JP2654774B2 - Development processing method and developer for silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method and a developing solution for developing a silver halide photographic light-sensitive material. The present invention relates to a method for developing a silver halide photographic light-sensitive material (hereinafter referred to as a "photosensitive material") and a developing solution, which suppress generation of dirt on a rack and a roller in a developing processing tank and enable low-concentration replenishment processing. It is.

[Background of the Invention] Processing of a photosensitive material basically comprises two steps of color development and desilvering, and desilvering comprises a bleaching and fixing step or a bleach-fixing step. In addition to the above, additional processing steps such as rinsing processing, stabilizing processing, or stabilizing processing in place of washing are added.

In color development, the exposed silver halide is reduced to silver while the oxidized aromatic primary amine developing agent reacts with the coupler to form a dye. During this process, halogen ions generated by the reduction of silver halide are eluted and accumulated in the developer. In addition, components such as an inhibitor contained in the light-sensitive material are also eluted and accumulated in the color developing solution. In the desilvering step, silver generated by development is bleached by an oxidizing agent, and then all silver salts are removed from the light-sensitive material as soluble silver salts by a fixing agent. A one-bath bleach-fixing method in which the bleaching step and the fixing step are collectively processed simultaneously is also known.

In the color developer, the development inhibitor accumulates by developing the photosensitive material as described above, while the color developing agent and a development accelerator such as benzyl alcohol are consumed or impregnated into the photosensitive material and taken out. And the concentration of those components decreases. Therefore, in a developing method in which a large amount of photosensitive material is continuously processed by an automatic developing machine,
In order to avoid a change in the development finish characteristics due to a change in the component concentration, a means for keeping the components of the color developing solution within a certain concentration range is required. As such means, a method is usually employed in which a replenisher for replenishing deficient components and diluting unnecessary increased components is replenished. Since the replenishment of the replenisher inevitably causes a large amount of overflow and is discarded, this method is a serious problem in terms of economy and pollution. Therefore, in recent years, in order to reduce the overflow solution, a method of regenerating a developer by an ion exchange resin method or an electrodialysis method, a method of replenishing with a low concentration, and further, a method of adding a regenerating agent to the overflow solution and using it as a replenisher again Have been proposed and put to practical use.

To regenerate the developer, unnecessary accumulation components such as halide,
For example, it is performed by removing bromide to make up for the missing components. This method (ion exchange resin method and electrodialysis method)
The disadvantage is that if the developer components are quantified and made constant by chemical analysis, the processing characteristics of the photosensitive material will be impaired. And so-called minilabs are almost impossible to introduce. There is also a disadvantage that the initial cost is extremely high.

Further, the method of regenerating the replenisher by adding a regenerant to the overflow solution does not require any particular skill, but requires a space such as a stock tank, and has a disadvantage that it is complicated for a developing station. It is extremely difficult to introduce them into mini labs.

However, the concentrated low replenishment method is particularly suitable for a small-scale lab such as a so-called mini lab because the method does not require a new device and the process management is easy. However, this method also has some disadvantages. For example, as the replenishment rate decreases, the eluate from the photosensitive material into the developing solution accumulates greatly, and further, a large amount of decomposed products due to air oxidation of the color developing solution components accumulate. Under these circumstances,
When development processing is performed discontinuously over a long period of time in a small lab such as a so-called mini lab with a small amount of processing, tar or sludge accumulates in a color development processing tank of an automatic developing machine and racks and rollers (automatic development) (U-turn rollers and the like used in the transport system of the machine) generate dirt, and the dirt causes a failure to contaminate the photosensitive material to be processed. The black-and-white developer has the same problem.

[Object of the Invention] Accordingly, an object of the present invention is to provide a developing method and a developing method for a photosensitive material in which a rack or a roller in an automatic developing machine developing tank is not stained even with a low throughput and a low renewal rate. To provide a liquid.

Other objects of the present invention will become apparent in the following description.

[Means for Solving the Problems] In the development processing method of the present invention for achieving the above object, a photosensitive material is subjected to imagewise exposure and then developed in the presence of a branched cyclodextrin and / or a water-soluble cyclodextrin polymer. It is characterized by.

Further, the developer of the present invention for achieving the above-mentioned object is characterized by containing a branched cyclodextrin and / or a water-soluble cyclodextrin polymer.

In this specification, the term “branched cyclodextrin” is a concept excluding simple cyclodextrin. In the following, the water-soluble cyclodextrin polymer may be simply referred to as a cyclodextrin polymer.

In the present invention, "development in the presence of a branched cyclodextrin and / or cyclodextrin polymer" means that the branched cyclodextrin and / or cyclodextrin polymer of the present invention is contained in a light-sensitive material and the branched The cyclodextrin and / or the cyclodextrin polymer may be eluted into the developer, or a pre-bath containing the branched cyclodextrin and / or the cyclodextrin polymer may be provided and attached to a photosensitive material or a conveyor belt, so that the Or a developing solution and / or a replenisher thereof may contain a branched cyclodextrin and / or a cyclodextrin polymer. The branched cyclodextrin and / or cyclodextrin may be added to the photosensitive material during processing with the developing solution. Other if the polymer is present Which means that may be by law.

However, in the present invention, the above is particularly preferable from the viewpoint of the effect.

The branched cyclodextrin used in the present invention is a known cyclodextrin in which a water-soluble substance such as a monosaccharide or disaccharide such as glucose, maltose, cellobiose, lactose, sucrose, galactose, and glucosamine is branched or added. And preferably, maltosyl cyclodextrin in which maltose is bound to cyclodextrin (the number of binding molecules of maltose is one molecule, two molecules,
Glucosylcyclodextrin in which glucose is bound to cyclodextrin (the number of binding molecules of glucose may be one, two, or three).

Specific methods for synthesizing these branched cyclodextrins are described in, for example, Starch Science, Vol. 33, No. 2, pp. 119-126 (19).
86), pp. 127-132 (1986), Starch Science, Vol. 30, No. 2
For example, maltosyl cyclodextrin can be synthesized using cyclodextrin and maltose as raw materials and using enzymes such as isoamylase and pullulanase. And a method of binding maltose to cyclodextrin. Glucosylcyclodextrin can be produced in a similar manner.

In the present invention, examples of the branched cyclodextrin preferably used include the following specific exemplified compounds.

