replenisher were supplied through the appropriate metering pumps at 30-minute intervals. As for the replenishing quantities per m² of the color photographic paper, 220 ml of the color developer replenisher were supplied to the color developer bath, 220 ml of the bleach-fix bath replenisher to the bleach-fix bath and 250 ml of the washing-substitute stabilizer replenisher to the stabilizer bath.
The replenishment of the washing-substitute stabilizer solution took place in a multibath counterflow system which is such that the stabilizer bath of the automatic processor consists of three baths: the first bath to the third bath in the light-sensitive material's running direction, and the replenisher solution is supplied to the last (third) bath, from which the supplied replenisher solution is overflown to the preceding (second) bath and then overflown again to the first bath. The running test (6.5m²/hr, the same shall apply hereinafter) lasted 24 hours.

Processing Manner-2:

A 24-hour running processing took place in the same manner as in the above Manner-1 except that the color developer bath was replenished at 30-minute intervals by a replenisher prepared by removing the preservative alone from the above color developer replenisher, and the preservative was added at three- hour intervals to the color developer bath. In addition, the replenishing amount of the preservative was 5-Og/iiter.

Processing Manner-3:

Processing was made in the same manner as in Processing Manner-2 except only that the preservative was added in the form of an inclusion compound of the invention. The replenishing amount was 5.6g/liter in terms of the amount of the preservative.

Processing Manner-4:

Processing was made in the same manner as in Processing Manner-3 except that the preservative- adding time intervals were changed from the 3 hours to 6 hours, and the replenishing amount was changed to 10g/iiter in terms of the amount of the preservative.
The yellow dye reflection density (Dmax) of the overall processed paper was measured to investigate its minimum density.
The obtained results are shown in Table 1, wherein the minimum density in each test is given in a value relative to the maximum density which is regarded as 100.
The Preservative Compounds 1 to 4 are:

Preparation of inclusion compounds enclosing the preservatives that were used in Manner-3 or -4:

An aqueous solution of each of the above Preservatives 1 to 4 was poured onto urea in the solid state, whereby inclusion compounds comprised of the urea and Preservatives 1 to 4 were prepared.
The developer solution was sampled at times while the running processing was making progress, and the concentration of each objective compound (Preservatives 1 to 4) in the sampled solution was measured. It was confirmed that in Processing Manners-3 and -4, the preservative's concentration fluctuation width, when compared with the case where the preservative which was not subjected to the above treatment of this invention was replenished or added, was not more than 1/2. (The concentration measurement was carried out by liquid chromatography.)
Also, it was confirmed that in Processing Manners-3 and -4, the time that was taken until when the preservative which was made in the form of the inclusion compoune of this invention was released by more than 90% by weight into the photographic processing solution was not less than three hours.
As is apparent from Table 1, according to this invention, Dmax is kept high with its fluctuation width being restrained to be small, thus providing an effect equal to or more than that of Processing Manner-1 which exerts processing, being replenished at 30-minute intervals, and thus it is understood that the invention exhibits an effect excellent in the long-term processing stability of processing solutions.
In place of the Preservatives 1 to 4, {3-cyclodextrin, uric acid, hydroxamic acid, hydroxyacetone, L-aspartic acid, glycine, grape sugar, cane sugar, fruit sugar, glucosamine hydrochloride, dihydroxytartaric acid, D-glucosamine, pentose and alanine were also used and similar experiments were performed with respect to these compounds. Consequently, similar results to those of Preservative 3 were obtained, thus proving that the use in the form of the inclusion compound of this invention is effective.
Inclusion compounds were prepared by using oxypentamethyl flavan, thiourea, deoxycholic acid, dioxytriphenylmethane, triphenylmethane and branched ,8-cyclodextrin as host compounds in place of the urea (reference can be made to the previously cited publications), and similar experiments were made with respect to these compounds. As a result, nearly the same effects were obtained.

