JP3379040B2 - Processing method of silver halide photographic material - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material and a development processing agent used therefor. More specifically, it is possible to obtain a high-density and low-fog image by a quick processing with a dry feeling. The present invention relates to a method for processing a silver halide photographic light-sensitive material which is also excellent in storage stability and a development processing agent used therefor.

[0002]

2. Description of the Related Art In the field of processing silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials), there is an ever-increasing demand for faster processing.

On the other hand, in order to comply with recent regulations regarding waste liquid,
In the so-called minilab, low replenishment is in progress. For this reason, the renewal rate of the processing solution tends to decrease in a minilab where the processing amount per day is small. Especially, a color developing solution having a high concentration for rapid processing is apt to undergo air oxidation, resulting in precipitation of precipitation or tar. And the deterioration of the liquid makes it difficult to maintain stable processing performance. On the other hand, Japanese Patent Application Laid-Open No. 6-324455 discloses a processing method in which a color developing solution is enclosed in a container having a good sealing property and sprayed in order to prevent air oxidation. In that case, sufficient developing characteristics cannot be obtained, and it cannot be put to practical use.

[0004]

By the way, in recent years, the number of minilab stores has increased rapidly, no waste liquid is generated, and even a person who is not accustomed to handling equipment has a dry feeling that does not make you feel that you are using the processing liquid. There is a need for a processing system that can be easily used. In addition, outdoors such as temperature changes,
There is also a demand for a system that can be stably processed in any environment.

In order to obtain processing stability, attempts have been made to keep the composition of the developer constant by directly supplying the developer to the image forming surface (also referred to as emulsion surface) of the light-sensitive material. The supply method is to supply a relatively large amount of developing solution to the emulsion surface, and not all of the supplied developing solution permeates into the light-sensitive material and liquid sagging occurs, so that the processing solution is supplied. The amount is small enough not to cause liquid sagging,
It is necessary for processing stability and a dry feeling.

In the case of color development processing, however, halide ions are eluted from the light-sensitive material as silver development progresses, and when the processing solution is small, the concentration becomes particularly high, which suppresses the progress of the development reaction and thus takes a short time. It is difficult to obtain the required density by the above process, and it is difficult to use the currently used color developing solution as it is.

It is conceivable to heat the light-sensitive material in order to accelerate the development reaction, but fog will occur if a high temperature is applied from the outside. Moreover, even if the processing liquid is heated with a small supply amount, the temperature of the photosensitive material cannot be sufficiently raised.
Further, if the processing liquid is heated, the developing agent is likely to be oxidized and tar or precipitate is generated.

The present invention has been made in view of the above circumstances, and its object is, firstly, to provide a process capable of quickly obtaining an image of high density and low fog even if a small amount of developer is supplied in a dry sense. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material which is possible and does not cause the problem of precipitation of a processing solution. Secondly, it is to provide a processing method of a silver halide photographic light-sensitive material capable of performing stable and rapid processing regardless of the processing amount even if the processing amount is small.

[0009]

SUMMARY OF THE INVENTION The above object of the present invention, developing processing solution is from at least two pH7 following concentrates and pH8 more concentrated solution, the pH7 following liquid and p
Both H8 and above solutions can be used as a silver halide photographic material through space.
The processing method of the silver halide photographic light-sensitive material supplied to the image forming surface of the optical material, the supply amount of the liquid having a pH of 7 or less and the liquid having a pH of 8 or more are respectively 1 m ^{2 of the} silver halide photographic light-sensitive material.
5 to 150 ml per pH, the solution having a pH of 7 or less contains 0.005 to 1.00 mol / l of a color developing agent, and the solution having a pH of 8 or more contains 0.1 to 0.1 alkali agent.
3.5 mol / l which contains the pH7 following liquid to be supplied to the image forming surface of the wafer androgenic halide photographic material and p
The volume ratio of the solutions of H8 or more is within 100 times that of the other solution, and the first solution of the developing treatment solution is supplied to the image forming surface of the silver halide photographic light-sensitive material. From the time when the photosensitive material reaches the next processing step is 5 to 4
It is 5 seconds, is achieved from two.

That is, the present inventor separates the developing treatment liquid into a concentrated liquid having a low pH and a concentrated liquid having a high pH, and supplies the respective liquids to the image forming surface of the light-sensitive material while controlling the amounts thereof. The present invention was devised to accelerate the development reaction by utilizing the heat of neutralization generated by directly mixing both solutions on the image forming surface of the light-sensitive material and / or in the photographic constituent layers. When the processing solution for development is for color development for color light-sensitive materials, it contains 0.005-1.0 color developing agent in a low pH solution.
It is effective to add a concentration of 0 mol / l to increase the concentration, and to add an alkaline agent to the high pH solution in a concentration of 0.1 to 3.5 mol / l to increase the concentration and the pH.

In JP-A-2-203338, a color developing solution is divided into a low pH solution containing a color developing agent and a high pH solution containing an alkaline agent. It is described that the treatment of color paper is speeded up by improving the permeability of the color developing agent by immersing in a liquid or applying the liquid with a roller. However, in this method, after the color developing agent is supplied, the alkali agent is supplied after a while, so that the initiation of the development reaction is delayed and the effect of promoting development is insufficient.

The present invention will be described in detail below item by item.

[Silver Halide Photosensitive Material] Examples of the photosensitive material processed by the method and the processing agent of the present invention include a silver halide color photographic photosensitive material containing a silver chloride emulsion,
Examples thereof include silver halide color photographic light-sensitive materials containing silver iodobromide or silver bromide emulsion. These light-sensitive materials generally include a light-sensitive emulsion layer such as a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a resin- or paper-based support. A photographic constituent layer comprising a hydrophilic colloid layer such as an antihalation layer, an intermediate layer, a filter layer and a protective layer is provided. The processing agent of the present invention functions by being directly mixed on and / or in these photographic constituent layers.