[Exemplary compounds] D-1 α-cyclodextrin having one molecule bonded to maltose, D-2 β-cyclodextrin having one molecule bonded to maltose, D-3 γ-cyclodextrin having one molecule bonded to maltose, D-4 maltose Α-cyclodextrin in which two molecules of D-5 maltose are bound, β-cyclodextrin in which two molecules of D-5 maltose are bound, γ-cyclodextrin in which two molecules of D-6 maltose are bound, D-7 α-cyclodextrin in which three molecules of maltose are bound Dextrin, D-8 β-cyclodextrin in which three molecules of maltose are bound, D-9 γ-cyclodextrin in which three molecules of maltose are bound, α-cyclodextrin in which one molecule of D-10 glucose is bound, and 1% of D-11 glucose Β-cyclodextrin and D-12 glucose with one molecule bound Γ-cyclodextrin, α-cyclodextrin in which two molecules of D-13 glucose are bonded, β-cyclodextrin in which two molecules of D-14 glucose are bonded, γ-cyclodextrin in which two molecules of D-15 glucose are bonded, D- 16 α-cyclodextrin in which three glucose molecules are bound, D-17 β-cyclodextrin in which three glucose molecules are bound, D-18 γ-cyclodextrin in which three glucose molecules are bound, For the structure of these branched cyclodextrins, see HP.
LC, NMR, TLC (thin layer chromatography), INEPT method (Ins
ensitive nuclei enhanced by polarization transfe
Although various measurement methods such as r) have been studied, they have not yet been determined even with current science and technology, and are in the stage of estimation structure. However, the fact that each monosaccharide or disaccharide or the like is bound to cyclodextrin is that there is no error in the above measurement method. Therefore, in the present invention,
When multiple molecules of monosaccharide or disaccharide are bonded to cyclodextrin, for example, as shown in the figure below, when they are individually bonded to each glucose of cyclodextrin, or linearly bonded to one glucose It is intended to include both of the above.

Since the ring structure of the existing cyclodextrin is retained as it is, it exhibits the same inclusion function as the existing cyclodextrin, and the addition of highly water-soluble maltose or glucose dramatically improves the solubility in water. The feature is that it is.

The cyclodextrin in the above exemplified compound is represented by the following general formula [A].

General formula [A] Of these, those particularly useful in the present invention are α-cyclodextrin with n ′ = 4, β-cyclodextrin with n ′ = 5, and γ-cyclodextrin with n ′ = 6. Also,
In the present invention, among these branched cyclodextrins,
Particularly particularly effective are branched β-cyclodextrins.

Further, the cyclodextrin moiety according to the present invention performs an inclusion function to form an inclusion compound. In the present invention, the inclusion compound can be used.

The inclusion compound of the cyclodextrin moiety is described, for example, by F. Cramer, “Einschluβ verbindungen”
r (1954) or M. Hagan, "Clathrate Inclusion Compound" (Clathrate)
Inclusion Conpounde) As described in Reinh ld (1962), there is a hole of an appropriate size inside a three-dimensional structure formed by bonding atoms or molecules, in which other atoms or molecules are fixed. A substance that forms a specific crystal structure by entering at a composition ratio. "

The cited documents of the production examples of the inclusion compound of cyclodextrin are described below, but these are merely a few examples, and are not limited to these.

◎ Journal of the American Chemical Society, Vol. 71, pp. 354, 1949 ◎ Chemishe Berichte, Vol. 90, pp. 2572, 1957 ◎ Also in the invention, by the method described in these,
Create cyclodextrin inclusion compound in advance,
The cyclodextrin can be added to the light-sensitive material and / or the developing solution.
Alternatively, the compound contained therein can be partially or entirely included by adding it to a developer.

The branched cyclodextrin used in the present invention can also be obtained as a commercial product. For example, maltosyl cyclodextrin can be obtained from Iso Elite (registered trademark) manufactured by Saiko Minato Seika.
It is commercially available as

The branched cyclodextrin used in the present invention may be a powder or a liquid (for example, a 70% liquid).

As the cyclodextrin polymer used in the present invention, those represented by the following general formula [B] are preferable.

General formula [B] The cyclodextrin polymer used in the present invention,
Cyclodextrin can be produced, for example, by cross-linking and polymerizing with epichlorohydrin.

The cyclodextrin polymer preferably has a water solubility, that is, a solubility in water of not less than 20 g per 100 ml of water at 25 ° C., for which purpose the above-mentioned general formula [B]
In this case, the degree of polymerization n ″ may be 3 to 4. The smaller the value, the higher the water solubility of the cyclodextrin polymer itself and the effect of solubilizing the substance.

These cyclodextrin polymers are disclosed, for example, in
It can be synthesized by a general method described in 61-97025, German Patent 3,544,842, and the like.

The cyclodextrin polymer may also be used as an inclusion compound of the cyclodextrin polymer as described above.

In one preferred embodiment of the present invention, at least one of the branched cyclodextrin and / or the cyclodextrin polymer according to the present invention is added to a hydrophilic colloid layer constituting a light-sensitive material, followed by development processing. Gelatin is preferred as the hydrophilic colloid. In a further preferred embodiment of the present invention, an emulsion layer containing at least one of the branched cyclodextrins and / or cyclodextrin polymers according to the present invention containing silver halide, a layer directly adjacent to the layer, and an intermediate layer interposed therebetween. That is, it is added to at least one of the layer, the protective layer and the undercoat layer, and is subjected to a development treatment.

Developing in the presence of cyclodextrin,
In particular, processing by adding to a developer to improve the variability of the development characteristics during development, and to give a certain photographic performance,
This is known from JP-A-53-48735. However,
With the increase in rapid processing shops called 1 hour photo (one hour photo) in recent years, the need for rapid processing has become stronger, and processing at a high temperature near 40 ° C tends to be performed. Dextrin is becoming a situation that cannot be compensated for. Cyclodextrin has the disadvantage that it has poor solubility, cannot be added in large amounts, and cannot be concentrated. For this reason, in addition to kitting,
The fact was that even a concentrated replenisher could not be prepared. By making this soluble, a kit can be made and a concentrated replenisher can be used, a low replenishment can be achieved, and the photographic performance can be more completely stabilized.
Furthermore, a branched cyclodextrin and / or an effect which cannot be found with conventional cyclodextrins, ie, reduction of tar and sludge in low renewal rate treatment.
Alternatively, the present inventors have found a new effect of the cyclodextrin polymer and have accomplished the present invention. The present inventors have further studied variously. As a result, ordinary cyclodextrin has no effect in preventing the crystal of the developing agent deposited on the liquid surface of the tank inner wall of the automatic developing machine developing tank, but the branched cyclodextrin and / or cyclodextrin is not effective. It has been found that dextrin polymers are extremely effective, and the present invention has been accomplished.

The branched cyclodextrin according to the present invention and / or
Or when adding at least one cyclodextrin polymer and performing development processing, from 0.1 g per liter of developer
Good range is 100g, especially 0.5g to 50g gives good results. The amount of addition is appropriately selected depending on the type of silver halide and the type of the branched cyclodextrin and / or cyclodextrin polymer of the present invention.