EXAMPLE 2

A running processing test was made in the same manner as in Processing Manner-3 of Example 1 except that as the treatment of this invention, the fallowing was used:
S0₂ was conducted into a saturated aqueous hydroquinone solution to crystallize a hydroquinone-S0₂ inclusion compound, which is to be used as a preservative of this invention.
The Dmax that was obtained in this Example was 80, which is a value equal to or more than those of the Preservatives 1 to 4 of Processing Manner-1 of Example 1, thus proving that the treatment of this invention is excellent in the long-term processing stability.
And, the same results were obtained also in the case where zeolite was used in place of the hydroquinone.

EXAMPLE 3

With respect to the fungicides, the following 4 different compounds were used in place of the orthophenyl phenol of the washing-substitute stabilizer solution in Example 1, and the following Processing Manners-5 and -6 were performed.

Processing Manner-5:

The same automatic processor and processing solutions as those of Processing Manner-1 were used, but the processing quantity per day was set to 1 m², and the processing lasted one month. And each of the fungicides that were subjected to the treatment of this invention was only initially put (5.0g/liter in terms of the amount of the fungicide) into the washing-substitute stabilizer solution, and no subsequent replenishment of the fungicide was made. As for the other constituents, 220ml of the color developer replenisher, 220ml of the bleach-fix bath replenisher and 250ml of the washing-substitute stabilizer replenisher was supplied. The procedure of the preparation of the inclusion compound of this invention that was applied is as follows: Branched β-cyclodextrin, water-soluble cyclophane, and thiourea were used as host compounds, whereby objective inclusion compounds were prepared.

Processing Manner-6:

The same as Processing Manner-5 except that 5.Og/liter each of the Fungicides 1 to 4 were used without being formed into inclusion compounds.
Changes with time in the washing-substitute stabilizer solution were evaluated in the following 4-step rating method:

- : No precipitation
+ : Precipitation occurs slightly
+ + : Precipitation occurs
+ + + : Precipitation occurs conspicuously

As is apparent from Table 2, according to this invention, a high effect of the fungicide to prevent precipitation and excellent long-term processing stabiliation effect can be displayed.

EXAMPLE 4

Preparation of a Negative Light-Sensitive Material Sample:

On a triacetate film base having thereon an antihalation layer and a gelatinlayer were coated a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emul sion layer, a yellow colloidal silver-containing filter layer and a blue-sensitive silver halide emulsion layer so that the coating weight of the whole silver was 62mg/100cm². The emulsion that was used in these emulsion layers comprises silver iodobromide containing 4.8 mole% silver iodide. In this instance, the blue-sensitive silver halide emulsion layer contains a yellow coupler α-(4-nitrophenoxy)-α-pivalyl-5-(γ-(2,4-di-t-aminophenoxy)butylamido]-2-chloroacetanilide, the green-sensitive silver halide emulsion layer contains a magenta couplers 1-(2,4,6-trichlorophenyl)-3-{[α-(2,4-di-t-amylphenoxy)acetamido]benzamido}-3-pyrazolone and 1-(2,4,6-trichlorophenyl)-3-{[α-(2,4-di-t-amylphenoxy)-acetamido]benzamido}-4-(4-methoxyphenylazo)-5-pyrazolone, and the red-sensitive silver halide emulsion layer contains the following Cyan Coupler C-2, and to these emulsions were added ordinary additives such as sensitizing dyes, hardening agents and others.
The following are the compositions of the respective bath solutions and their replenishers:

(Washing-substitute Stabilizer A Bath Solution and Replenisher)
Water to make 1 liter. Adjust the pH to 7.0 by using sulfuric acid or aqueous ammonia.

Processing Manner-7:

The foregoing color negative sample was exposed through a step wedge in usual manner and then subjected to a running processing test in the manner that the sample was processed in a KONICA Nice Printing System Automatic Processor whose baths were filled with the above-prepared color developer bath solution, bleach-fix bath solution and stabilizer bath solution, respectively, and while the processing was making progress, the above color developer replenisher, bleach-fix bath replenisher and stabilizer replenisher were supplied through the appropriate metering pumps at 30-minute intervals. As for the replenishing quantities per m² of the color negative sample, 220 ml of the color developer replenisher were supplied to the color developer bath, 220 ml of the bleach-fix bath replenisher to the bleach-fix bath and 250 ml of the washing-substitute sabilizer replenisher to the stabilizer bath.
The running test (1.0-m²/hr, the same shall apply hereinafter) lasted 24 hours.