[Supply of Treatment Liquid] In the present invention, the pH is 7
At least one of the following concentrated liquids and concentrated liquids having a pH of 8 or more is preferably supplied through a space. Through the space here is not a form in which the photosensitive material is completely immersed in the bath of the processing liquid like the processing in a normal automatic developing machine, but the processing liquid is allowed to fly to the image forming surface of the photosensitive material, It refers to applying the treatment liquid using a curtain coater or sponge.

As a concrete processing liquid supplying means, a processing liquid flying means for flying the processing liquid onto the photosensitive material through the space, or a processing for applying the processing liquid onto the photosensitive material through the space like a curtain coater. Liquid application means and the like can be mentioned. As the processing liquid flying means for flying the processing liquid to the light-sensitive material through the space, a processing liquid having a structure similar to that of the inkjet head portion of an inkjet printer, a structure described in JP-A-6-324455, or the like is used. A liquid is applied to the photosensitive material through a space to generate a pressure in the post-processing flying means to actively fly, or a liquid such as a spray bar that is applied to the post-processing flying means through the space to the photosensitive material. The thing which makes it fly by pressure is mentioned. As a processing liquid flying means for flying a processing liquid having a structure similar to that of the inkjet head portion of an inkjet printer to a photosensitive material through a space, a processing liquid is supplied by vibration or a processing liquid is supplied by bumping. And the like, and it is preferable because the processing liquid supply amount can be controlled and the processing position of the photosensitive material can be selected.

The amount of the liquid supplied through the space may be increased or decreased depending on the supply position. Further, it is preferable that both the concentrated liquid having a pH of 7 or less and the concentrated liquid having a pH of 8 or more are supplied through a space.

As the processing liquid supply means, even if the processing liquid is supplied from the linear supply head to the photosensitive material through the space, the processing liquid is supplied from the planar supply head to the photosensitive material through the space. Alternatively, the processing liquid may be supplied from the dot-shaped supply head to the photosensitive material through a space, or any other method may be used. If the photosensitive material is a sheet, a planar supply head corresponding to the size of the photosensitive material is used to expose the processing liquid from the supply head while the positional relationship between the photosensitive material and the supply head is fixed. The material may be supplied through a space, but it is preferable to supply the processing liquid from the supply head to the photosensitive material through the space while shifting the positional relationship between the supply head and the photosensitive material, even if the supply head is small. It is preferable because the processing solution can be sufficiently supplied to the light-sensitive material. When a linear supply head is used, the supply head may move, but in order to rapidly supply the processing liquid to the photosensitive material, a linear supply head is used instead of the linear supply head. It is preferable to move the photosensitive material in a direction other than the parallel direction. In particular, in order to keep the processing time constant, it is preferable to move the photosensitive material in the direction perpendicular to the linear supply head.

The supply amount in the present invention is the amount of the processing solution directly supplied to the emulsion surface when passing through a space, and when the processing solution is supplied by immersing the light-sensitive material, the replenisher is replenished. Refers to quantity. The solution containing at least a color developing agent is preferably supplied directly to the emulsion surface of the light-sensitive material.

[Development Processing Step] In the present invention, the development processing solution refers to all solutions containing a compound capable of contributing to the development reaction of the light-sensitive material, such as a color developing agent and an alkali agent. For example, an aqueous solution containing a surfactant, a solubilizing agent for a color developing agent, a preservative, and the like are included. In the present invention, at least two treatment liquids of a concentrated liquid having a pH of 7 or less and a concentrated liquid having a pH of 8 or more are used.
It is preferable that the pH is not more than 10 and not less than 10.

In the development processing step of the present invention, from the supply of the first developing solution to the light-sensitive material to the supply of the processing solution of the next step (for example, bleach-fix solution, bleach solution, stop solution, etc.). ,
Alternatively, it refers to the process up to immersion in the treatment liquid of the next step. The time for passing through the development processing step is the time from the supply of the developing solution to the photosensitive material until the supply of the processing solution of the next step or the immersion of the processing solution of the next step. 5
It is about 45 seconds, preferably 5 to 20 seconds.

The ratio of the supply amount of the liquid having a pH of 7 or less to that of the liquid having a pH of 8 or more is preferably 100 times or less than that of the other, more preferably 10 times or less, and further preferably 2 times or less. is there. Photosensitive material 1
About ^{5 to} 150 ml, preferably 10 to 10 per m ^2.
0 ml, and further 10 to 50 ml, and the total supply amount of all processing solutions is about 10 to 300 ml per 1 m ² of the light-sensitive material,
It is preferably 10 to 100 ml, more preferably 20 to 60 ml.

The time during which the processing solution for development is entirely supplied onto the image forming surface (hereinafter also referred to as the emulsion surface) of the light-sensitive material is within 2/3 of the initial time of passing through the developing step, preferably 1/3. It is preferably within 1/10.

The supply of the developing treatment liquid is preferably proportional to the amount of exposure of the photosensitive material, but it need not be proportional. Further, in the case of a color photographic light-sensitive material, the following examples are preferably given as the supply order of each partial liquid.

(1) Color developing agent-containing solution → alkali agent containing solution (2) Color developing agent-containing solution → alkali agent and color developing agent-containing solution (3) Water → Color developing agent-containing solution → Alkaline agent-containing solution (4 ) Water-> liquid containing color developing agent-> liquid containing alkaline agent and color developing agent (5) Liquid containing alkaline agent-> liquid containing color developing agent (6) Liquid containing alkaline agent and color developing agent-> liquid containing color developing agent (7) Water → Alkaline agent-containing solution → Color developing agent-containing solution (8) Water → Alkali agent and color developing agent-containing solution → Color developing agent-containing solution Preferred examples among these (1), (2), (3),
(4) is mentioned, and more preferably (1) and (3).