In the photographic processing of the photosensitive material of the present invention, for example,
Disclosure (Research Disclosure) 176 No. 28
To page 30 (RD-17643), any of the known methods and known processing solutions can be applied. This photographic processing may be either development processing for forming a silver image (black and white development processing) or development processing for forming a dye image (color development processing), depending on the purpose.
The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

In the processing method of the light-sensitive material of the present invention, the above-mentioned developing bath can be used. In addition, various treatments such as a bath treatment and various other treatments such as a spray method for spraying a treatment liquid, a wet method by contact with a carrier impregnated with a treatment liquid, and a development method using a viscous treatment liquid A method can be used.

In addition to the above, the processing method of the light-sensitive material of the present invention is not particularly limited, and any processing method can be applied. For example, if the photosensitive material to be processed is a color photosensitive material,
Typical examples thereof include a method of performing bleach-fixing after color development and further performing washing and / or stabilization if necessary. After color development, performing bleaching and fixing separately, and further performing washing and / or Or a method of performing a stable treatment;
Alternatively, forehardening, neutralization, color development, stop fixing, washing, bleaching, fixing, washing with water, post-hardening, washing in the order of washing, color development, washing, supplemental color development, stop, bleaching, fixing, washing, Processing may be carried out using any method such as a method in which the development is carried out in the order of stabilization, or a development method in which the developed silver produced by color development is subjected to halogenation bleaching, and then color development is performed again to increase the amount of the produced dye.

In a preferred embodiment of the present invention, the developer contains a compound represented by the following general formula [I].

When these compounds are used in combination with the compound represented by the general formula [I], not only the effect of the object of the present invention is exerted more favorably, but also another effect that the occurrence of fogging at the time of low renewal rate treatment is suppressed. Play.

General formula [I] R-OA _n B _m D [wherein, R is an alkyl group having 4 to 25 carbon atoms which may have a linear or branched substituent or Wherein R ₁ and R ₂ each represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a substituent,
Represents an integer of 4. ). A and B are respectively They may be the same or different (provided that n ₁ , m ₁ and l ₁
Represents 0, 1, 2 or 3, respectively. ). D represents a hydrogen atom or -SO ₃ M (where, M represents hydrogen atom, sodium, potassium, ammonium or lithium.).

n and m each represent 0 or an integer of 1 to 25. In another preferred embodiment of the present invention, the developer contains at least one of the compounds represented by the following general formulas [II] to [VI].

When used in combination with the compounds represented by the general formulas [II] to [VI], not only the effects of the present invention can be obtained well, but also the storage stability of the developer in an automatic developing machine having a large air contact area can be improved. Another effect is also achieved that is improved.

General formula [II] In the formula, A ₁ represents a carboxylic acid group, a phosphate group or a salt thereof, and X represents a hydroxyl group or a salt thereof. B ₁ represents a halogen atom, a hydroxyl group, an alkyl group, a carboxylic acid group, a phosphonic acid group, or a salt of a hydroxyl group, an ervonic acid group or a phosphonic acid group. r and l ₂ each represent 0, 1 or 2, n ₂ represents an integer of 1 to 4, and m ₂ represents an integer of 0 to 3.

General formula [III] In the formula, R ₃ represents an alkyl group or an amino group which may have a substituent having 1 to 5 carbon atoms.

General formula [IV] General formula [V] Wherein R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each a hydrogen atom,
Halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, -OR _9, -COOR _10, Alternatively, it represents a substituted or unsubstituted phenyl group. Also, R ₉ ,
R ₁₀ , R ₁₁ and R ₁₂ are each a hydrogen atom or carbon number 1 to 1
8 represents an alkyl group.

In the formula [VI] NA _n B _m H] ₃ , n, m, A and B have the same meanings as the corresponding symbols in the formula [I].

Next, preferred representative specific examples of the compound of the present invention represented by the general formula [I] will be described.

(Exemplary compound)

(I-12) (n) C 13 H 27 -OCH 2 CH 2 O 5 SO 3 Na (I-13) (n) C 12 H 25 -OCH 2 CH 2 O 3 SO 3 Na (I-14) ( _{n) C 10 H 21 -OCH 2} CH 2 O 4 SO 3 K (I-15) (n) C 16 H 33 -OCH 2 CH 2 O 4 SO 3 Na (I-18) (n) C 13 H 27 -OCH 2 CH 2 O 4 H Among the compounds represented by the general formula [I], from the viewpoint of the object of the present invention, (I-1), (I-12),
(I-13) is particularly preferably used.

These compounds are synthesized by a general synthesis method as described in British Patent 1,022,878, US Pat. No. 3,723,341, US Pat. No. 3,437,598 and the like. Alternatively, commercially available products (for example, Olin Mathieson Chemica
l Corp.).

Further, when the compound represented by the general formula [I] is used in the range of 0.001 to 10 g per 1 developer of the present invention, the above-mentioned object of the present invention is achieved particularly well, and furthermore,
Particularly when used in the range of 0.01 to 3 g, the effects of the present invention are particularly excellent.

Next, preferred representative specific examples of the compound according to the present invention represented by the general formula [II] will be described.

(Exemplary compound)

These compounds are disclosed in U.S. Patent No. 3,632,637 and Journal of the American Chemical Society Vo.
Synthesized by a general synthesis method as described on page 837 of l.89 (1967).

Next, typical specific examples of the compound represented by the general formula [III] and preferably used in the present invention will be described.

(III-1) 1-hydroxyethylidene-1,1-diphosphonic acid (III-2) 1-hydroxypropylidene-1,1-diphosphonic acid (III-3) 1,2-dihydroxyethane-1,1-diphosphonic acid Acid (III-4) 1-hydroxybutane-1,1-diphosphonic acid (III-5) 1-hydroxy-2-carboxy-ethane-
1,1-Disulfonic acid (III-6) 1-amino-ethylidene-1,1-diphosphonic acid Specific illustrative compounds represented by the general 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, 1,2,3-trihydroxybenzene-5-carboxymethyl ester, 1,
2,3-trihydroxybenzene-5-carboxy-n-propyl ester, 5-t-butyl-1,2,3-trihydroxybenzene, 2,3-dihydroxynaphthalene-6-sulfonic acid, 2,3,
Examples include, but are not limited to, 8-trihydroxynaphthalene-6-sulfonic acid. Among the above compounds, compounds particularly preferably used in the present invention include 1,2-dihydroxybenzene-3,5-disulfonic acid and its sodium and potassium salts, and 1,2-dihydroxybenzene-3,4,6- Trisulfonic acid and its sodium and potassium salts, exemplified compound (III-1),
(II-2) and (II-10), more particularly preferably, 1,2-dihydroxybenzene-3,5-disulfonic acid and salts thereof (sodium salt, potassium salt).

The compounds of the general formulas [II] to [V] are preferably used in the range of 0.01 g to 10 g, more preferably in the range of 0.03 g to 3 g per developer of the present invention.

