JPH08314088A - Color image forming method - Google Patents

Abstract

PURPOSE: To decrease changes in the photographic sensitivity in a rapid process with a small amt. of replenishing liquid even when continuous processing is carried out for a long time including inactive periods, by using a specified photosensitive material, using a specified replenishing liquid for a color developer in the color developing process, and spraying a processing liquid circulated in a specified range of flow rate to the photosensitive material. CONSTITUTION: The photosensitive material used in this method has an emulsion layer containing silver halide having >=95mol% silver chloride content and contains a compd. expressed by formula I. The color developing process is carried out by using a replenishing liquid containing a compd. expressed by formula II by 40-200mmol/l concn. Further one process is carried out by spraying a processing liquid circulated at 1-10l/min flow rate to the emulsion layer side of the photosensitive material. In formula I, R1 , R2 are electron withdrawing groups having 0.3-0.6 Hammett substitution const. σp , R3 , R4 are hydrogen atoms, etc., A is an alkyl group, etc., M<1> , M<2> are hydrogen atoms, etc., p, q are integers 1 to 5. In formula II, L is an alkylene group, B is a carboxyl group, etc., and R is hydrogen atom, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide color photographic light-sensitive material, and a color capable of obtaining a higher quality and stable photographic image in an ultra-rapid development process with low replenishment. The present invention relates to an image forming method. More specifically, the present invention provides a color photographic image with less variation in photographic performance due to deterioration of a developer and less stain on a white background portion of a print even after performing continuous processing for a long period of time with intervening quiet periods. The present invention relates to an image forming method that can be performed.

[0002]

2. Description of the Related Art Among silver halide color photographic light-sensitive materials, one widely used is a light-sensitive material for color printing. In such a light-sensitive material, not only a high-quality image is provided to the user, but also a developing station, which is a production site, is required to have a simple developing operation and high productivity. For example, in light-sensitive materials for color printing in recent years, it is generally widespread that a color photographic light-sensitive material containing a so-called high silver chloride emulsion having a high silver chloride content is rapidly finished by an automatic processor. The development process using an automatic processor is usually continuously performed by replenishing a developer component which is deteriorated or consumed. For example, a small automatic developing machine called a minilab produces color prints for a long period of time by actually operating and stopping for several hours per day, but in order to reduce the labor required for the automatic developing machine, it is finished. It is preferable that the preparation is fast and the preparation of the replenisher and the disposal of the waste liquid can be performed as easily as possible. For this reason,
In recent years, the amount of replenishment and the amount of waste liquid have been reduced, and the development processing time tends to be shortened.

Since stable and high-quality performance is required for the development processing of the color light-sensitive material by the automatic processor, many studies have been made in the industry to improve the stability of the color developing solution used therein. On the other hand, in color development, replenishment is low, and after a long time, preservatives and color developing agents are deteriorated and constant photographic performance cannot be obtained. To reduce the quality of the photo. It is known that a developing agent is reduced or prevented from deterioration by a preservative, and particularly as a preservative for a high silver chloride color light-sensitive material, for example, JP-A-63-106655 and WO87-0.
No. 45345 and the like disclose methods using hydroxylamines. In addition, when the improvement with the preservative alone is not enough to stabilize the development performance, the structure of the developing tank is devised to reduce the contact area with air, and the floating lid is used for developing solution or replenishing solution. Attempts have been made to improve the preservability of Japanese Patent Application Laid-Open No. 61-278383 and Japanese Patent Application Laid-Open No. 2-2783283.
No. 96139 discloses a method of reducing the liquid opening ratio. Further, JP-A-3-121450 discloses a method for improving the stability of photographic performance during continuous processing by reducing the liquid opening ratio and using a specific hydroxyamine as a preservative. It has been shown that these methods improve photographic property fluctuations in automatic development processing, such as sensitivity and gradation fluctuations, and stably obtain good photographic performance. However, with the conventional developer preserving technique, if the substantial replenishment amount is made extremely small, sufficient performance cannot always be achieved in a simple and rapid process for finishing a color print in a short time.

Further, the photographic light-sensitive material usually contains an anti-irradiation dye in the light-sensitive layer in order to improve sharpness of image quality. In recent years, color print materials are required to have further improved sharpness, and thus the amount of dye used tends to increase more and more in recent years. Oxonol-based and cyanine-based dyes are widely used as dyes used for coloring the photosensitive emulsion layer. For example, European Patent EP03
Examples thereof include those described in 37490A2. The properties required of such dyes are that they have little effect on other photographic performances such as photographic gradation and that they are easily decolorized during development processing. However, as described above, in recent color print materials, due to speeding up of processing and reduction of replenishment amount, increase in accumulation of dyes and other eluted components eluted from the light-sensitive material in the developing solution is remarkable, and The processing conditions are becoming increasingly severe. For this reason, for example, stains during continuous processing are likely to deteriorate, and it is required that the dyes used for color print materials have better decolorizing properties than before and be inactive for photographic performance. However, a light-sensitive material satisfying this requirement has not yet been developed.

As a method of improving the stain and photographic performance as described above, a method of improving agitation of a developing processing apparatus is known. For example, there is a method in which the liquid in the processing tank is circulated by a pump and the circulating liquid is sprayed on the photosensitive material in the liquid, which is described in JP-A-4-145434. However, the conventional stirring technology has not always been sufficiently effective in the ultra-rapid treatment in which the replenishment amount is remarkably low.