The color developing agent is preferably a p-phenylenediamine compound having a water-soluble group. Wherein the water-soluble group, p- least one there things listed phenylenediamine amino group of the compound or benzene supranuclear As specific water-soluble group _{- (CH 2) n -CH 2} O
_{H, - (CH 2) m} -NHSO 2 - (CH 2) n CH 3, -
_{(CH 2) m -O- (CH} 2) n -CH 3, - (CH 2 CH 2
O) _n C _m H _{2m + 1} , (m and n each represent an integer of 0 or more.) —COOH group, —SO ₃ H group and the like are preferable.

Examples of specific compounds preferably used in such a color developing agent include the following (C-1) to (C-
18).

[0027]

[Chemical 1]

[0028]

[Chemical 2]

[0029]

[Chemical 3]

Of these compounds, preferred ones are (C
-1), (C-2), (C-3), (C-4), (C-
15), (C-17) and (C-18).

Other color developing agents preferably used are para-phenylenediamine type color developing agents having a water-soluble group represented by the following general formula [P].

[0032]

[Chemical 4]

(In the general formula [P], R ₁ and R ₂ represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an acylamino group. R ₃ represents an alkyl group and R ₄ represents an alkylene group. R ₅ represents a substituted or unsubstituted alkyl group or aryl group.) Examples of these specific compounds include the following compounds (C
-19) to (C-35). These compounds are shown by showing the concrete group of R < ₁ > -R < ₅ > of General formula [P].

[0034]

[Chemical 5]

Of the above-exemplified compounds, (C-
20), (C-27), (C-29), (C-30),
(C-33), and most preferably (C-1) among all the exemplified compounds. The compound of the general formula [P] can be synthesized according to the method described in JP-A-4-37198. The above color developing agents are usually hydrochlorides, sulfates, p
-Used in the form of salts such as toluene sulfonate.

The color developing agents may be used singly or in combination of two or more kinds, and may be optionally used in combination with a black and white developing agent such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone or methol. You may use it.

The concentration of the main agent in the liquid containing the para-phenylenediamine color developing agent is 0.005 to 1.00 mol /
It is about l, preferably 0.01 to 0.25 mol / l, and more preferably 0.06 to 0.13 mol / l. The concentration is 0.0
When it is 5 mol / l or more, the pH of the liquid is preferably 4 or less, more preferably pH 2 or less from the viewpoint of solubility of the main drug. Further, when the concentration is 0.25 mol / l or more, the pH is preferably 2 or less.

The inclusion of the compound represented by the following general formula [H] or [B] in the processing solution for color development has the advantage that it is stable in photographic performance and causes less fog in unexposed areas.

[0039]

[Chemical 6]

In the general formula [H], R ₆ and R ₇ are not a hydrogen atom at the same time, respectively, an alkyl group, an aryl group,
R'-CO- represents a group or a hydrogen atom, an alkyl group represented by R ₆ and R ₇ may be the same or different, preferably an alkyl group having 1 to 3 carbon atoms, respectively. Further, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group. R'represents an alkoxy group, an alkyl group or an aryl group. The alkyl group and aryl group of R ₆ , R ₇ and R ′ include those having a substituent, and
R ₆ and R ₇ may be combined to form a ring, for example, a heterocycle such as piperidine, pyridine, triazine or morpholine.

[0041]

[Chemical 7]

In the general formula [B], R ₈ , R ₉ and R ₁₀ represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group or a heterocyclic group, and R ₁₁ represents a hydroxy group or a hydroxyamino group. Represents a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group. The heterocyclic group is a 5- or 6-membered ring, is composed of C, H, O, N, S and a halogen atom and may be saturated or unsaturated. R ₁₂ is -CO -, - SO ₂ - or -C (= NH) - represents a divalent group selected from, n is 0 or 1. Particularly when n = 0, R ₁₁ represents a group selected from an alkyl group, an aryl group and a heterocyclic group, and R ₁₀ and R ₁₁ may together form a heterocyclic group.

Among the compounds represented by the general formula [H], the compounds represented by the following general formula [D] are particularly preferable.

[0044]

[Chemical 8]

(In the general formula [D], L represents an alkylene group, A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, an amino group, an ammonio group, a carbamoyl group or a sulfamoyl group, R represents a hydrogen atom or an alkyl group, and L, A, and R each include a straight chain and a branched chain, and may be unsubstituted or substituted. Good) The compound represented by the general formula [D] will be described in more detail. In the formula, L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene, and propylene are mentioned as preferable examples.
Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group and an ammonio group which may be alkyl-substituted, and a carboxyl group, a sulfo group, a phosphono group and a hydroxyl group are preferred examples. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an alkyl-substituted amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, which is a carboxyl group, a sulfo group, a hydroxyl group, or a phosphono group. A group and a carbamoyl group which may be alkyl-substituted are preferred examples.
Examples of -LA include carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group,
A phosphonoethyl group and a hydroxyethyl group can be mentioned as preferable examples, and a carboxymethyl group, a carboxyethyl group, a sulfoethyl group, a sulfopropyl group, a phosphonomethyl group, and a phosphonoethyl group can be mentioned as a particularly preferable example. R is a hydrogen atom, having 1 to 10 carbon atoms
Represents a linear or branched alkyl group which may be substituted,
It preferably has 1 to 5 carbon atoms. The substituent represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group which may be substituted with an alkyl group, an ammonio group, a carbamoyl group or a sulfamoyl group. There may be two or more substituents. R as a hydrogen atom, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group,
Sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group can be mentioned as a preferred example, hydrogen atom, carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group is mentioned as a particularly preferred example. be able to. L and R may combine to form a ring.

Typical examples of the compounds represented by the general formula [D] are shown below, but the present invention is not limited to these compounds.

[0047]

[Chemical 9]

[0048]

[Chemical 10]

[0049]

[Chemical 11]

[0050]

[Chemical 12]

The compounds represented by the general formula [H] or the general formula [B] are usually free amines, hydrochlorides, sulfates,
It is used in the form of p-toluenesulfonate, oxalate, phosphate, acetate and the like.