Next, typical specific examples of the compound represented by the general formula [VI] and preferably used in the present invention will be described.

Exemplified Compound] (VI-1) N- ( CH 2 CH 2 OH) 3 (VI-2) N - [(CH 2 CH 2 O) 2 H] 3 (VI-5) N- (CH ₂ CH ₂ CH ₂ OH) ₃ (VI-6) N- (CH ₂ CH ₂ CH ₂ CH ₂ OH) ₃ Among the compounds represented by the above general formula [VI], the present invention Compounds that are particularly preferably used in (VI-1)
And (VI-2).

The compound represented by the above general formula [VI] is preferably used in the range of 0.3 to 50 g per 1 developer of the present invention, and particularly when the compound is used in the range of 1 g to 20 g, the effect of the present invention is particularly improved. Plays well.

When the developer of the present invention is used in combination with an aminocarboxylic acid compound or an aminophosphonic acid compound, the object of the present invention can be more effectively achieved,
Another effect of improving the precipitation of the developing agent that occurs during low-temperature storage is also exhibited. Therefore, in the present invention, addition of an aminocarboxylic acid compound or an aminophosphonic acid compound is preferred. The aminocarboxylic acid-based compound or the aminophosphonic acid-based compound represents an amino compound having at least two or more carboxylic acid groups and an amino compound having at least two or more phosphonic acid groups, and is preferably represented by the following general formula [VII] ] And [VIII].

General formula [VII] General formula [VIII] Wherein, E is a substituted or unsubstituted alkylene group, a cycloalkylene group, a phenylene _{group, -R 13 OR 13 OR 13 -} , - R 13
ZR ₁₃ - represents, Z is> N-R ₁₃ -A _6, represents> N-A _6, R
_{9 to} R ₁₃ represent a substituted or unsubstituted alkylene group, and A ₂ to
A ₆ represents a hydrogen atom, -OH, -COOM, and -PO ₃ M _2, M represents a hydrogen atom, an alkali metal atom.

Next, preferred specific examples of the compounds represented by the general formulas [VII] and [VIII] are shown below.

[Example compound] [VII-1] Ethylenediaminetetraacetic acid [VII-2] Diethylenetriaminepentaacetic acid [VII-3] Ethylenediamine-N- (β-hydroxyethyl) -N, N ', N'-triacetic 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- Diaminopropan-2-ol-tetraacetic acid [VII-9] ethyl ether diamine tetraacetic acid [VII-10] glycol ether diamine tetraacetic acid [VII-11] ethylenediamine tetrapropionic acid [VII-12] phenylenediamine tetraacetic acid [VIII -1] nitrilotriacetic acid [VIII-2] iminodiacetic acid [VIII-3] hydroxyethyliminodiacetic acid [VIII-4] nitrilotri Lopionic acid [VIII-5] nitrotrimethylenephosphonic acid [VIII-6] Iminodimethylenephosphonic acid [VIII-7] Hydroxyethyliminodimethylenephonic acid Among these aminocarboxylic acid compounds and aminophosphonic acid compounds, Compounds which are particularly preferably used in view of the effects of the object of the invention include (VII-1) and (VII-
2), (VII-5), (VII-8), (VIII-1), (VI
II-3) and (VIII-5).

These aminocarboxylic acid compounds and aminophosphonic acid compounds can be used arbitrarily as salts such as sodium salt, potassium salt and lithium salt.

The addition amount of the aminocarboxylic acid compound and the aminophosphonic acid-based compound according to the present invention may be
It is preferably used in the range of 0.1 to 20 g, and particularly preferably in the range of 0.3 to 5 g for the purpose of the present invention.

When a color developing solution is used as the developing solution of the present invention,
In the color developing solution, a p-phenylenediamine-based color developing agent is used, and these are generally used in the form of a salt, for example, a hydrochloride or a sulfate, because they are more stable than a free state.
The p-ferenediamine-based color developing agent is generally used at a concentration of about 0.5 g to about 30 g for the color developing solution 1.

In the present invention, a particularly useful p-phenylenediamine-based color developing agent from the viewpoint of better achieving the effects of the object of the present invention is an aromatic primary amine color developing agent having at least one water-soluble amino group. And particularly preferably a compound represented by the following general formula [IX].

General formula [IX] In the formula, R ₁₄ represents a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group is a straight-chain or branched carbon atom having 1 to 5 carbon atoms.
And may have a substituent. R ₁₅
And R ₁₆ represent a hydrogen atom, an alkyl group or an aryl group, and these groups may have a substituent. And R
_14, at least one of R ₁₅ and R ₁₆ are hydroxyl group, a carboxylic acid group, a sulfonic acid group, an amino group, an alkyl group or a CH _{2 t} O _{r R 17} water-soluble group is substituted, such as a sulfonamide group.

R ₁₇ represents a hydrogen atom or an alkyl group, and the alkyl group represents a linear or branched alkyl group having 1 to 5 carbon atoms, and t and r each represent an integer of 1 to 5.

Next, typical specific examples of the compound represented by the general formula [IX] will be described, but the invention is not limited thereto.

(Exemplary compound)

These p-phenylenediamine derivatives represented by the general formula [IX] can be used as salts of organic acids and inorganic acids, for example, hydrochloride, sulfate, phosphate, p-toluenesulfonate, sulfite, oxalic acid Salts and benzyl disulfonates can be used.

In the present invention, the p-type represented by the general formula [IX] is used.
Among the phenylenediamine derivatives, when R ₁₅ and / or R ₁₆ are those represented by CH _{2 t} O _r R ₁₇ (t, r and R ₁₇ are as defined above), the effects of the present invention can be particularly improved. Play.

When a triazylstilbene-based fluorescent whitening agent is used in the color developing solution of the present invention, the effect of the present invention is more favorably exhibited, and another effect that tar characteristics during storage of the replenisher is further improved is also exhibited. It is more preferably used in the present invention for performing.

The triazylstilbene-based fluorescent whitening agent used in the present invention is preferably represented by the following general formula [X].

General formula [X] In the formula, X ₁ , X ₂ , Y ₁ and Y ₂ each represent a hydroxyl group, a halogen atom such as chlorine or bromine, a morpholino group, an alkoxy group (for example, methoxy, ethoxy, methoxyethoxy, etc.),
An aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.), an alkyl group (eg, methyl, ethyl, etc.),
Aryl group (eg, phenyl, methoxyphenyl, etc.), amino group, alkylamino group (eg, methylamino, ethylamino, propylamino, dimethylamino,
Cyclohexylamino, β-hydroxyethylamino,
Di (β-hydroxyethyl) amino, β-sulfoethylamino, N- (β-sulfoethyl) -N′-methylamino, N- (β-hydroxyethyl-N′-methylamino, etc.), arylamino group (for example, 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.). M has the same meaning as M in the general formula [I].