That is, in the conventional continuous processing using hydroxylamines, in the case of practical off-the-shelf processing performed in a developing place, specifically, the replenishment amount per day is 20% of the capacity of the color developing tank. Continuing the processing below the value causes the adverse effect that the stain increases remarkably, and even if the processing solution circulated in the processing solution is sprayed on the photosensitive material in order to improve such stain, the sensitivity fluctuation is rather caused in the long-term continuous processing. It turned out to increase.

[0007]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a color image forming method for continuously producing a high quality color print image by using an automatic processor.
It is an object of the present invention to provide a color image forming method in which fluctuations in photographic sensitivity are small even when long-time continuous processing having a quiet period is performed by a low-replenishment ultra-rapid processing, and an increase in density of a white background is suppressed. .

[0008]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventor has found that when a photosensitive material containing a specific dye is used and a hydroxylamine compound having a specific substituent is used in a developing solution, a stain is produced. Further, it was found that when such a light-sensitive material and a preservative are used, spraying a circulated processing solution can improve the stain with very few adverse effects of the above-mentioned sensitivity decrease. . Even more surprisingly, it has been found that such a method for processing a light-sensitive material is extremely effective in the case of continuous continuous processing in which the replenishing amount per day is less than 20% of the capacity of the color developing tank. That is, the problems of the present invention can be solved by the following methods. (1) In an image forming method in which a silver halide color photographic light-sensitive material is imagewise exposed, and then subjected to color development, desilvering, stabilization and / or washing, and then dried, at least one of the light-sensitive materials on a support is At least one light-sensitive silver halide emulsion layer containing silver halide having a silver chloride content of 95 mol% or more is provided on the side, and the following general formula [I-
color development using a replenisher containing at least one compound represented by the formula a) and the color developing step containing the compound of the following general formula [II] at a concentration of 40 mmol / liter or more and 200 mmol / liter or less. It is carried out by processing with a liquid, and at least one step is carried out at a rate of 1 liter / minute or more and 10 liters / minute or less by spraying the circulated processing solution on the emulsion layer coating side of the light-sensitive material. Color image forming method. General formula [Ia]

[0009]

Embedded image

In the formula, R ₁ and R ₂ each represent an electron-withdrawing group having a Hammett's substituent constant σ _p of 0.3 to 0.6, and R ₃ and R ₄ represent a hydrogen atom, a halogen atom and a hydroxyl group, respectively. Represents a group, a methyl group or a methoxy group, A represents an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms, and M ¹ and M ² are hydrogen atoms or an atomic group serving as a monovalent cation. Alternatively, it represents a metal atom, and p and q each represent an integer of 1 to 5. General formula [II]

[0011]

[Chemical 4]

In the formula, L represents an alkylene group, B represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted,
It represents an ammonio group which may be alkyl-substituted, a sulfamoyl group which may be alkyl-substituted, or an alkylsulfonyl group which may be alkyl-substituted. R represents a hydrogen atom or an alkyl group. (2) The replenishing amount of the color developing solution is 10 per 1 m ^{2 of the} light-sensitive material.
The color image forming method as described in the item (1), wherein it is not less than ml / m ^{2 and not} more than 45 ml / m ² . (3) The color image formation according to item (1) or (2), wherein the color development time is 10 to 30 seconds and the processing from the beginning of the developing step to the end of the drying step is 50 to 90 seconds. Method. (4) The replenishing amount of the color developing replenisher solution per day is 0.1% or more and 20% or less of the capacity of the color developing tank. (1), (2) or (3) The described color image forming method. Furthermore, preferred embodiments of the present invention include (5) to
It writes in (10). (5) The color image forming method as described in the item (1), wherein A in the general formula [Ia] is an alkyl group having 1 to 4 carbon atoms. (6) The processing solution used in at least one of the steps of development, desilvering and washing and / or stabilization is represented by the following general formula [III].
(1) characterized by containing a compound represented by
The color image forming method according to item (2), (3), (4) or (5). General formula [III]

[0013]

Embedded image

In the general formula [III], L ¹ and L ² may be the same or different and may be --OR ₇ or --NR ₈ R ₉ (R
₇ , R ₈ and R ₉ are each a hydrogen atom or an alkyl group), and the four substituents represented by L ¹ and L ² are a total of 4 substituents selected from the following general formula [IV] group. ~ 8
I have one. General formula [IV] group

[0015]

[Chemical 6]

In the general formula [IV] group, X is a halogen atom and R
Represents an alkyl group. Further, in the general formulas [III] and [IV], M represents a hydrogen atom, an alkali metal or another monovalent cation. (7) At least 1 liter / minute or more and 10 liters / in the developing step and the stabilizing and / or washing step.
A processing solution circulated at a speed of not more than a minute is sprayed onto the photosensitive material for processing (1), (2),
The color image forming method according to item (3), (4), (5) or (6). (8) A silver halide color photographic light-sensitive material is exposed by a scanning exposure method under the condition that the exposure time per pixel is 10 ⁻⁷ to 10 ⁻⁴ seconds, and then developed (1),
(2), (3), (4), (5), (6) or (7)
The method for forming a color image according to item. (9) The support is printed through a color negative film made of polyethylene terephthalate or polyethylene naphthalate (1), (2),
(3), (4), (5), (6), (7) or (8)
The method for forming a color image according to item. (10) The silver halide color photographic light-sensitive material contains a dye represented by the following general formula [Ib] (1), (2), (3), (4), (5). ), (6),
The color image forming method according to item (7), (8) or (9).