Sulfite can be used as a preservative in the color developing treatment liquid. As the sulfite, sodium sulfite, potassium sulfite, sodium bisulfite,
Examples include potassium bisulfite and the like. It is desirable that the sulfite be contained in the same partial liquid as the color developing agent, but this is not necessary. Sulfite concentration is 1 × 10 ^{-4 to} 5 × 10
^-2 mol / l is preferred.

A buffer may be used in the processing solution for color development, and examples of the buffer include potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate and phosphoric acid. Dipotassium, sodium borate, potassium borate, sodium tetraborate (borate), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5-sulfo-2-hydroxy Sodium benzoate (sodium 5-sulfosalicylate),
Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate) is preferred.

An alkaline agent is used in the processing solution for color development, and examples of the alkaline agent include lithium hydroxide, sodium hydroxide and potassium hydroxide in addition to the above-mentioned buffering agent. The concentration of the alkaline agent is about 0.1 to 3.5 mol / l,
It is preferably 0.3 to 1.2 mol / l. When the alkaline agent does not dissolve so much due to the influence of temperature or other solutes, it is preferable to use it within the range of the amount that can dissolve it.

A development accelerator can be used in the processing solution for color development, and as the development accelerator, a thioether compound, a p-phenylenediamine compound, a quaternary ammonium salt, a p-aminophenol compound, an amine compound can be used. Compound,
If necessary, polyalkylene oxide, 1-phenyl-3-pyrazolidones, hydrozines, mesoionic compounds, ionic compounds, imidazoles, etc. can be added.

The processing solution for color development preferably contains substantially no benzyl alcohol.

Chlorine ions and bromine ions can be added to the processing solution for color development for the purpose of preventing fog and the like. When added directly to the color developing solution, chloride ion supplying substances include sodium, potassium, ammonium, nickel, magnesium, manganese, calcium or cadmium chlorides, of which sodium chloride and potassium chloride are preferred. . It may also be supplied in the form of a salt against the fluorescent whitening agent added to the color developing solution. Examples of the bromide ion supplying substance include bromide of sodium, potassium, ammonium, lithium, calcium, magnesium, manganese, nickel, cadmium, cerium or thallium, of which potassium bromide and sodium bromide are preferable. The content of these halogen ions is at most 0.02 mol / l, preferably 0.001 mol / l or less, but it is most preferable that they are not substantially contained.

The processing solution for color development preferably contains a triazinyl stilbene type fluorescent whitening agent, and specifically, a compound represented by the following general formula [E] is preferable.

[0059]

[Chemical 13]

In the above formula, X ₂ , X ₃ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group,

[0061]

[Chemical 14]

Alternatively, it represents --OR ₁₇ . Where R ₁₃ and R ₁₄
Each represents a hydrogen atom, an alkyl group (including a substituent), or an aryl group (including a substituent), R ₁₅ and R ₁₆ represent an alkylene group (including a substituent), and R ₁₇ represents a hydrogen atom, an alkyl group ( (Including a substituent) or an aryl group (including a substituent), and M represents a cation.

Furthermore, various other additives such as stain inhibitors, sludge inhibitors, and stacking effect accelerators can be used.

Further, it is preferable to add a chelating agent represented by the following general formulas [KI] to [KV] to the processing solution for color development.

[0065]

[Chemical 15]

[0066]

[Chemical 16]

[0067]

[Chemical 17]

[0068]

[Chemical 18]

[0069]

[Chemical 19]

[0070]

[Chemical 20]

[0071]

[Chemical 21]

[0072]

[Chemical formula 22]

[0073]

[Chemical formula 23]

Among these chelating agents, especially K
-I-2, K-II-1, K-II-5, K-III-10,
K-IV-1 and K-V-1 are preferably used.

Further, an anion is contained in the processing solution for color development,
Cationic, amphoteric, and nonionic surfactants can be contained, and if necessary, various surfactants such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid can be added. Good.

[Bleaching Treatment] At least 1 is contained in the bleaching treatment liquid.
It is preferable to contain a ferric aminopolycarboxylic acid ferric complex / hydrate. Two or more different ferric aminopolycarboxylic acid complexes / hydrates may be mixed and used.

The ferric aminopolycarboxylic acid complex is preferably used in the form of an iron complex of the following free acid of aminopolycarboxylic acid (compound represented by the following general formula [I]). It is more preferable to use a diiron complex and a free acid of aminopolycarboxylic acid in combination. Particularly preferably, the ferric complex is used in combination with the free acid of the same kind of aminopolycarboxylic acid that constitutes the ferric complex. The ferric aminopolycarboxylic acid complex / hydrate can be used as a potassium salt, a sodium salt, an ammonium salt, and the free acid of the aminopolycarboxylic acid is a free acid, a potassium salt, a sodium salt, or the like. Can be used.

[0078]

[Chemical formula 24]

R _{25 to} R ₂₉ are a hydrogen atom, a hydroxy group,
Represents a carboxy group, a sulfo group, a carbamoyl group, a phosphono group, a phosphone group, a sulfamoyl group, a sulfone acid group, an acylamino group, a hydroxam group, and R _{25 to} R
_At least one of the ₂₉ is a carboxy group.

L _{1 to} L ₇ represent an alkylene group which may be substituted or unsubstituted, an arylene group, an alkenylene group, a cycloalkylene group or an aralkylene group. l
₁ to l ₇ represents an integer of 0 to 6. However, l ₅ ~l ₆ is not equal to 0 at the same time.

Specific examples of the aminopolycarboxylic acid (exemplary compound I) represented by the general formula [I] which constitutes the ferric aminopolycarboxylic acid complex / hydrate are shown below.