Specific examples include the following compounds, but are not limited thereto.

(Exemplary compound)

The triazylstilbene-based brightener of the present invention is, for example, “Fluorescent brightener” edited by The Chemical Industry Association of Japan (issued in August 1976).
It can be synthesized by the usual method described on page.

These triazylstilbene-based brighteners are preferably used in the range of 0.2 to 6 g per color developing solution of the present invention,
Particularly preferably, it is in the range of 0.4 to 3 g.

The color developing solution according to the present invention may contain an alkali agent usually used in the developing solution, for example, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And various additives such as benzyl alcohol, an alkali metal halide such as potassium bromide or potassium chloride, or a development regulator such as citrazic acid, and a preservative such as hydroxylamine or sulfite. Good.

The pH of the color developing solution according to the present invention is usually 7 or more, preferably about 9 to 13.

When the developing solution of the present invention is a color developing solution, a bleaching step is usually used as the subsequent step.Bleaching agents used in the bleaching solution or the bleach-fixing solution in the bleaching step include aminopolycarboxylic acid, oxalic acid, and citric acid. Iron with organic acids such as
Coordination of metal ions such as cobalt and copper is generally known. The following are typical examples of the above aminopolycarboxylic acids.

Ethylenediaminetetraacetic acid Diethylenetriaminepentaacetic acid Propylenediaminetetraacetic acid Nitrilotriacetic acid Iminodiacetic acid Glycoletherdiaminetetraacetic acid Ethylenediaminetetrapropionic acid The bleaching solution may contain various additives together with the above-mentioned bleaching agent. When a bleach-fix solution is used in the bleaching step,
A liquid having a composition containing a silver halide fixing agent in addition to the bleaching agent is used. The bleach-fixing solution may further contain a halogen compound such as potassium bromide.

Examples of the silver halide fixing agent include, for example, sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, or thiourea, thioether, etc. The compound which forms the silver salt of this can be mentioned.

The photosensitive material of the present invention is disclosed in JP-A-58-14834 and JP-A-58-10514.
No. 5, No. 58-134634, No. 58-18631 and Japanese Patent Application No. 58
Alternatively, a washing substitute stabilizing treatment as shown in JP-A-2709 and JP-A-59-89288 may be performed.

Color developing solution of the present invention, color negative film, color paper, color positive film, color reversal film,
It can be applied as any color developing solution of a general photosensitive material such as color reversal paper.

The crystal of the silver halide grains of the light-sensitive material to which the processing of the present invention is applied may be a normal crystal, a twin crystal, or another crystal, [1.
Any ratio can be used for the [0.0] plane and the [1.1.1] plane. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered or phased structure (core-shell type) in which the inside and the outside are different. . These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

Various yellow couplers, magenta couplers and cyan couplers can be used without particular limitation as the coupler usable in the light-sensitive material of the present invention. These couplers may be so-called 2-equivalent couplers or 4-equivalent couplers, but in the present invention, 2-equivalent couplers are more preferably used in view of the effects of the present invention. When used in combination with a cyclodextrin derivative of the formula (I), another effect of improving dye dyeing on the turn roller portion of the color developing tank is also exerted, so that it is more preferably used in the present invention.

It is also possible to use a diffusible dye-releasing coupler in combination with these couplers.

In the present invention, the two-equivalent coupler is used at least in the green-sensitive silver halide emulsion layer. In particular, when the two-equivalent coupler is simultaneously used in other red-sensitive and blue-sensitive silver halide emulsion layers, the sensitivity can be improved. In addition, remarkable effects can be achieved in terms of high contrast, silver saving, reduction of processing time, and the like.

Representative examples of the coupler nucleus of the 2-equivalent yellow coupler among the 2-equivalent couplers are described in U.S. Pat.
No. 057, No. 2,407,210, No. 3,265,506, No. 2,298,443
Nos. 3,048,194 and 3,447,928. Among these yellow couplers, acylacetamide derivatives such as benzoylacetanilide and pivaloylacetoanilide are preferred.

Therefore, as the yellow coupler residue (Cp), those represented by the following general formulas [XI] and [XII] are preferable.

General formula [XI] General formula [XII] In addition, * represents the position where the leaving group (described later) of the 2-equivalent yellow coupler is bonded.

Here, R ₂₁ represents a non-diffusible group having 8 to 32 carbon atoms when the leaving group does not have a non-diffusible group. When the leaving group has a non-diffusible group (eg, UK Patent No. 2,083,640) Represents a hydrogen atom, one or more halogen atoms, a lower alkyl group, a lower alkoxy group or a non-diffusible group having 8 to 32 carbon atoms in total. R ₂₂ is a hydrogen atom,
Represents one or more halogen atoms, lower alkyl groups, lower alkoxy groups, or diffusion-resistant groups having 8 to 32 carbon atoms in total. If R ₂₂ is two or more, they may be the same or different.

As the leaving group of the 2-equivalent yellow coupler, for example,
JP-B-49-12660, 49-12661, 49-13576, 51
-10783, 51-25733, 54-38497, JP-A-47-261
No. 33, No. 48-66834, No. 48-66835, No. 48-73147, No.
49-10736, 49-1229, 50-6341, 50-34232
No., No. 50-117423, No. 51-102636, No. 50-158329,
No. 51-17438, No. 51-3631, No. 51-26039, No. 51-5073
No. 4, No. 51-53825, No. 51-89730, No. 52-28318, No. 5
2-58922, 52-90932, 53-135625, 54-48541
No. 54-121126, No. 54-99433, No. 54-13329, Res
earch Disclosure 180531, U.S. Patent No. 3,894,875,
No. 933,501. Among them, those having O-acyl substitution at the active site of the coupler, -hydantoin substitution, -urazole substitution, -monooxoimide substitution, -pyridanone compound substitution, -sulfonyl substitution and the like are preferable. .

Representative examples of the coupler core of a 2-equivalent magenta coupler are described in U.S. Pat. Nos. 2,600,788, 2,369,489 and 2,34.
3,703, 2,311,082, 3,152,896, 3,519,429
No. 3,062,653, No. 2,908,573, No. 3,733,335,
It is described in British Patent 1,334,515 and the like. Of those magenta couplers, pyrazolone or pyrazoloazoles (pyrazolopyrazole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, etc.)
Is preferred.

Therefore, as the magenta coupler residue, those represented by the following general formulas [XIII], [XIV] and [XV] are preferable.

General formula [XIII] General formula [XIV] General formula [XV] In addition, * represents the position where the leaving group (described later) of the 2-equivalent magenta coupler is bonded.

Here, R ₂₁ and R ₂₂ are represented by the general formulas [XI] and [XII]
Has the same meanings as R ₂₁ and R ₂₂ in.