Processing Manner-8:

A 24-hour running processing took, place in the same manner as in the above Processing Manner-7 except that a replenisher prepared by removing the bleach accelerating agent alone from the bleach-fix bath replenisher was supplied at 30-minute intervals, and this bleach accelerating agent was added at 6- hour intervals, In addition, the replenishing amount of the bleach-fix agent was set to 5.0g/liter.

Processing Manner-9:

A running processing took place in the same manner as in the above Processing Manner-8 except that the bleach accelerating agent was used in the form of an inclusion compound. The replenishing amount of the bleach accelerating agent was set to 5.6giliter in terms of the amount of the bleach accelerating agent.

Processing Manner-10:

The same automatic processor and the same processing solutions as those of Processing Manner-7 were used, but the processing quantity per day was set to 1 m² and the running processing lasted one week.

Processing Manner-11:

A running test was performed in the same manner as in Processing Manner-8 except that the processing quantity per day was set to 1 m², and the running processing lasted one week.

Processing Manner-12:

A running test took place in the same manner as in Processing Manner-9 except that the processing quantity was set to 1 m², and the running processing lasted one week.
The bleach-fix bath solution was sampled at times while the running processing was making progress, and the concentration of each objective compound (Bleach Accelerating Compounds 1 to 4) in the sampled solution was measured. It was confirmed that in Processing Manners-9 and -12, the bleach accelerating agent's concentration flucturation width, when compared with the case where the bleach accelerating agent which was not formed into an inclusion compound was replenished or added, was not more than 1/2. (The concentration measurement was carried out by liquid chromatography.)
Also, it was confirmed that in Processing Manners-9 and -12, the time that was taken until when the bleach accelerating agent which was made into the form of the inclusion compound of this invention was released by more than 90% by weight into the photographic processing solution was not less than three hours.
In addition, in this example, experiments were made with use of the following Bleach Accelerating Agents 1 to 4 in place of the bleach accelerating agent in the bleach-fix bath replenisher of Example 1.
The procedure of preparing the inclusion compound of this invention that was used in Processing Manners-9 and -12 are as follows: Branched ,8-cyclodextrin was used as a host compound, whereby the inclusion compound was prepared.
And, as the host compound in this invention, cellulose and amylose were also used, and similar experiments took place.
Bleach Accelerating Compounds:
The residual silver amount remaining in the maximum density area of the processed film sample (Processing Manners-7 to 9) was measured in accordance with the fluorescent radiation method. The maximum values of the residual silver amount obtained in the respective whole film samples in the above experiments are given in the following table.
Also, the degree of precipitation that occured in the one-week running processing was examined with respect to Processing Manners-10 through -12.
In both Processing Manners-10 and -11, precipitation occurred one week later, whereas in Processing Manner-12 (invention) no precipitation was found.

EXAMPLE 5

An internal latent image-type silver halide emulsion was prepared.
To an aqueous gelatin solution, with its temperature being kept at 50 C, were added simultaneously by the controlled double-jet method an aqueous silver nitrate solution and an aqueous solution of potassium bromide and sodium chloride (molar ratio: KBr:NaCl=60:40), whereby a cubic silver halide grain-having emulsion having an average grain diameter of 0.38µm was obtained. The thus obtained core emulsion, with the addition of sodium thiosulfate and potassium chloroaurate thereto, was subjected to chemical ripening at 55 C for 120 minutes. This emulsion was regarded as Emulsion A.
To this Emulsion A, as a core emulsion, were further added simultaneously an aqueous silver nitrate solution and an aqueous potassium bromide/sodium chloride solution (molar ratio KBr:NACI=20:80), whereby a tetradecahedral silver halide grain-having emulsion having an average grain diameter of 0.51µm was obtained. This emulsion was regarded as Emulsion F.
This Emulsion F, with the addition of sodium thiosulfate thereto, was chemically ripened, and upon completion of the chemical ripening, 1-phenyl-5-mercaptotetrazole was added in an amount of 10mg per mole of the silver halide of the emulsion.