[0082]

[Chemical 25]

[0083]

[Chemical formula 26]

[0084]

[Chemical 27]

[0085]

[Chemical 28]

Preferred compounds include (I-1) to
(I-8), (I-12), (I-14) to (I-2
0), (I-22), (I-23) and (I-27), and particularly preferred compounds include (I-1),
(I-2), (I-3), (I-6), (I-12),
(I-14), (I-15) and (I-17) can be mentioned.

Specific exemplified compounds of the ferric aminopolycarboxylic acid complex / hydrate (Exemplified Compound IIs) are shown below.

[0088]

[Chemical 29]

Further, the bleaching treatment liquid preferably contains an organic acid compound represented by the following general formula [A].

[0090] Formula (A) A '(- _{COOM) n} wherein, A' is an organic radical of valency n, n is an integer of 1 to 6, M is ammonium, alkali metal (sodium,
Potassium, lithium, etc.) or a hydrogen atom.

In the general formula [A], n represented by A '
Examples of the valent organic group include an alkylene group (methylene group, ethylene group, trimethylene group, tetramethylene group, etc.), alkenylene group (ethenylene group, etc.), alkynylene group (ethynylene group, etc.), cycloalkylene group (1,4-cyclohexane). Diyl group, etc.), arylene group (o-phenylene group, p-phenylene group, etc.), alkanetriyl group (1,
2,3-propanetriyl group) and arenetriyl group (1,2,4-benzenetriyl group).

The n-valent group represented by A'includes those having a substituent (hydroxy group, alkyl group, halogen atom, etc.) (1,2-dihydroxyethylene, hydroxyethylene, 2-hydroxy-group). 1,2,3-propanetriyl, methyl-p-phenylene, 1-hydroxy-2-chloroethylene, chloromethylene, chloroethenylene, etc.). Preferred specific examples of the compound represented by formula [A] are shown below.

[0093]

[Chemical 30]

[0094]

[Chemical 31]

Among the above exemplified compounds, particularly preferable are the exemplified compounds (A-1), (A-3), (A-4),
(A-5), (A-6), (A-13), (A-1
4), (A-15) and (A-20), and particularly preferred are (A-1), (A-5), (A-6) and
(A-13), (A-14), and (A-20).
Examples of the acid salt include ammonium salt, lithium salt, sodium salt, potassium salt and the like, and sodium salt and potassium salt are preferable from the viewpoint of storage stability. These organic acids or salts thereof can be used alone or in combination of two or more kinds.

Further, the bleaching treatment liquid may contain a rehalogenating agent. Known rehalogenating agents can be used, for example, ammonium bromide, potassium bromide, sodium bromide, potassium chloride, sodium chloride,
Examples thereof include compounds such as ammonium chloride, potassium iodide, sodium iodide and ammonium iodide.

[0097]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 FIG. 1 is a schematic configuration diagram of a main part of an automatic processor (hereinafter, also referred to as an automatic processor) used here. FIG. 2 is a perspective view of the main part of this automatic processor. FIG. 3 is a perspective view of the vicinity of the supply port drying preventing means of this automatic developing machine.

[Apparatus] As a conveying means for conveying the silver halide photographic light-sensitive material P at a predetermined conveying speed, in addition to a conveying roller (not shown), a heating drum 11, a pressure belt 15, a heating belt 33, and a bleach-fixing processing tank and after. There are transport rollers. Then, the photosensitive material detecting means 70 for detecting the presence of the photosensitive material P is provided at a predetermined position on the upstream side in the transport direction of the transport means with respect to the destination where the processing liquid supply means 52 supplies the processing liquid.
The heating means 10 for heating the silver halide photographic light-sensitive material P is located downstream of the light-sensitive material P conveyance path of the light-sensitive material detection means 70. The heating means 10 has a heating drum 11. Further, there is an outlet side roller 12 on the upper side of the heating drum 11. On the left side of the heating drum 11, there is an inlet side roller 13. On the left side of the outlet side roller 12 and above the inlet side roller 13, there is a pressure belt drive roller 14. Crimping belt 15
Are laid over the outlet side roller 12, the inlet side roller 13 and the pressure-bonding belt drive roller 14, and move while being pressure-bonded to the heating drum 11 over a 90 ° section of the peripheral surface of the heating drum 11. Then, the photosensitive material P is pressure-bonded and conveyed. With these, the photosensitive material P is heated.

Development processing means 50 is provided downstream of the conveying path for the photosensitive material P on the heating drum 11. The developing processing means 50 has a first processing liquid container 51 and a second processing liquid container 56 as a processing liquid container for containing a processing liquid (processing liquid for color development) for processing the photosensitive material P. The first processing liquid container 51 and the second processing liquid container 56 are sealed from the outside air. A supply head described later is used as the processing liquid supply means 52 in this embodiment. As a result, the processing liquid supply means 52 supplies the processing liquid (color development processing liquid) to the emulsion surface of the photosensitive material P heated by the heating means 10 through the space. A circulation pump 54 is provided above the first processing liquid container 51 and to the left of the second processing liquid container 56, and a filter 55 is provided on the partition wall between the first processing liquid container 51 and the second processing liquid container 56. By operating the circulation pump 54, the processing solution for color development is circulated in the order from the first processing solution container 51 to the circulation pump 54, the second processing solution container 56, and the filter 55 in the direction indicated by the arrow in FIG. Further, the rotor 57 rotates in the second processing liquid container 56 to stir the processing liquid in the second processing liquid container 56.

As a result, a filter means (filter 55) is provided between the second processing liquid container 56 and the processing liquid supply means 52 for filtering the processing liquid from the second processing liquid container 56. Further, the replenisher is supplied from the replenisher supplying means 59 to the second processing liquid container 56.