[0017]

[Chemical 7]

In the formula, R ₅ represents a hydrogen atom or an alkyl group. R ₆ represents a substituent such that the sum of the atomic weights of the atoms contained in R ₅ and R ₆ (R ₅ + R ₆ ) is 160 or less. n represents 0, 1, or 2. M represents a hydrogen atom or an alkali metal.

In the present invention, it is not clear why the use of the preservatives as described above improves the fluctuation of the photographic properties in the ultra-rapid processing with a particularly low replenishment rate. Balance between the rate of oxidative decomposition due to heat and the decomposition of the developer due to heat, while the amount of new preservative supplied by replenishment against it, and the elution components such as dyes from the photosensitive material during continuous processing. It is considered that this is due to the effects on the photographic characteristics due to the accumulation of
Generally, it is known that the stain generation due to the deterioration of the developing agent is suppressed by the preservative, but the yellow stain generated in the continuous processing is difficult to be improved by the conventional preservative, and thus the constitution of the present invention The improvement was easily and unexpectedly.

The dye relating to the present invention is preferably a compound represented by the above formula [Ia] from the viewpoint of the influence on the photographic property due to the accumulation in the developing solution and the stain.

The compound represented by the general formula [Ia] of the present invention will be described in detail below. Examples of the electron-withdrawing group represented by R ₁ and R ₂ having a Hammett's substituent constant σ _p of 0.3 or more and 0.6 or less include, for example, a carbamoyl group (0.3
6), methylcarbamoyl group (0.36), carboxyl group (0.45), methoxycarbonyl group (0.4
5), ethoxycarbonyl group (0.45), methylsulfinyl group (0.49), methylsulfonyl group (0.7
2), sulfamoyl group (0.60), benzoyl group (0.43), acetyl group (0.50), trifluoromethyl group (0.54), diethylphosphono group (0.6
0) etc. can be mentioned. Where σ _p is Chemical
Reviews, 91, 168-175 (1991). The method of measuring σ _p is Chemical Revie
ws, Vol. 17, pages 125-136 (1935). R ₁ and R ₂ are particularly preferably an alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl) or a carbamoyl group (eg carbamoyl, methylcarbamoyl). Further, R ₁ and R ₂ are preferably the same group.

R ₃ and R ₄ represent a hydrogen atom, a halogen atom, a hydroxyl group, a methyl group or a methoxy group, preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

Examples of the alkyl group having 1 to 8 carbon atoms represented by A include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group and an octyl group. Further, it may have a substituent. Preferred substituents are a halogen atom (eg fluorine, chlorine, bromine), hydroxyl group, carboxyl group, sulfo group, cyano group, aryl group having 6 to 7 carbon atoms (eg phenyl, p-tolyl), 1 to 7 carbon atoms. Alkoxy group (eg, methoxy, ethoxy, butoxy), an acyl group having 2 to 7 carbon atoms (eg, acetyl, benzoyl), an alkoxycarbonyl group having 2 to 7 carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl), 0 carbon atoms.
To 7 amino groups (for example, amino, dimethylamino, diethylamino) and the like.

Examples of the aryl group having 6 to 10 carbon atoms represented by A include a phenyl group, a 1-naphthyl group and a 2-naphthyl group, which may further have a substituent. Preferred substituents are halogen atoms (eg fluorine, chlorine, bromine), hydroxyl groups, carboxyl groups,
Sulfo group, cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, butyl), alkoxy group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, butoxy), acyl group having 2 to 4 carbon atoms (eg, Acetyl), an alkoxycarbonyl group having 2 to 4 carbon atoms (for example, methoxycarbonyl,
Ethoxycarbonyl), an amino group having 0 to 4 carbon atoms (for example, amino, dimethylamino, diethylamino) and the like.

A is preferably an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, sulfoethyl), and particularly preferably a methyl group.

M ¹ and M ² each represent a hydrogen atom or an atomic group (for example, ammonium, triethylammonium, pyridinium) which becomes a monovalent cation or a metal atom (for example, lithium, sodium, potassium), and M
² is preferably sodium or potassium, and M ¹ is preferably a hydrogen atom, sodium or potassium.

P and q each represent an integer of 1 to 5, preferably 2 or 3, and more preferably 2. Particularly, at least one substitution position of SO ₃ M ² groups on the phenyl group is at the 2-position (ortho-position) with respect to pyrazolone.
It is preferred that

A preferred combination of the substituents of the compound represented by the formula [Ia] is that R ₁ and R ₂ are both a methoxycarbonyl group or a methylcarbamoyl group,
R ₃ and R ⁴ are a hydrogen atom or a methyl group, A is a methyl group, an ethyl group or a sulfoethyl group, and M ¹
Is a hydrogen atom, sodium or potassium, and M ²
Is sodium or potassium, and p and q are both 2. More preferable combination of substituents is that R ₁ and R ₂ are both methylcarbamoyl groups, R ₃ and R ⁴ are methyl groups, A is a methyl group, and M ¹ is a hydrogen atom, sodium or potassium. Where M ² is sodium or potassium and both p and q are 2.

Examples of the dye represented by the general formula [Ia] are shown below, but the invention is not limited thereto.