Preparation of an Internal Latent Image-Type Silver Halide Light-Sensitive Material:

On a polyethylene-laminated paper support were coated in order from the support side the following layers, whereby an internal latent image-type light-sensitive material was prepared.

Layer 1: Cyan color-forming red-sensitive silver halide emulsion layer:

Ninety grams of a cyan coupler C-1 2,4-dichloro-3-methyl-6-[α-(2,4-di-tert-amylphenoxy)butylamido]-phenol, 2g of 2,5-di-tert-octyihydroquinone, 50g of tricresyl phosphate, 200g of paraffin and 50g of ethyl acetate are mixed to be dissolved, and to this solution is added a gelatin solution containing sodium dodecylbenzenesulfonate, and to this mixture is added the foresaid internal latent image-type silver halide emulsion, which is optically sensitized by 3.5x10^-5 mole per mole of silver halide of the foregoing Sensitizing Dye III, and also added Antiirradiation Dye AI-I. This emulsion was coated so that the coating weight of silver was 400mg/m², that of AI dye III was 20mg/m² and that of the coupler was 360mg/m^2.

Layer 2: Intermediate layer:

One hundred milliliters of a 2.5% gelatin solution containing 5g of grey colloidal silver and 10g of 2,5-di-tert-octylhydroquinone that is dispersed into dibutyl phthalate. This was coated so that the coating weight of the colloidal silver was 400mg/m².

Layer 3: Magenta color-forming green-sensitive silver halide emulsion layer:

One hundred grams of a magenta coupler M-1 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-octadecyls- uccinimidoanilino)-5-pyrazolone, 5g of 2,5-di-tert-octylhydroquinone, 50g of Sumilizer MPD (product of Sumitomo Chemical Industry Co.), 200g of paraffin, 100g of dibutyl phthalate and 50g of ethyl acetate are mixed to be dissolved, to this solution is added a gelatin solution containing sodium dodecylbenzenesulfonate, and to this mixture is added the aforesaid internal latent image-type silver halide emulsion, which is optically sensitized by 3.0x10^-4 mole per mole of silver halide of the foregoing Sensitizing Dye II, and also added Antiirradiation Dye IV. This emulsion was coated so that the coating weight of silver of 400mg/m², that of AI Dye IV was 20mg/m² and that of the coupler was 400mgim².

Layer 4: Yellow filter layer:

A 2.5% gelatin solution containing 5g of a yellow col loidal silver and 5g of 2,5-di-tert-octylhydroquinone dispersed into dibutyl phthalate. This was coated so that the coating weight of the colloidal silver was 200mg/m^2.

Layer 5: Yellow color-forming blue-sensitive silver halide emulsion layer:

One hundred and twenty grams of a Yellow Coupler Y-1 ^q-[4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-pivalyl-2-chloro-5-[γ-(2,4-di-tert-aminylphenoxy)butylamido]acetanilide, 3.5g of 2,5-di-tert-octylhydroquinone, 200g of paraffin, 100g of Tinuvin (product of Ciba Geigy), 100g of dibutyl phthalate and 70ml of ethyl acetate are mixed to be dissolved, and to this solution is added a gelatin solution containing sodium dodecylbenzenesulfonate, and to this mixture is added the aforementioned internal latent image-type silver halide emulsion, which is optically sensitized by 3.0x10^-4 mole per mole of silver halide of the foregoing Sensitizing Dye I. This emulsion was coated so that the coating weight of silver was 400mg/m² and that of the coupler was 400mg/m^2.

Layer 6: Protective layer:

A gelatin solution was coated so that the coating weight of the gelatin was 200mg/m².
In addition, saponin as a coating aid was incorporated into the above whole layers. Also, sodium 2,4-dichloro-6-hydroxy-S-triazyine as a hardening agent was added in an amount of 0.02g per gram of gelatin to Layers-2, -4 and -6.
The above light-sensitive material sample was exposed through an optical wedge, and then processed in accordance with the following processing procedure:
The compositions of the respective processing solutions are as follows: (Color Developer Solution)

Water to make 1 liter. Adjust the pH to 10.1 by using 20% potassium hydroxide or 10% sulfuric acid.
The spectral reflection maximum density of the cyan color of the processed sample was measured by means of a PDA-65 Densitometer (manufactured by Konica Corp.).