The processing liquid supply means 52 is provided with a first shutter 62 and a second shutter 64 which stop the supply of the processing liquid to the supply head in the middle of the width of the photosensitive material P. The first shutter 62 is driven by the first shutter drive unit 61 so as to be freely inserted into and removed from the supply path of the processing liquid to the supply head, and the second shutter 64 is driven by the second shutter drive section 63 to the supply path of the processing liquid to the supply head. It is driven so that it can be inserted and removed freely. FIG. 2 shows a state in which the second shutter 64 is inserted in the processing liquid supply path to the supply head.

Below the processing liquid supply means 52, in order to prevent the processing liquid in the supply port of the supply head of the processing liquid supply means 52 from being dried, the supply of the supply head is performed when the processing liquid is not supplied to the photosensitive material P. There is a supply port drying prevention means 80 for covering the mouth. The supply port dry prevention unit 80 includes a movable lid 81, a support rod 82 that supports the movable lid 81, and a motor 83 that moves the support rod 82 up and down. The support rod 82 is vertically driven by the motor 83 by providing a rack on the support rod 82 and a pinion on the motor 83. The movable lid 81 has a concave cross section, and as will be described later, the processing liquid supply means 52 supplies the processing liquid periodically even in the standby operation state in which the photosensitive material P is not processed, but at this time, it is slightly movable. The lid 81 moves downward, receives the treatment liquid supplied from the treatment liquid supply means 52, and discharges the treatment liquid to a waste liquid portion through a hole (not shown) provided in the support rod 82, whereby the treatment liquid is discharged. Prevents surrounding devices from getting dirty.

There is the second heating means 30 for heating the photosensitive material P on the downstream side of the conveyance path of the photosensitive material P where the processing liquid is supplied through the space by the processing liquid supply means 52. The second heating means 30 includes a heating roller 31, a driving roller 32, and a heating belt 33. The heating belt 33 is stretched around the heating roller 31 and the driving roller 32. Heating roller 31
Is on the downstream side of the conveyance path of the photosensitive material P to which the processing liquid is supplied through the space by the processing liquid supply means 52, and heats the heating belt 33. Photosensitive material P from heating roller 31
The driving roller 32 on the downstream side of the conveyance path of the heating belt 3 is
3 is driven. As a result, the photosensitive material P is heated while the heating belt 33 is heated. Then, the silver halide photographic light-sensitive material, to which the processing liquid is supplied to the emulsion surface through the space by the processing liquid supply means 52, is heated by the second heating means 30.
Will be heated.

Thereafter, the light-sensitive material P, which has been subjected to color development processing by the development processing means 50, is bleach-fixed in the bleach-fixing processing solution tank BF, and stabilized in the stabilization processing tank ST.

FIG. 4 shows a schematic configuration diagram of a main part of an automatic developing machine having two developing processing means 50. In this embodiment, processing method 1 is a case where processing is performed using the automatic developing machine shown in FIG. 1, and processing method 2 is a case where processing is performed using the automatic developing machine shown in FIG.

FIG. 5 is a schematic view of a processing tank portion of an automatic developing machine for immersion development which can supply two kinds of processing solutions for color developing. After being exposed, the photosensitive material P is conveyed by a plurality of pairs of feed rollers and first processed in the development processing tank CD1. After that, color development processing tank CD2, bleach-fixing processing tank BF, stabilization tank S
The particles are sequentially transferred to TB by a roller transfer unit and processed. The photosensitive material P which has been subjected to each of these processes is dried in the drying section and discharged outside the machine. The processing using this automatic processor is referred to as processing method 3.

In FIG. 6, after the partial solution of the color developing processing solution is supplied to the photosensitive material P through the space by the processing solution supply means CD1, the photosensitive material P is dipped in the processing solution in the processing bath CD2 to change the other. It is a schematic diagram of an automatic developing machine of the type that supplies a partial liquid. After the color development processing, the light-sensitive material P is subjected to bleach-fixing processing and stabilization processing, dried, and then discharged outside the machine. The processing using this automatic processor is referred to as processing method 4.

FIG. 7 is a schematic view of an automatic developing machine capable of supplying two types of color developing treatment liquids and then supplying them to the emulsion surface of the light-sensitive material P through a space. The processing using this automatic processor is referred to as processing method 5.

[Processing Liquid Supplying Means] A linear supplying head is used as the processing liquid supplying means of the automatic developing machines shown in FIGS. The linear supply head is perpendicular to the conveyance direction of the photosensitive material P. The array of supply ports is a two-row staggered array.
The distance between the supply ports is 100 μm, which is the distance between the edge and the nearest supply port.
Is. Diameter of supply port 100μm (Area 7.85 × 10
^-9 m ² ), the number of times the processing solution is supplied per second is 5000 times, and the processing solution supply amount per 1 m ^{2 of the} silver halide photographic light-sensitive material is 50 ml in the processing methods 1 and 5 and 25 ml in the processing methods 2 and 4.
Is.

[Photosensitive Material] Konica QA-A6 paper exposed by a conventional method is processed.

[Treatment liquid formulation: per liter] << Color developer-1 >> Sodium sulfite 0.2 g Bis (sulfoethyl) hydroxylamine disodium 12.0 g Diethylenetriamine pentaacetic acid 5 sodium 3.0 g Polyethylene glycol # 4000 8.0 g Carbonic acid Potassium 45.0 g Sodium p-toluenesulfonate 15.0 g 4-Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) aniline sulfate (CD-3) 10.0 g Hydroxylated Adjust the pH to 10.0 with potassium or sulfuric acid.

<Color developer-2> Partial liquid A Sodium sulfite 0.4 g Diethylenetriamine pentaacetic acid 5 sodium 3.0 g Polyethylene glycol # 4000 6.0 g Sodium p-toluenesulfonate 30.0 g CD-3 40.0 g Hydroxylation Adjust to the pH given in the table with potassium or sulfuric acid.

Partial liquid B Diethylenetriamine pentaacetic acid 5 sodium 3.0 g Polyethylene glycol # 4000 10.0 g Potassium carbonate 90.0 g Adjust to the pH shown in the table with potassium hydroxide or sulfuric acid.