As the leaving group of the 2-equivalent magenta coupler, for example,
JP-B-49-37854, JP-B-50-37540, JP-B-50-10100, JP-B52
-34937, and JP-A-49-29635, JP-A-49-129538,
No. 50-13041, No. 50-122935, No. 50-159336, No. 51-3
232, 51-3233, 51-17437, 51-16929,
51-20826, 51-36938, 51-108842, 51-1123
No. 41, No. 51-112343, No. 52-58922, No. 53-123129,
No. 54-33032, No. 54-48539, No. 54-80744, No. 54-857
No. 24, No. 55-62454, No. 55-83044, No. 55-118034,
56-38043, 56-38044, 56-40825, 56-126
No. 833, No. 57-4044, No. 57-35858, No. 57-96334, No.
Nos. 57-96335 and 57-96337. Of these, those containing a nitrogen-containing hetero ring (eg, azoles such as pyrazole, imidazole, and triazole)-those substituted with an alkylthio compound, those substituted with an -aryl compound thio, those substituted with an aryloxy compound, those substituted with an ashiruoxy compound And those substituted with a compound complexed with an arylaldehyde group or an alkylaldehyde group.

Examples of the coupler core of the 2-equivalent cyan coupler include, for example, U.S. Pat. Nos. 2,772,162, 2,895,826, and 3,002,83.
No. 6, 3,034,892, 2,474,293, 2,423,730,
Nos. 2,367,531 and 3,041,236. Of those cyan couplers, phenols or naphthols are preferred.

Therefore, as the cyan coupler residue (Cp), the following general formulas [XVI], [XVII], [XVIII] and [XIX]
The following is preferable.

General formula [XVI] General formula [XVII] General formula [XVIII] General formula [XIX] * Represents the position where the leaving group of the 2-equivalent cyan coupler is bonded.

Here, R ₂₁ and R ₂₂ are represented by the general formulas [XI] and [XII]
Has the same meanings as R ₂₁ and R ₂₂ in.

Examples of the leaving group of the 2-equivalent cyan coupler include, for example, JP-B-49-17735, JP-B-37-4896, JP-A-47-21139, and JP-A-47-21139.
7-37425, 50-10135, 50-25228, 50-91323
No., No. 50-117422, No. 50-120334, No. 50-130441,
No. 51-17437, No. 51-21825, No. 51-25828, No. 51-108
No. 841, No. 51-110328, No. 51-146828, No. 52-18315
No. 52-20023, No. 52-555529, No. 52-90932, No. 5
3-39126, 53-39743, 53-45524, 53-47827
Nos. 53-52423, 53-105226, 54-14736, 5
4-48237, 54-66129, 55-32071, 55-65957
Nos. 56-1935, 56-6234, 56-12643, 56-2
7147, 55-65957, 56-80044, 56-126832
No. 57-200039; U.S. Pat.Nos. 3,749,735; 3,737,31
No. 5, 3,839,044, 4,225,233 and the like. Of these, those substituted with arylalkoxy, those substituted with alkylalkoxy, those substituted with carbonylmethoxy, those substituted with halogen atoms (F, Cl, Br, I), those substituted with sulfonyloxy compounds, those substituted with sulfonamide compounds Are preferred.

Specific examples of the two-equivalent coupler used in the present invention are shown below, but are not limited thereto.

[Example of 2-equivalent yellow coupler] [Example of 2-equivalent magenta coupler] [Example of 2-equivalent cyan coupler] Other specific examples of 2-equivalent couplers are described in
(Y-1) to (Y-23), (M-1) to (Y-29) described on pages 337 to 345 in JP-A-61-73595.
(C-1) to (C-32).

The coating amount of the 2-equivalent coupler used in the present invention is preferably 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol / m ² , more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻³ mol / m ² in the case of a cyan coupler or a yellow coupler. 2 × 10 ⁻³ mol / m ² , particularly preferably 2 × 10 ⁻³ mol / m 2
× 10 ^{-4 to} 2 × 10 ^-3 mol / m ² , and in the case of a magenta coupler, preferably 2 × 10 ^-5 to 1 × 10 ^-3 mol / m ² , more preferably 5 × 10 ^-5 to It is 1 × 10 ⁻³ mol / m ² , particularly preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻³ mol / m ² .

In the present invention, the ratio (molar ratio) of Ag / coupler in the blue-sensitive emulsion layer is preferably 2 to 100, and more preferably 3 to 100.
50 to 50, preferably 4 to 300, more preferably 6 to 200 in the green-sensitive emulsion layer, and 8 to 500 in the red-sensitive emulsion layer.
And more preferably 10 to 300.

When there are two or more layers of the same photosensitive layer, the two-equivalent coupler is used for the layer having higher sensitivity (for example, in the case of three layers consisting of a high-sensitive layer, a medium-sensitive layer, and a low-sensitive layer, (Sensitive layer or high-sensitive layer and medium-sensitive layer).

Further, among the 2-equivalent couplers, from the viewpoint of better achieving the effects of the object of the present invention, the 2-equivalent magenta coupler represented by the general formula (XV) and the general formulas (XVI), (XVII) or (XVII) XVIII] is preferably used.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 The following color developing solution No. 1 was placed in a color developing tank of a color paper processor CL-RP500 (manufactured by Konishi Roku Kogyo Kogyo Co., Ltd.) of Sakura Nice Print System, and the temperature was adjusted to 39.8 ° C.
Maintain the operation state for 12 hours per day (the circulation pump and the agitating pump are operated), and then leave it for 12 hours for 10 consecutive days. After 10 days, the condition of the color developing tank (tar and sludge generation, liquid level Crystal precipitation state).

On the other hand, as shown in Table 1 below, the same storage experiments were carried out for Color Developer Nos. 2 to 12 in which cyclodextrin and its derivatives were added to Color Developer No. 1 (for comparison). In each case, the state of the color developing tank after 10 days was observed, and the results are summarized in Table 1.

In the table, () indicates the amount of addition. × is tar,
This indicates that the amount of crystals deposited on the inner wall of the tank of the sludge or the color developing tank is large, and the larger the number of X, the worse the situation. In addition, △ is slightly generated, ○
Means that no occurrence is seen.

From Table 1, those using the developing solution using the branched cyclodextrin or the cyclodextrin polymer according to the present invention does not generate tar or sludge in the color developing tank,
Further, it can be seen that there is almost no crystal precipitation at the interface of the liquid in the color developing tank, which is favorable. However, those not added are inferior, and the usual cyclodextrins (α, β, γ
Type) cannot obtain the performance according to the present invention.

Example 2 Exemplified compound (D-D) used in color developer No. 6 of Example 1
The same experiment as in Example 1 was conducted except that the addition amount of 2) was changed as shown in Table 2 below. Table 2 summarizes the results.