Processing Manner-13:

In accordance with the Processing Manner-1 of Example 1, a one A4-size sheet per day one-month consecutive processing test was performed.

Processing Manner-14:

A one A4-size sheet per day one-month consecutive processing test took place, provided that 5.0g of potassium sulfite were added as an additive once every three days to the color developer bath.

Processing Manner-15:

A one A4-size sheet per day one-month consecutive process ing test took place, provided that 30.0g of potassium sulfite were added prior to starting the consecutive processing.

Processing Manner-16:

A one A4-size sheet per day one-month consecutive processing test took place, provided that potassium sulfite was made into the form of inclusion compound of this invention in the same procedure as in the Processing Manner-3 of Example 1, and the treated potassium sulfite in an amount equivalent to potassium sulfite was added to the color developer bath prior to the commencement of the consecutive processing test.
The cyan dye densities (Dmax) of the above processed samples were measured, then the obtained minimum values were as follows:
As is apparent from the above, according to this invention, a high Dmax can be obtained and a better effect than that of Processing Manner-14, which processes with the replenishment that is made once every three days, can also be obtained, thus proving that the effect excellent in the long-term processing stability is exhibited.
We inventors have confirmed that the following compounds, when formed into the inclusion compound of this invention, are also significantly improved in the photographic processing stability as in the above examples:
That is, the confirmation was made on the hydroxylamin sulfate-substitute preservative of the photographic processing solution described in U.S. Patent No. 3,615,503; the preservative of the photographic processing solution disclosed in U.S. Patent No. 2,384,663; the anilinoethanol of the photographic processing solution described in U.S. Patent No. 3,823,017; the glycol of the photographic processing solution described in U.S. Patent No. 3,754,619; the ascorbic acid of the photographic processing solution described in U.S. Patent No. 3,721,563; the preservative of the photographic processing solution described in U.S. Patent No. 3,982,042; the ascorbic acid of the photographic processing solution described in U.S. Patent No. 2,923,627; the polyethyleneimine of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 94349/1981; the alkanolamine, monoaminomonocarboxylid acid and aminobenzoic acid of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 3532/1979; the a-hydroxy-aromatic-alcohol of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 7729/1977; the hydroxamic acid of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 27638/1977; the pyrogallol, p-pyrrolidinophenol and p-morpholinophenol of the photographic process ing solution described in Japanese Patent O.P.I. Publication No. 153437/1977; the chromotropic acid of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 49828/1977; the sodium metabisulfite of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 81336/1975; the unsaturated organic metal compound having B or Si in its a position of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 26223/1977; the pyrosulfite of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 21084/1980; the a-aminocarbonyl compounds (particularly, D-glucosamine and 1-deoxy-1-piperidino-D-fractose) of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 143020/1977; the G-D-glucolsamine of the photographic processing solution de- - scribed in Japanese Patent O.P.I. Publication No. 89425/1978; the N,N-di-substituted-p-phenylenediamine phosphate of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 26543/1976; the preservative (concentrated solution) of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 16137/1974; the N,N-diethylethylhydroxylamine of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 32035/1978; the pentose, methyl- pentose and hexose of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 102727/1977; the glycine, alanine and N-acetylglycine of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 140324/1977; the-aldehyde's hydrogensulfite addition product of the photographic processing solution described in Japanese Patent No. 185434/1982; the preservative of the photographic processing solution described in Japanese Patent O.P.I. Publication No. 16137/1972; the sulfite used in the photographic processing solution described in Japanese Patent Examined Publication No. 37957/1970; the ethylhydroxylamine of the photographic processing solution described in Japanese Patent Examined Publication No. 22198/1970; the ascorbic acid of the photographic processing solution described in Japanese Patent Examined Publication No. 35753/1970; the hydroxylamine oxalate of the photographic processing solution described in Japanese Patent Examined Publication No. 14345/1963; the preservative of the photographic processing solution described in British Patent No. 1,306,176; and the nitro compound used in the photographic processing solution described in British Patent No. 1,468,015.