<< Bleaching, Fixing and Stabilizing Process >> Konica Corporation: CPK-2-J1 process was carried out using the same process treating agent under the treating conditions.

Color papers were processed at a rate of 10 m ² per day for 3 consecutive weeks using the automatic processors shown in FIGS. 1, 4, 5, 6, and 7. In the processing method 1, the color developing solution-1 was used and the color developing processing time was 10 seconds. Color developer-1 was used as a replenisher. The color developing solution-2 was used for the processing methods 2 and 5, and the processing was carried out at a color developing processing time of 10 seconds. As the replenishing solution, the partial solutions A and B were used as they were. In treatment method 2, the partial liquid A and the partial liquid B were supplied in this order at a supply interval of 0.3 seconds.

<< Processing Conditions of Color Developing Step of Processing Method 3 >> Processing Solution Supply Means Used Solution Processing Time Processing Temperature Supply Amount (sec) (° C.) (ml / m ² ) CD1 Color Developing Solution-2 Partial Solution A 5 39 .25 25 (pH 1.5) CD2 color developer-2 partial solution B 5 39.5 25 (pH 13.0) KCl 3.7 g / l addition The processing time here is that the photosensitive material is immersed in the processing solution. It is the time from the immersion to the next processing liquid.

<< Processing Conditions of Color Development Step of Processing Method 4 >> Processing Solution Supply Means Used Solution Processing Time Processing Temperature Supply Volume (sec) (° C.) (ml / m ² ) CD1 Color Development Solution-2 Partial Solution A-- 25 (pH 1.5) CD2 color developer-2 partial solution B 5 39.5 25 (pH 13.0) KCl 3.7 g / l Color developer-2 from the processing solution supply means CD1
Five seconds after the partial liquid A was supplied, it was immersed in the treatment bath CD2.

<< Replenisher used in CD1 and CD2 of Treatment Method 3 and CD2 of Treatment Method 4 >> Replenisher for Partial Liquid A ~ 1 liter Sodium sulfite 0.6 g Diethylenetriamine pentaacetic acid 5 sodium 4.3 g Polyethylene glycol # 4000 8 0.6 g Sodium paratoluene sulfonate 42.9 g CD-3 64.0 g Replenisher for partial solution B-5 g sodium diethylenetriamine pentaacetate per liter 4.3 g Polyethylene glycol # 4000 14.3 g Potassium carbonate 129.0 g At the start of continuous treatment, After 1 week, 2 weeks, and 3 weeks, the sample was treated, and the spectral reflection densities D _min (Y) (440 nm) and D _min (C) (6) of the unexposed portion at 440 nm and 660 nm were processed.
60 nm) and the maximum blue reflection density D _max (Y) (440
nm) was measured.

Further, the partial solutions A and B of the color developer-2 were stored in the processing container or the processing tank at room temperature for 2 weeks, and the container and the tank after the storage were observed and evaluated according to the following criteria. .

⊚: No precipitate is observed at all ◯: Turbidity of the liquid is confirmed, but precipitate is not observed Δ: Precipitate is slightly confirmed on the liquid surface, but there is no problem × : A considerable amount of precipitate is seen.

Further, in the processing method 2, a color developing solution-
The same evaluation was performed by changing the pH values of the partial liquids A and B of No. 2 as shown in Table 1.

The above results are shown in Table 1.

[0124]

[Table 1]

In the treatment method 5, the treatment liquid supply means was clogged on the second day of the continuous treatment, so that the continuous treatment was stopped.

From Table 1, it is possible to obtain a sufficient concentration, suppress fog to a low level, and prevent the formation of precipitates by supplying a liquid having a pH of 7 or less and a liquid having a pH of 8 or more to the sample and mixing them directly. I understand. It is also found that the effect of the present invention is fully exhibited when the pH of the liquid containing the color developing agent is 4 or less.

Furthermore, stable continuous processing can be performed by supplying at least one of the two concentrated solutions to the light-sensitive material through a space, and the method in which both are through a space improves the storage stability of the processing solution, which is preferable. I understand.

Example 2 Regarding the treatment method 2, the amount of supply was changed as shown in Table 2, and the samples treated at the start of the continuous treatment in the same manner as in Example 1 were treated.
The maximum blue reflection density D _max (Y) (440 nm) and the spectral reflection density D _min (Y) of 440 nm of the unexposed portion and 660
The spectral reflection density D _min (C) of nm was measured. The results are shown in Table 2.

[0129]

[Table 2]

From this, it can be seen that when the supply amount of each liquid to the light-sensitive material is 5 to 150 ml / m ² , the required concentration can be obtained and fog can be suppressed to a low level.

Example 3 In the processing method 2, the concentration of the color developing agent in the partial liquid A of the color developing solution-2 was changed as shown in Table 3, and the pH of the partial liquid B was changed.
Was set to 13.0, and the maximum blue reflection density D _max (Y) (44) of the sample at the start of continuous processing which was processed in the same manner as in Example 1
0 nm) and the spectral reflection density D of the unexposed part at 660 nm
_{The min} (C) was measured. Further, the partial liquid A was stored at −5 ° C. while being enclosed in the treatment container, and the container was observed after 3, 10, 20, and 30 days, and the low temperature precipitation property was evaluated according to the following criteria. The results are shown in Table 3.

⊚: No precipitate is confirmed even after 30 days ◯: A deposit was confirmed after 20 days Δ: A deposit was confirmed after 10 days X: A precipitate was confirmed after 3 days.

[0133]

[Table 3]

As a result, the pH of the partial liquid A of the color developing solution-2 is set to 7 or less, and the concentration of the color developing agent is 0.005 to 0.005.
It can be seen that when the amount is 1.00 mol / l, the required concentration can be obtained, the fog is small, and the problem of precipitation does not occur even when stored at low temperature.