[0030]

[Table 1]

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

[Table 4]

The light-sensitive material of the present invention has the general formula [I
In addition to containing at least one of the dyes represented by -a], other dyes may also be contained in combination. When a plurality of types of dyes are contained, the dye to be used in combination is represented by the general formula [I-
It is preferable in that the stain when the dye represented by b] is accumulated in the color developing solution is reduced.

The general formula [Ib] will be described in more detail below. R ₅ and R ₆ of the dye represented by the general formula [Ib] are CONR ₁₀ R ₁₁ (R ₁₀ and R ₁₁ represent a hydrogen atom or an alkyl group and may form a ring),
COOR ₁₂ (R ₁₂ represents an alkyl group), CN, a hydrogen atom, an alkyl group, OR ₁₃ (R ₁₃ represents a hydrogen atom or an alkyl group), NR ₁₄ R ₁₅ (R ₁₄ and R ₁₅ represent a hydrogen atom or alkyl) Represents a group and may form a ring), NR ₁₆ CO
R ₁₇ (R ₁₆ and R ₁₇ represent a hydrogen atom or an alkyl group), NR ₁₈ CONR ₁₉ R ₂₀ (R ₁₈ , R ₁₉ and R ₂₀ represent a hydrogen atom or an alkyl group, and R ₁₉ and R ₂₀ represent a ring. It may be formed). Furthermore, it is preferable that R ₅ and R ₆ do not have a dissociative group. The dissociative group of these substituents is a substituent that is substantially dissociated in water at 25 ° C. and has a pKa of 12 or less and 1 or more. Specific examples of such a dissociative group include a sulfonic acid, a carboxyl group, and a phosphoric acid group.

The alkyl group represented by R ₅ is preferably an alkyl group having a carbon number of 3 or less such as a methyl group, an ethyl group and a propyl group, and may have a substituent. Examples of such a substituent include a hydroxyl group, an ether group, an ester group, a carbamoyl group, a sulfone group, a sulfamoyl group and a cyano group, and among them, a hydroxyl group and an ether group are particularly preferable.
It is particularly preferable that R ₅ is a methyl group.

Alkali metals represented by M ³ are Li, N
Preferred are a, K and Ca.

When the substituent represented by R ₆ is represented by CONR ₁₀ R ₁₁ , R ₁₀ and R ₁₁ may be a hydrogen atom or an alkyl group, but at least one is preferably an alkyl group. As the alkyl group, a methyl group, an ethyl group,
An alkyl group having a carbon number of 3 or less such as a propyl group is preferable, and they may have a substituent. A hydroxyl group and an ether group are particularly preferable as the substituent. Also, R ₁₀ and R
₁₁ may combine with each other to form a ring. A morpholine ring is particularly preferred as the ring formed in that case.

When the substituent represented by R ₆ is represented by COOR ₁₂ , the alkyl group of R ₁₂ is preferably an alkyl group having 4 or less carbon atoms such as methyl group, ethyl group, propyl group,
A methyl group or an ethyl group is particularly preferable.

When the substituent represented by R ₆ is hydrogen or an alkyl group, the alkyl group is particularly preferably an alkyl group having a carbon number of 4 or less, such as a methyl group, an ethyl group, a propyl group and a butyl group. The ethyl group is particularly preferred.

The substituent represented by R ₆ is OR ₁₃ or NR
When represented by ₁₄ R ₁₅ , R ₁₃ , R ₁₄ and R ₁₅ may be a hydrogen atom or an alkyl group. In the case of an alkyl group, a methyl group,
An alkyl group having a carbon number of 3 or less such as an ethyl group or a propyl group is particularly preferable, and may have a substituent. A hydroxyl group and an ether group are particularly preferable as the substituent. Also R
₁₄ and R ₁₅ may combine to form a ring.

When the substituent represented by R ₆ is represented by NR ₁₆ COR ₁₇ , R ₁₆ and R ₁₇ may be a hydrogen atom or an alkyl group. As the alkyl group, a methyl group, an ethyl group,
A propyl group and the like are preferable, and a methyl group is particularly preferable.
It may also have a substituent. The substituent is preferably a hydroxyl group or an ether group.

The substituent represented by R ₆ is NR ₁₈ CONR ₁₉
When represented by R ₂₀ , R ₁₈ , R ₁₉ , and R ₂₀ may be a hydrogen atom or an alkyl group. As the alkyl group, a methyl group, an ethyl group, a propyl group and the like are preferable, and a methyl group is particularly preferable. It may also have a substituent. The substituent is preferably a hydroxyl group or an ether group.

R ₆ preferably has a total sum of atomic weights of atoms contained in R ₅ and R ₆ (R ₅ + R ₆ ) of from 16 to 160, more preferably from 18 to 140, and most preferably. It is 80 or more and 130 or less.

[0045] Preferred combinations of the substituents of the general formula [I-b] the compound represented by, R ₆ is R ₁₀ and R ₁₁ are linked methyl group or together form a morpholine ring together at CONR ₁₀ R ₁₁ And R ₆ is a methyl group or an ethyl group, in which case the total atomic weight (R ₅ + R ₆ ) is 87 or more and 129 or less. A more preferred combination is when R ₆ is CONR ₁₀ R ₁₁ and R ₁₀ and R ₁₁ are linked to each other to form a morpholine ring, and when R ₆ is a methyl group, the total atomic weight (R ₅ + R ₆ ) is 115.