Claims

1. A photographic processing agent which is used in a photographic processing solution for processing an imagewise ecposed photographic material, wherein said agent is an inclusion compound comprised of a host enclosing therin an effective component for photographic processing as its guest.

2. The agent of claim 1, wherein a time necessary for releasing 90% of said effective component from said inclusion cmpound is not less than three hours.

3. The agent of claim 2, wherein a time necessary for releasing 90% of said effective component from said inclusion compound is not less than six hours.

4. The agent of claim 3, wherein a time necessary for releasing 90% of said effective component from said inclusion compound is not less than twelve hours.

5. The agent of claim 1, wherein said effective component is a compound represented by the following Formula C;

wherein R_1c and R_2c each is a hydrogen atom or a substituted or un substituted alkyl group having 1 to 5 carbon atoms, provided that the R_1c and R_2c are not hydrogen atoms in the same time, and the R_1c and R_2c are allowed to form a ring together.

6. The agent of claim 1, wherein said effective component is a compound capable of releasing sulfite ions.

7. The agent of claim 6, wherein said compound is selected from the group consisting of sulfite, . hydrogen sulfite, metabisulfite, hydrosulfite and aldehyde-bis hydrogensulfite of an alkali metal or ammonium.

8. The agent of claim 1, wherein said effective component is a compound represented by the following Formula 1, 2, 3, 4, 5, 6, 7, 8 or 9:

wherein Q is a group of atoms necessary to form a nitrogen-containing heterocyclic ring; R₁ is a hydrogen atom, an alkyl group, having from 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic group or amino group,

wherein R₂ and R₃ each is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, hydroxy group, carboxy group, amino group, acyl group having from 1 to 3 carbon atoms, aryl group or alkenyl group; A is

or a n₁-valent heterocyclic residue; X is =S, =O, or =NR"; R and R' are the same in definition as the R₂ and R₃, res pectively; X' is is the same in definition as X; Z is a hydrogen atom, an alkali metal atom, an ammoniun group, amino group, nitrogen-containing heterocyclic residue, alkyl group, or

group; M is a divalent metal atom; R is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms; cycloalkyl group, aryl group, heterocyclic residue or amino group; n₁ and n₆ and m₁ to m_s each is an integer of from 1 to 6; B is an alkenyl group having from 1 to 6 carbon atoms; Y is -N = or -CH=; R₄ and R₅ are the same in definition as R₂ and R₃, respectively, provided that the R₂ and R₃, R', and R₄ and R₅ may combine with each other to form a ring,

wherein R₆ and R₇ each is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, hydroxy group, carboxy group, amino group, acyl group having from 1 to 3 carbon atoms, aryl group, alkenyl group or -B₁-S-Z₁ group, provided that the R₆ and R₇ are allowed to combine with each other to form aring; Y₁ is

a =N- or =CH- group: B₁ is an alkenyl group having from 1 to 6 carbon atoms; Z₁ is a hydrogen atom, alkali metal atom, ammonium group, amino group, nitrogen-containing heterocyclic residue or

group; an n₇ is an integer of from 1 to 6.

wherein R₈ an d R₉ each is

R₁₀ is an alkyl group or -(CH₂)n₈SO₃⊖, provided that when the R₁₀ is -(CH₂)n₈SO₃⊖, I is zero, while when the R₁₀ is an alkyl group, I is 1; G is an anion; and n₈ is an integer of from 1 to 6.

wherein Q₁ is a group of atoms necessary to form a nitrogen- containing heterocyclic ring; R₁₁ is a hydrogen atom,

or an alkyl group, provided that Q' and Q₁ are the same in definition,

wherein Di, D₂, O₃ and D₄ each is a simple bond or an alkylene or vinylene group having from 1 to 8 carbon atoms; q₁, q₂, q₃ and q₄ each is an integer of zero, 1 or 2; and each ring formed along with the sulfur atom may be condensed with 5- or 6-member saturated or unsaturated ring,