Example 4 The concentrations of the color developing agent and potassium carbonate and the supply amounts of the respective solutions in the color developing solution-2 were changed as shown in Table 4, and the pHs of the partial liquid A and the partial liquid B were set to 1.5, respectively. And 13.0
The maximum blue reflection density D _max (Y) of the sample at the start of continuous processing which was processed in the same manner as in Example 1 except that
(440 nm) and the spectral reflection density D _min (Y) of 440 nm and the spectral reflection density D _min (C) of 660 nm of the unexposed portion.
Was measured.

The results are shown in Table 4.

[0137]

[Table 4]

From Table 4, it can be seen that if the ratio of the supply amount of the low pH liquid to the supply amount of the high pH liquid is in the range of 1 to 100, the required concentration can be obtained and the fog can be suppressed to a low level.

Example 5 In the processing method 2, except that the color development processing time was changed as shown in Table 5 and the pHs of the partial solutions A and B of the color developing solution-2 were adjusted to 1.5 and 13.0, respectively. The maximum blue reflection density D _max (Y) (440 nm) and the unexposed part 4 of the sample at the start of the continuous processing which was processed in the same manner as in Example 1
The 40 nm spectral reflection density D _min (Y) and the 660 nm spectral reflection density D _min (C) were measured. The results are shown in Table 5.

[0140]

[Table 5]

From Table 5, it can be seen that if the developing treatment time is in the range of 5 to 45 seconds, the required density can be obtained and the fog can be suppressed to a low level.

Example 6 In the processing method 2, the concentration of potassium carbonate in the partial liquid B of the color developer-2 was changed as shown in Table 6, and the pHs of the partial liquid A and the partial liquid B were 1.5 and 13, respectively. The maximum blue reflection density D _max (Y) (440) of the sample at the start of the continuous processing which was processed in the same manner as in Example 1 except that the adjustment was made to 0.0
nm) and the spectral reflection density D _min of the unexposed portion at 440 nm
(Y) and the spectral reflection density D _min (C) at 660 nm were measured. Further, the low temperature precipitation property of the partial liquid B was evaluated in the same manner as in Example 3. The results are shown in Table 6.

[0143]

[Table 6]

From Table 6, it can be seen that good results can be obtained by increasing the concentration of the alkaline agent in the high pH liquid to 0.1 to 4.5 mol / l.

[0145]

According to the present invention, it is possible to obtain a method for processing a silver halide photographic light-sensitive material which is dry and has excellent rapid processability and which has good storage stability of a developing solution.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a main part of an automatic developing machine used in an embodiment.

FIG. 2 is a perspective view of a main part of the automatic processor of FIG.

FIG. 3 is a perspective view of the vicinity of the supply port drying prevention unit of the automatic processor of FIG.

FIG. 4 is a schematic configuration diagram of a main part of an automatic developing machine having two developing processing means.

FIG. 5 is a schematic view of a processing tank section of a developing machine for immersion development capable of supplying two kinds of processing solutions for color development.

FIG. 6 is a schematic view of a color developing unit of an automatic developing machine, which supplies two types of color developing treatment liquids, one through a space and the other by immersion.

FIG. 7 is a schematic view of an automatic developing machine capable of supplying two types of processing solutions for color development to the emulsion surface of a photosensitive material through a space.

[Explanation of symbols]

10 Heating means 11 heating drum 30 Second heating means 33 heating belt 50 Development Processing Means 51 First treatment liquid container 52 processing liquid supply means 54 Circulation pump 55 Filter 56 Second processing liquid container 57 rotor 70 photosensitive material detecting means 80 Supply port drying prevention means

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-2-269335 (JP, A) JP-A-5-181245 (JP, A) JP-A-2-136850 (JP, A) JP-A-56- 165142 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7/407 G03C 7/00 520 G03C 7/413 G03D 3/08

Claims (7)

(57) [Claims] 1. A developing processing solution is from at least 2 of pH7 following concentrates and pH8 more concentrated solution, pH7
Both the following concentrated liquids and concentrated liquids with a pH of 8 or higher are passed through the space.
A method for processing a silver halide photographic light-sensitive material, which comprises supplying the image-forming surface of the silver halide photographic light-sensitive material. 2. An image forming surface of a silver halide photographic light-sensitive material.
The concentrated liquid of pH 7 or lower and the pH of 8 or higher supplied to
The volume ratio of the concentrated liquid is such that one liquid is 10 with respect to the other liquid.
The halo according to claim 1, which is within 0 times.
A method for processing a silver photographic light-sensitive material. 3. A concentrated liquid having a pH of 7 or less and a pH of 8 or more
One of the concentrated liquids of
The liquid is supplied to the image forming surface of the silver halide photographic light-sensitive material.
From the start of processing the photosensitive material to the next processing step is 5
It is ~ 45 seconds, The claim 1 or 2 characterized by the above-mentioned.
Method for processing silver halide photographic light-sensitive material. 4. A concentrated liquid having a pH of 7 or less and a pH of 8 or more
On the image forming surface of the silver halide photographic light-sensitive material.
Claims characterized by supplying a predetermined amount of each and developing
Item 1. A silver halide photographic light-sensitive material according to item 1, 2 or 3.
Processing method. 5. A concentrated liquid having a pH of 7 or less and a pH of 8 or more
The supply amount of the concentrated liquid of
It is characterized in that it is 5 to 150 ml per 1 m ² of material.
A method of processing a silver halide photographic light-sensitive material according to claim 4.
Law. 6. A concentrated developer having a pH of 7 or less is a color developing agent.
Of 0.005 to 1.00 mol / l
The silver halide according to claim 1, 2, 3, 4 or 5.
Processing method of photographic light-sensitive material. 7. The concentrated liquid having a pH of 8 or more contains an alkaline agent.
A content of 0.1 to 3.5 mol / l is included.
Item 1. The silver halide photograph as described in 1, 2, 3, 4, 5 or 6.
Method of processing photosensitive material.