Specific examples of the compound represented by the formula [Ib] are shown below.

[0047]

[Table 5]

[0048]

[Table 6]

[0049]

[Table 7]

[0050]

[Table 8]

[0051]

[Table 9]

[0052]

[Table 10]

Dyes [Ia] and [Ib] of the present invention
Can be molecularly dispersed in the photosensitive layer or the non-photosensitive layer by various known methods. A method in which the compound is directly dispersed in the photosensitive layer or the non-photosensitive layer, or a suitable solvent (for example, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A No. 4).
No. 8-9715, US Pat. No. 3,756,830, and the like, which is dissolved in halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof) and added in the form of a solution. . The compound of the present invention, when added to either the photosensitive layer or the non-photosensitive layer, diffuses substantially uniformly throughout the photosensitive material constituting layer during coating.

Dyes [Ia] and [Ib] of the present invention
The amount used is not particularly limited, but is 0.1 mg / m ^{2 to} 200 mg
/ M ² is preferably used, and particularly preferably 1 mg / m ²
˜100 mg / m ² . In addition, the dye of the present invention [I
-A] and [Ib] can be used in combination with a dye other than the present invention. When used in combination, it is preferable that the coating amount of the dye of the present invention is equal to or more than the coating amount of the dye other than the present invention, and the total coating amount is within the above coating amount range.

Next, the general formula [II] will be described in detail. In the formula, L represents a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, preferred examples include methylene, ethylene, trimethylene, and propylene. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphine residue, a hydroxy group, an ammonio group which may be substituted with an alkyl group, and among these, preferred examples include a carboxyl group, a sulfo group, a phosphono group and a phosphine group. To be B is a carboxyl group, a sulfo group, a phosphono group, a phosphine residue, a hydroxy group, an amino group which may be alkyl-substituted, an alkyl group (preferably having a carbon number of 1 to 5), an ammonio group which may be substituted, an alkyl group (preferably a carbon group). Number 1
To 5) a carbamoyl group which may be substituted, an alkyl (preferably having a carbon number of 1 to 5) a sulfamoyl group which may be substituted, of which a carboxyl group, a sulfo group, a hydroxy group, an alkyl (preferably having a carbon number of 1 to 5) 5) A carbamoyl group which may be substituted is particularly preferable. Examples of -LB include a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group,
Sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group can be mentioned as a preferred example, carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as a particularly preferred example. it can. R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and more preferably 1 to 5 carbon atoms. As the substituent, a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxy group, an amino group which may be alkyl-substituted, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, an alkyl-substituted May be sulfamoyl group, optionally substituted alkylsulfonyl group, acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group, alkyl-substituted amino group, arylsulfonyl group, nitro group,
Represents a cyano group and a halogen atom. There may be two or more substituents. R as a hydrogen atom, a methyl group, an ethyl group, a propyl group, a carboxymethyl group, a carboxyethyl group,
Carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, hydroxyethyl group is preferable, hydrogen atom, carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group is Particularly preferred. L and R may combine to form a ring. Specific examples of the compound represented by the general formula [II] are shown below.
It is not limited to these.

[0056]

Embedded image

[0057]

[Chemical 9]

[0058]

[Chemical 10]

[0059]

[Chemical 11]

The amount of the compound of the general formula [II] added is preferably 10 to 200 mmol / liter, and more preferably 20 to 150 mmol / liter per liter of the color developing solution. In particular, in order to obtain good performance in continuous processing, it is preferable that the developing replenisher contains 20 to 200 mmol / liter or less, preferably 30 to 150, and most preferably 40 to 100.

The processing method of the present invention is effective in developing any light-sensitive material containing a silver halide emulsion, and is effective in any processing method, but it contains a high silver chloride emulsion having a silver chloride content of 95 mol% or more. This is particularly effective when processing color photographic paper in a rapid replenishment process with low replenishment. The high silver chloride emulsion preferably comprises silver chlorobromide or silver chloride having a silver chloride content of 98 mol% or more.

The replenishing method of the developing step, the desilvering step, the water washing or the rinsing step in the present invention is not limited to the case of replenishing the replenishing solution having a single composition, but it is separated into a plurality of replenishing solutions having different compositions. When replenishing, it can be replenished by any method of replenishing one or more replenishing liquids or water and separating the addition of the solid substance consisting of replenishing components. The amount of replenishment per step in the present invention is represented by the amount of increase in volume when the replenishers are separated and replenished, and a single or a plurality of replenishers or water is added. Separated replenishment and addition of solid substances consisting of replenishment components are also represented by the increase in volume when they are replenished.

The reduction in replenishment of processing in the present invention differs depending on the type of the light-sensitive material. For example, in the case of development processing for color printing, the replenishment amount per 1 m ^{2 of} the light-sensitive material is 10 times the replenishment amount of the color developing solution. -60 ml / m ² , more preferably 20-45 ml / m ^2, at the same time, the replenishing amount of the bleach-fixing solution is 20-50 ml / m ² , and the replenishing amount of the washing and / or stabilizing solution is 50-100 ml. / M ² is preferred. In addition, the total replenishment amount of all processes at this time is 70 to
0 ml / m ² is preferable, and 90 to 160 ml / m ² is more preferable.