As can be seen from Table 2, the amount of the branched cyclodextrin was 0.1 g / l.
From the above, it can be seen that the desired effects of the present invention are favorably exhibited, and that the effect is more favorable at 0.5 g / l or more. When the amount exceeds 50 g / l, the effects of the present invention are sufficiently exhibited, but are not economically preferable. Further, there is a slight effect on sensitometry (decrease in maximum density) when color paper is developed. Was done. Further, when the amount exceeds 100 g / l, this tendency becomes stronger, so that the branched cyclodextrin or the cyclodextrin polymer according to the present invention is preferably in the range of 0.1 to 100 g / l, particularly preferably in the range of 0.5 to 50 g / l. It is preferably used.

Example 3 The sodium tripolyphosphate of the color developing solution No. 7 used in Example 1 was replaced with the exemplified compounds (II-2), (II-10), and (III-
1) Change to 1,1,2-dihydroxybenzene-3,4,6-trisulfonic acid sodium salt (VI-1) and (VI-2) respectively, and conduct the same experiment. It was measured by the residual amount of sodium sulfite.

As a result, those to which the compounds represented by the general formulas [II] to [VI] are respectively added, the effect of the present invention (tar or sludge generation state, crystal precipitation on the liquid surface) is good, In addition, the amount of the residual sulfite was 20 to 30% larger than that in the case where no sulfite was added (color developing solution No. 7).

Example 4 The color developing solution No. 6 used in Example 1 was replaced with an exemplified compound (VI
I-1), (VII-2), (VII-5), (VII-8), (VIII-
1), (VIII-3) and (VIII-5) were each added in an amount of 2 g / l, the storage period was doubled, and the experiment was carried out in the same manner as in Example 1 except that tar or sludge was generated. The results were even better as compared with those in which the compounds of the general formulas [VII] to [VIII] were not added.

When each of the color developing solutions after storage was allowed to stand at 2 ° C. for 3 days, no crystal precipitation of the developing agent was observed in the case where the compounds represented by the general formulas [VII] to [VIII] were added. On the other hand, when no additive was added, crystals were precipitated.

Example 5 The following layers were sequentially coated on a polyethylene-coated paper support from the support side to prepare a light-sensitive material.

The average molecular weight of polyethylene coated paper is 10
200 parts by weight of polyethylene with a density of 0,000 and a density of 0.95 and an average molecular weight
A mixture of 20 parts by weight of polyethylene having a density of 2000 and a density of 0.80 was added with 6.8% by weight of anatase-type titanium oxide, and a coating layer having a thickness of 0.035 mm was formed on the surface of a high-quality paper having a weight of 170 g / m ² by an extrusion coating method. The one provided with a coating layer having a thickness of 0.040 mm using only polyethylene was used. After performing a pretreatment by corona discharge on the polyethylene-coated surface of the support, the following layers were sequentially applied.

First layer: a blue-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 95 mol% of silver bromide, which emulsion contains 328 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. Sensitizing dye (a) As 2,5-di-t-butylhydroquinone and yellow coupler sensitized with 2.3 × 10 ^-4 mol (using isopropyl alcohol as a solvent) and dissolved and dispersed in dibutyl phthalate α- [4- (1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidyl)]-α-pivalyl-2-chloro-5- [γ- (2,4-di-
t-amylphenoxy) butyramide] acetanilide per mol of silver halide 2.2 × 10 ^-1 mol, silver amount 300mg
is applied so that the / m ^2.

Second layer: 290 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate, 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, a mixture of 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (1: 1: 1: 1) 205 mg / m ² is coated with a gelatin layer containing 2100 mg / m ² of gelatin.

Third layer: A green-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 95 mol% of silver bromide, which emulsion contains 430 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. 2,5-di-t-butylhydroquinone and magenta coupler sensitized with 2.5 × 10 ^-4 mol of sensitizing dye (b) dissolved and dispersed in a solvent consisting of dibutyl phthalate and tricresyl phosphate 3: 1 The following [M'-1] was contained in an amount of 1.6 × 10 ⁻¹ mol per mol of silver halide, and the silver amount was 300 mg / m 2.
² is applied. Here, 0.28 mol of 2,2,4-trimethyl-6-lauryloxy-7-t-octylchroman was used as an antioxidant per 1 mol of the coupler.

Fourth layer: 33 mg / m ^{2 of} di-t-octylhydroquinone dissolved and dispersed in dibutyl phthalate and 2- as an ultraviolet absorber
(2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'
-T-butylphenyl) benzotriazole, 2- (2'-
Hydroxy-3'-t-butyl-5'-methylphenyl)
Mixture of -5-chloro-benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chloro-benzotriazole (1.9: 1.5: 1.5: 2.1) 510mg / m
^This is a gelatin layer containing ² and is coated so as to be 2100 mg / m ² of gelatin.

Fifth layer: A red-sensitive silver halide emulsion layer comprising a silver chlorobromide emulsion containing 99 mol% of silver bromide, which emulsion contains 490 g of gelatin per mol of silver halide and has the following structure per mol of silver halide. 2,5-di-t-butylhydroquinone sensitized with 2.4 × 10 ^-4 mol of a sensitizing dye (c), dissolved and dispersed in dibutyl phthalate, and a cyan coupler [C′-
1] per mol of silver halide of 3.7 × 10 ^-1 mol;
It is applied so that the silver amount becomes 290 mg / m ² .

Sixth layer: This is a gelatin layer, which is coated with gelatin at 1100 mg / m ² .

The silver halide emulsions used for the respective photosensitive emulsion layers (first, third, and fifth layers) were prepared by the method described in JP-B-46-7772, and each was prepared by using sodium thiosulfate pentahydrate. Chemically sensitized, 4-hydroxy-6-methyl- as stabilizer
1,3,3a, 7-tetrazaindene (per mole of silver halide
2.5g), bis (vinylsulfonylmethyl) as hardener
Ether (10 mg / g of gelatin) and saponin as a coating aid were included.

Further, experimental samples were prepared by changing the magenta coupler and cyan coupler of the color paper sample thus prepared to the couplers shown in Table 3 below.

After exposing the color paper prepared by the above method, continuous processing was performed using the following processing steps and processing liquid.

Standard processing step (1) Color development 35 ° C 45 seconds (2) Bleaching and fixing 35 ° C 45 seconds (3) Stabilization processing 25 ° C to 35 ° C 90 seconds (4) Drying 60 ° C to 80 ° C Approx. 1 minute Processing solution composition [ Color developing tank solution] Potassium sulfite 0.3 g Potassium bromide 0.05 g Sodium chloride 2.0 g Potassium carbonate 24.0 g Exemplary compound (E-1) sulfate 5.7 g Exemplary compound (A-2) 1.0 g Diethylhydroxylamine 3.0 g Add water To 1 and pH with potassium hydroxide and 20% sulfuric acid
It shall be 10.20.