wherein X₂ is a -COOM', -OH, SO₃M', -CONH₂, -S0₂NH₂, -NH₂, -SH, -CN, -CO₂R₁₆, -SO₂R₁₆, -OR₁₆, -R₁₆R₁₇, -R₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHSO₂R₁₆, -OCOR₁₆ or -SO₂R₁₆ group; Y₂ is

or a hydrogen atom; ms and ns each is an integer of from 1 to 10; R₁₁, R₁₂. R₁₃, R₁₄, R_1S, R₁₇ and R₁₈ each is a hydrogen atom, a lower alkyl group, acyl group or

group; R₁₆ is a lower alkyl group; and R₁₉ is a-NHR₂₀R₂₁, -OR₂₂ or -SR₂₂ group, wherein R₂₀ and R₂₁ each is a hydrogen atom or a lower alkyl group; R₂₂ is a group of atoms necessary to form a ring together with the R₁₈; and the R₂₀ or R₂₁ is allowed to form a ring together with the R₁₈; and the M is a hydrogen atom or a cation,

wherein Ar is an arylene group or a divalent group formed in combination of an arylene group with an oxygen atom and/or an alkylene group; 8₂ and B₃ each is a lower alkylene group; R₂₃, R24, R₂₅ and R₂₆ each is a hydroxy-substituted lower alkylene group; x and y each is an integer of zero, 1 or 2; G' is a cation; and z is an integer of zero, 1 or 2,

wherein R₂₉ and Rao each is a hydrogen atom, an alkyl group, aryl group or heterocyclic group; Ra₁ is a hydrogen atom or an alkyl group; and R₃₂ is a hydrogen atom or a carboxy group.

9. The agent of claim 1, wherein said effective component is a fungicide.

10. The agent of claim 10, wherein said fungicide is selected from the group consisting of sorbic acid, benzoic acid-type compounds, phenol-type compounds, thiazole-type compounds, pyridine-type compounds, guanidine-type compounds, carbamate-type compounds, triazole-type compounds, morpholine-type compounds, quatenary phosphonium-type compounds, ammonium-type compounds, urea-type compounds, isoxazole-type compounds, propanolamine-type compounds, sulfamide-type compounds, pyronone-type compounds and amino-type compounds.

11. A method for processing a imagewise exposed photographic material comprising a step for processing said photographic material with a photographic processing solution containing a photographic . processing agent wherein said photographic processing agent is an inclusion compound comprised of a host enclosing therein an effective component for photographic processing as its guest.

12. The method of claim 11, wherein a time necessary for releasing 90% of said effective component from said inclusion cmpound is not less than three hours.

13. The method of claim 12, wherein a time necessary for releasing 90% of said effective component from said inclusion compound is not less than six hours.

14. The method of claim 13, wherein a time necessary for releasing 90% of said effective component from said inclusion compound is not less than twelve hours.

15. The method of claim 11, wherein said effective component is a compound represented by the following Formula C;

wherein R_1c and R_2c each is a hydrogen atom or a substituted or un substituted alkyl group having 1 to 5 carbon atoms, provided that the R_1c and R_2c cannot be hydrogen atoms in the same time, and the R_ic and R_2c are allowed to form a ring together.

16. The method of claim 11, wherein said effective component is a compound capable of releasing sulfite ions.

17. The method of claim 16, wherein said compound is selected from the group; consisting of sulfite, hydrogen sulfite, metabisulfite, hydrosulfite and aldehyde-bis hydrogensulfite of an alkali metal or ammonium.

18. The method of claim 11, wherein said effective component is a compound represented by the following Formula 1, 2, 3, 4, 5, 6, 7, 8 or 9:

wherein Q is a group of atoms necessary to form a nitrogen containing heterocyclic ring; R₁ is a hydrogen atom, an alkyl group, having from 1 to 6 carbon atoms, cycloalkyl group, aryl group, heterocyclic group or amino group,

or a n₁-valent heterocyclic residue; X is = S, = 0, or =NR"; R and R are the same in definition as the R₂ and R₃, respectively; X' is is the same in definition as X; Z is a hydrogen atom, an alkali metal atom, an ammoniun group, amino group, nitrogen-containing heterocyclic residue, aryl group or