The continuous processing in the present invention refers to processing of the light-sensitive material which requires substantial replenishment of the processing solution. More specifically, it refers to carrying out a development process for a plurality of days in which the replenishment amount associated with the color print process is equivalent to 0.1 to 20% of the capacity of the processing tank on average per day. In particular, the condition that the effect of reduction of stain and stabilization of photographic performance can be obtained by simple and rapid processing is such that the average replenishment amount per day is preferably 0.1 to 20% of the capacity of the development processing tank, and more preferably 0. 0.2 to 10%, most preferably 0.5 to 6%.
At this time, the capacity of the color developing tank is not particularly limited, but is usually 50 liters or less, preferably 0.2 to 20 liters, and most preferably 1 to 10 liters. Also,
The processing amount is an amount determined by the replenishing amount per 1 m ² of the light-sensitive material and the average replenishing amount per day. Specifically, in the case of a color printing light-sensitive material, the average amount per day is 0.
Is preferably 1~80m ^2, more preferably 0.2~60m ^2, and most preferably 0.1 to 30
m ² .

Accelerating the processing in the present invention means shortening the time required to develop the exposed photosensitive material and obtain an image through the drying step. Specifically, by shortening the time of one or more of the color development step, the desilvering step, the washing and / or stabilizing step, and the drying step, the total processing step is 30 to 90 seconds, preferably 50 to 90 seconds. Making seconds is a preferred embodiment of the invention. Regarding each processing step, the processing time of the developing step and the desilvering step is preferably within 30 seconds, more preferably 10 to 15 seconds. At the same time, the ratio (Tw / Tbf) of the processing time (Tw) of the washing and / or stabilizing step and the processing time (Tbf) of the bleach-fixing step is 1.
It is preferably 3 or less. In the present specification, the ultra-rapid type processing means that all the processing steps of a light-sensitive material containing a silver halide emulsion having a silver chloride content of 95 mol% or more are processed in the above-mentioned time.

The processing time of the step in the present invention means the time required from the start of the processing of the photosensitive material in a certain step to the start of the processing in the next step. In the present invention, the beginning of the developing step means when the light-sensitive material is immersed in the color developing solution, and the end of the drying step means when the light-sensitive material passes through the final conveying roller of the drying step.

The actual processing time by the automatic processor is usually determined by the linear velocity and the capacity of the processing bath. The linear velocity in the present invention may be in the range of 500 to 4000 mm / min, but particularly in the case of a small developing machine called a minilab, 500 to 2500 mm / min is preferable.

In the present invention, washing and / or stabilizing treatment is preferably carried out in a multi-stage countercurrent bath. At this time, it is more preferable that the light-sensitive material is moved between the tanks in a liquid so as not to come into contact with air. . As a method of moving between the tanks in the liquid, for example, a photosensitive material passage is provided between the tanks, and the passage can be opened and closed by shutter means. At this time, it is preferable that the shutter means is provided with a pair of flexible blades so that only the tips of the blades elastically contact each other.

In the present invention, a processing roller is provided in the processing solution of at least one of the washing or stabilizing step and the desilvering step, and the photosensitive material is brought into contact with the peripheral surface on which the processing roller is rotated for processing. Is preferable, and the processing time is further shortened. The rotation number of the processing roller is 75 to 25
00 rpm is preferable, and 100 to 1500 rpm is more preferable. In this case, the rotating direction may be the same as or opposite to the conveying direction of the photosensitive material, and the peripheral surface of the rotating roller preferably has grooves along the spiral direction or the axial direction.

In the present invention, at least one of the steps of development, desilvering, washing with water and / or stabilization is carried out in the presence of the diaminostilbene type fluorescent brightening agent represented by the above general formula [III]. It is preferable. As specific examples of the compound represented by the general formula [III] and the constitution of use, those described in JP-A-6-332127 are preferable.