[Color developing replenisher] Potassium sulfite 0.5 g Potassium carbonate 30.0 g Diethylhydroxylamine 4.0 g Exemplified compound (E-1) Sulfate 7.5 g Exemplified compound (A-2) 2.5 g Add water to make 1; PH with 20% sulfuric acid
10.70.

[Bleaching and fixing tank solution] Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60.0 g Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Ammonia water or glacial acetic acid to pH 7.1 And adjust the total amount to 1 by adding water.

[Bleach-fix replenisher A] Ferric ammonium ethylenediaminetetraacetate dihydrate 260.0 g Potassium carbonate 42.0 g Water is added to make the total amount to 1.

The pH of this solution is adjusted using glacial acetic acid or aqueous ammonia so as to be 6.7 ± 0.1.

[Bleaching-fix replenisher B] Ammonium thiosulfate (70% solution) 500.0 ml Ammonium sulfite (40% solution) 250.0 ml Ethylenediaminetetraacetic acid 17.0 g Glacial acetic acid 85.0 ml Add water to make the total amount 1.

The pH of this solution is adjusted using glacial acetic acid or aqueous ammonia so as to be 5.3 ± 0.1.

[Washing alternative stable tank solution and replenisher] 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g ethylene glycol 1.0 g 2-octyl-4- isothiazolin-3-one 0.01 g 1-hydroxyethylidene-1,1-diphosphonic acid (60% aqueous solution) 3.0 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g of ammonia water (ammonium hydroxide 25% Aqueous solution) 2.5g Nitrilotriacetic acid / tri-sodium salt 1.5g Adjust to 1 with water and adjust to pH 7.0 with aqueous ammonia and sulfuric acid.

An automatic processor is filled with the color developing tank solution, the bleach-fixing tank solution and the stabilizing tank solution, and the color developing sample replenishing solution and the bleach-fix replenishing solution A and B are processed every three minutes while processing the color paper sample. A running test was performed while replenishing the stable replenisher with a quantitative cup. The replenishment amount is 190 ml as a replenishment amount to the color developing tank per 1 m ² of color paper, the replenishment amount to the bleach-fixing tank is 50 ml for each of the bleach-fix replenishers A and B, and the replenishment amount to the stabilization tank is a washing replenishment stable replenisher. Was supplemented with 250 ml.

The stabilizing bath of the automatic developing machine is a stabilizing bath which becomes the first to third tanks in the flow direction of the photosensitive material, and replenishment is performed from the last tank, and the overflow solution from the last tank is transferred to the preceding tank. A multi-tank countercurrent method was adopted in which the overflow liquid was allowed to flow into the tank at the preceding stage.

Discontinuous processing was performed for 20 days until the total replenishment of the color developing solution was three times the capacity of the color developing tank.

Thereafter, the treatment was stopped, the solution was stored at room temperature for one week, and the state of the tar and sludge generation in the tank solution in the color developing tank after storage was observed. Further, the dyeing condition of the turn roller portion of the color developing tank was observed. As shown in Table 2, cyclodextrin and derivatives were added to the color developing tank solution and the color developing replenisher, respectively, and the same experiment was performed.

Further, the magenta stain density of the unexposed portion of each color paper sample treated with each developer after storage was measured with a Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.).

 Table 3 below summarizes the above results.

In the table, the x mark indicates that much tar and sludge are generated,
Alternatively, it indicates that the turn roller portion is more contaminated, and the larger the number of crosses, the worse the degree. △
Indicates that there is some occurrence, and を means that the occurrence is not recognized.

Further, the 4-equivalent couplers [M'-1] and [C '
-1] to the following 4-equivalent couplers [M'-2], [M '
-3], [C'-2], and [C'-3], and similar experiments were performed. The results were almost the same as above.

From Table 3, when the cyclodextrin derivative according to the present invention is used in the color developing solution, the generation of tar and sludge during storage over time is excellently suppressed, and there is no stain (dyeing) on the turn roller portion of the color developing tank. You can see that. Further, when the two-equivalent coupler according to the present invention is used in combination, it is found that not only this effect is further improved, but also the suppression of the occurrence of magenta stain in the unexposed portion is excellent.

Example 6 In the color developer used in Example 5, the color developing agent (E-
1) was changed to the following (B-1) or (B-2), and the same experiment was carried out. As a result, the magenta tin in the unexposed portion was deteriorated by 0.02, and the generation of tar also worsened. .

Similarly, the color developing agent (E-1) of Example 1 was
When the same experiment as in Example 1 was carried out except that the exemplified compounds (E-2), (E-4) and (E-15) were respectively changed, almost the same results were obtained.

Example 7 The fluorescent whitening agent (A-2) in the color developing solution used in Experiment No. 5-4 of Example 5 was changed as shown in Table 4 below, and the number of storage days after the running treatment was changed to 10 The experiment was carried out in the same manner as in Example 5 except for days.

At that time, the occurrence of tar and the unexposed area magenta stain were measured. The results are summarized in Table 4 below.

In the table, ○ indicates that no tar was generated, and x indicates that tar was generated to such an extent that the photosensitive material was stained.

From Table 4, it can be seen that the use of the triazylstilbene-based fluorescent whitening agent represented by the general formula [X] in combination with the color developing solution or processing method of the present invention further improves the tar suppressing property and magenta stain. You can see that.

Example 8 The color developing solution (tank solution and replenisher) used in Experiment No. 7-1 of Example 7 was changed to Exemplified Compounds (I-1), (I-5) and (I-1).
The same experiment as in Example 7 was performed by adding 0.2 g / l of each of 2) and (I-13).

 The results are summarized in Table 5.

From these results, it can be seen that the use of the compound represented by the above general formula [I] in combination in the present invention improves the tar suppressing property and also improves the stain in the unexposed portion.

Example 9 The yellow coupler used in Example 5 was changed to the following [Y'-
1], [Y'-2] and [Y'-3] (4-equivalent yellow coupler), and the same experiment as in Example 5 was conducted except that the turn roller portion of the color developing tank was used. Slightly worsened.

Next, the yellow couplers are represented by the above-mentioned exemplified yellow couplers (Y-2), (Y-5), (Y-10), (Y-15),
When similar experiments were performed by changing to (Y-16) and (Y-20), almost the same results as in Example 5 were obtained.

From the above, it can be seen that the effect of the present invention is more favorably exhibited by using a 2-equivalent yellow coupler.

Claims (2)

(57) [Claims] An imagewise exposure of a silver halide photographic light-sensitive material,
Branched cyclodextrin (excluding cyclodextrin)
And / or developing in the presence of a water-soluble cyclodextrin polymer. 2. A developing solution for a silver halide photographic light-sensitive material, comprising a branched cyclodextrin (excluding cyclodextrin) and / or a water-soluble cyclodextrin polymer.