M is a divalent metal atom; R is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms; cycloalkyl group, aryl group, heterocyclic residue or amino group; n₁ to n₆ and m₁ to m_s each is an integer of from 1 to 6; B is an alkenyl group having from 1 to 6 carbon atoms; Y is -N = or -CH =; R₄ and R₅ are the same in definition as R₂ and R₃, respectively, provided that the R₂ and R₃, R', and R₄ and Rs may combine with each form a ring,

I wherein R₆ and R₇ each is a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms, hydroxy group, carboxy group, amino group, acyl group having from 1 to 3 carbon atoms, aryl group, alkenyl group or -B₁-S-Z, group, provided that the R₆ and R₇ are allowed to combine with each other to form aring; Y₁ is a =N- or =CH- group: B₁ is an alkenyl group having from 1 to 6 carbon atoms; Z₁ is a hydrogen atom, alkali metal atom, ammonium group, amino group, nitrogen-containing heterocyclic residue or

and n₇ is an integer of from 1 to 6,

wherein R₆ an d R₉ each is

R₁₀ is an alkyl group or -(CH₂)n₈SO₃⊖, provided that when the R₁₀ is -(CH₂)n₈SO₃⊖, I is zero, while when the R₁₀ is an alkyl group, I is 1; G is an anion; and n₈ is an integer of from 1 to 6,

wherein Q₁ is a group of atoms necessary to form a nitrogen-containing heterocyclic ring; R₁₁ is a hydrogen atom,

or an alkyl group, provided that Q and Q₁ are the same in definition.

wherein D₁, D₂, D₃ and D₄ each is a simple bond or an alkylene or vinylene group having from 1 to 8 carbon atoms; q₁, q₂, q₃ and q₄ each is an integer of zero, 1 or 2; and each ring formed along with the sulfur atom may be condensed with 5- or 6-member saturated or unsaturated ring,

wherein X₂ is a -COOM', -OH, SO₃M', -CONH₂, -SO₂NH₂, -NH₂, -SH, -CN, -CO₂R₁₆, -SO₂R₁₆, -OR₁₆, -R₁₆R₁₇, -R₁₆, -SO₃R₁₆, -NHCOR₁₆, -NHSO₂R₁₆, -OCOR₁₆ or -SO₂R₁₆ group; Y₂ is

or a hydrogen atom; m_s and n_s each is an integer of from 1 to 10; R₁₁, R₁₂, R₁₃, R₁₄, R₁₅, R₁₇ and R₁₉ each is a hydrogen atom, a lower alkyl group, acyl group or

group; R₁₆ is a lower alkyl group; and R₁₉ is a -NHR₂₀R₂₁, -OR₂₂ or -SR₂₂ group, wherein R₂₀ and R₂₁ each is a hydrogen atom or a lower alkyl group; R₂₂ is a group of atoms necessary to form a ring together with the R₁₈; and the R₂₀ or R₂₁ is allowed to form a ring together with the R₁₈; and the M is a hydrogen atom or a cation,

wherein Ar is an arylene group or a divalent group formed in combination of an arylene group with an oxygen atom and/or an alkylene group; B₂ and B₃ each is a lower alkylene group; R₂₃, R₂₄., R₂₅ and R₂₆ each is a hydroxy-substituted lower alkylene group; x and y each is an integer of zero, 1 or 2; G is a cation; and z is an integer of zero, 1 or 2,

wherein R₂₉ and R₃₀ each is a hydrogen atom, an alkyl group, aryl group or heterocyclic group; R₃, is a hydrogen atom or an alkyl group; and R3₂ is a hydrogen atom or a carboxy group.

19. The method of claim 12, wherein said effective component is a fungicide.

20. The agent of claim 20, wherein said fungicide is selected from the group consisting of sorbic acid, benzoic acid-type compounds, phenol-type compounds, thiazole-type compounds, pyridine-type compounds, guanidine-type compounds, carbamate-type compounds, triazole-type compounds, morpholine-type compounds, quatenary phosphonium-type compounds, ammonium-type compounds, urea-type compounds, isoxazole-type compounds, propanolamine-type compounds, sulfamide-type compounds, pyronone-type compounds and amino-type compounds.