The compound represented by the general formula [III] is a known compound as described in, for example, JP-A-4-249243. In the present invention, in the general formula [III], L ¹ , L ² ,
L ³ and L ⁴ must not have a substituted or unsubstituted aryl group. In the general formula [III], L ¹ and L ² may be the same or different and may be —OR ⁷ or —NR ⁸ R ⁹ (R
⁷ , R ⁸ and R ⁹ are each a hydrogen atom, an alkyl group,
Or an alkyl group having a substituent). The alkyl group is a linear or branched alkyl group, and the hydrogen atom of the alkyl group may be substituted with another group.
The substitutable group may be any group, but is preferably a substituent selected from the above general formula [IV] group. The carbon number of the alkyl group represented by R ⁷ , R ⁸ and R ⁹ is preferably 1-10, more preferably 1-5. The substituents in the general formula [IV] group are those generally known as hydrophilic groups. The compound of the general formula [III] has a total of four or more substituents represented by L ¹ and L ² selected from the group of the general formula [IV], and forms a stilbene benzene ring. Combined with the number of the above two sulfo groups, it has a total of 6 or more strongly hydrophilic groups in the molecule. Specific examples of the substituents L ¹ and L ² in the general formula [III] include a methoxy group, an ethoxy group, a propoxy group,
Isopropoxy group, butoxy group, isobutoxy group, pentyloxy group, hexyloxy group, methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, 2-hydroxyethoxy group, 3- Hydroxypropoxy group, 4-hydroxybutoxy group, 2-hydroxyethylamino group,
3-hydroxypropylamino group, 4-hydroxybutylamino group, 2-hydroxyethylethylamino group, 3
-Hydroxypropylpropylamino group, 4-hydroxybutylbutylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group, di2-
Hydroxyethylamino group, di3-hydroxypropylamino group, dihydroxybutylamino group, 2-sulfoethoxy group, 3-sulfopropoxy group, 4-sulfobutoxy group, 2-sulfoethylamino group, 3-sulfopropylamino group, 4-sulfobutylamino group, di2-sulfoethylamino group, di3-sulfopropylamino group, di4-
Sulfobutylamino group, 2-sulfoethylmethylamino group, 3-sulfopropylmethylamino group, 4-sulfobutylmethylamino group, 2-sulfoethylethylamino group, 3-sulfopropylethylamino group, 4-sulfobutylethyl group Amino group, 2-carboxyethoxy group, 3-
Carboxypropoxy group, 4-carboxybutoxy group,
2-carboxyethylamino group, 3-carboxypropylamino group, 4-carboxybutylamino group, di2-carboxyethylamino group, di3-carboxypropylamino group, di4-carboxybutylamino group, 2-carboxyethylmethyl group Amino group, 3-carboxypropylmethylamino group, 4-carboxybutylmethylamino group,
2-carboxyethylethylamino group, 3-carboxypropylethylamino group, 4-carboxybutylethylamino group, 2-sulfoethoxy group, 3-sulfoxypropoxy group, 4-sulfoxybutoxy group, 2-sulfoxyethylamino Group, 3-sulfoxypropylamino group, 4
-Sulfoxybutylamino group, di2-sulfoxyethylamino group, di3-sulfoxypropylamino group, di4-
Sulfoxybutylamino group, 2-sulfoxyethylmethylamino group, 3-sulfoxypropylmethylamino group,
4-sulfoxybutylmethylamino group, 2-sulfoxyethylethylamino group, 3-sulfoxypropylethylamino group, 4-sulfoxybutylethylamino group, trimethylammoniomethylamino group, trimethylammonioethylamino group, Examples thereof include a trimethylammoniopropylamino group, a triethylammoniomethylamino group, a triethylammonioethylamino group and a triethylammoniopropylamino group. More preferably, methoxy group, ethoxy group, 2-hydroxyethoxy group, 2
-Hydroxyethylamino group, 2-sulfoethylamino group, di2-sulfoethylamino group, 2-carboxyethylamino group, di2-carboxyethylamino group, di2-
Examples thereof include hydroxyethylamino group. General formula [II
Specific examples of the diaminostilbene-based fluorescent whitening agent of [I] are preferably the compounds described in Tables 1 to 6 of JP-A-6-332127, and among these, compounds (SR-1) to
(SR-16) is particularly preferable.

The compound of the general formula [III] in the present invention can be contained in either the light-sensitive material or the processing solution, but it is preferably contained in the processing solution.

When the compound of the general formula [III] is contained in the processing liquid, (1) development, (2) desilvering, (3) water washing and /
Alternatively, it is preferably contained in the treatment liquid of any of the stabilization steps, but it is preferably contained substantially in the treatment liquid of a plurality of steps. Here, the desilvering step includes any step of bleaching, fixing, or bleach-fixing and a combination thereof. In the present invention, the general formula [III]
It is preferable to add the compound (1) to the processing bath as early as possible in all processing steps, and particularly preferably to be used by adding it to the developing solution.

The preferred concentration of the compound of the general formula [III] in the treatment liquid during the continuous treatment is 5 × 10 ^-5 to 1 × 10 ^-2 mol / mol.
Liter, more preferably 1 × 10 ^{−4 to} 5 × 10 ⁻³ mol / liter, in which case the concentration in the replenisher required to keep the concentration of the treating solution constant, specifically 1 It is preferably 0.5 × 10 ^{−4 to} 1.5 × 10 ⁻² mol / liter.

In the present invention, as described above, the spraying amount of the circulating treatment liquid is usually 1 liter / min or more and 10 liter / min.
Not more than a minute. The circulation amount is 1 to achieve the above spray amount.
-15 liters / min, preferably 2-10 liters / min, which is equal to or more than the spray amount. The circulation amount and the blowing amount may be the same. In the present invention, it is necessary that this condition is satisfied at least when processing the light-sensitive material. Further, this condition may be satisfied even when the power of the processor is turned on. The circulation and spraying may be in the form of circulating in the processing tank or spraying the circulating liquid onto the photosensitive layer side of the photosensitive material. In the present invention, the circulating liquid is sprayed onto at least the photosensitive layer side of the photosensitive material. Spraying is preferably in liquid. The circulating liquid is filtered through a filter by a conventional method and then returned to the treatment tank. The spraying rate of the circulating treatment liquid is preferably 2 to 7 liters / minute. The circulating amount of the treatment liquid is preferably 0.5 to 20 liters / minute, and more preferably 1 to 10 liters / minute per one treatment tank. If the amount of spraying is small, the effect of the present invention is difficult to obtain. On the other hand, if the amount of spraying is too large, deterioration of the treatment liquid tends to proceed, which is not preferable. The circulating holes of the processing solution have a diameter of 1 to 4 mm, and the number of the holes directed vertically to the photosensitive layer of the photosensitive material is 10 to 10 per tank.
It is preferable that 0 holes are provided, and more preferably, 5 to 50 blow holes are provided per tank. Further, the distance between the blowing hole and the surface of the photosensitive layer is preferably 1.0 to 50 mm, more preferably 2.0 to 20 mm. Further, the flow rate from one blowing hole is preferably 1 to 100 cm / sec or more, more preferably 5 to 50 cm / sec.

In the present invention, the circulating liquid spraying means as described above may be provided in any processing step, but it is preferable that it is provided at least in the developing step, and the developing step and washing and / or stabilization are performed. It is more preferable that the step is provided in each step, and the aspect that is provided in all the steps is most preferable because the effect of improving the stain of the present invention can be obtained. Furthermore, as a preferred embodiment in which a spraying means is provided in the washing and / or stabilizing step, the washing and / or stabilizing step is divided into at least three tanks, and at least a final tank is provided with a circulating liquid spraying means. Is preferably provided in the final tank and its pre-tank, and most preferably in all tanks for washing and / or stabilization. Further, the washing and / or stabilizing step is preferably divided into 3 to 12 tanks, and 5 to 10
More preferably, it is divided into tanks. In addition, it is preferable that the photosensitive material is conveyed between the divided water washing and / or stabilizing tanks in a liquid through a blade provided on the wall of the tank from the viewpoint of shortening the air time. The nozzle for spraying the liquid is preferably provided between the transport roller and the inter-tank blade. At this time, the spray nozzle may be provided only on the photosensitive layer side of the photosensitive material, but a method of spraying from both sides of the surface of the photosensitive material in a multi-chamber water washing step is preferable because jamming or the like during transport is unlikely to occur.

The processing material and processing method used in the present invention will be described in detail. In the present invention, the light-sensitive material is color-developed, desilvered, washed with water or stabilized. The color developing solution used in the present invention contains a known aromatic primary amine developing agent. A preferred example is p
-A phenylenediamine derivative, a typical example of which is
N, N-diethyl-p-phenylenediamine, 4-amino-N, N-diethyl-3-methylalinine, 4-amino-N- (β-hydroxyethyl) -N-methylaniline, 4-amino-N-ethyl. -N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β-
Hydroxyethyl) -3-methylaniline, 4-amino-N-ethyl-N- (3-hydroxypropyl) -3-
Methylaniline, 4-amino-N-ethyl-N- (4-
Hydroxybutyl) -3-methylaniline, 4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) -3-methylaniline, 4-amino-N, N-diethyl-3- (β-hydroxyethyl) ) Aniline, 4-amino-N-ethyl-N- (β-methoxyethyl) -3-
Methylaniline, 4-amino-N- (β-ethoxyethyl) -N-ethyl-3-methylaniline, 4-amino-
N- (3-carbamoylpropyl) -Nn-propyl-3-methylaniline, 4-amino-N- (3-carbamoylbutyl) -Nn-propyl-3-methylaniline, N- (4-amino -3-Methylphenyl) -3-hydroxypyrrolidine, N- (4-amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine, N-
(4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide.

Further, salts of these p-phenylenediamine derivatives with sulfates, sulfites, hydrochlorides, naphthalenedisulfonates, p-toluenesulfonates and the like may be used. The amount of the aromatic primary amine developing agent used is the amount of developer 1
It is preferably 0.002 to 0.2 mol, and more preferably 0.005 to 0.1 mol per liter.
The treatment temperature at that time is 20 to 50 ° C., preferably 35 to 4
8 ° C, most preferably 37-46 ° C.

In practicing the present invention, it is preferable that substantially no benzyl alcohol is contained. The term "substantially free from" means that the concentration of benzyl alcohol is preferably 2 ml / liter or less, more preferably 0.5 ml / liter or less, and most preferably, benzyl alcohol is not contained at all.

The color developing solution used in the present invention suppresses fluctuations in photographic characteristics due to continuous processing, and does not substantially contain sulfite ion in order to achieve the effects of the present invention. That is, the sulfite ion concentration is 3.0 × 10 ⁻³ mol / liter or less. Sulfite ion is preferably 1.0 × 10 ⁻³ mol / liter or less, and most preferably contains no sulfite ion. However, in the present invention, however, a very small amount of sulfite ion used for the oxidation prevention of the processing agent kit in which the developing agent is concentrated before preparing the use solution is excluded. The color developing solution used in the present invention should further contain substantially no hydroxylamine in order to suppress fluctuations in photographic characteristics due to fluctuations in the concentration of hydroxylamine. 5.0 × 10 ⁻³ mol / liter or less) is more preferable. Most preferably, it contains no hydroxylamine at all.

In the present invention, it is preferable that the color developer contains chlorine ions in an amount of 3.0 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. Particularly preferably 3.5 × 10 ^-2
˜1.0 × 10 ⁻¹ mol / liter. When the chlorine ion concentration is more than 1.5 × 10 ^-1 mol / liter, it has the drawback of delaying the development, which is not preferable for achieving the object of the present invention that it is rapid and the maximum concentration is high. Also, 3.
If it is less than 0 × 10 ^-2 mol / liter, it is not preferable for preventing fog. In the present invention, bromine ions are contained in the color developing solution in an amount of 0.5 × 10 ⁻⁵ mol / liter to 1.0 ×.
It is preferably contained at 10 ⁻³ mol / liter. More preferably, it is 3.0 × 10 ^{−5 to} 5 × 10 ⁻⁴ mol / liter. When the bromine ion concentration is higher than 1 × 10 ^-3 mol / liter, development is delayed, the maximum concentration and sensitivity are lowered, and when it is less than 0.5 × 10 ^-5 mol / liter, fog is sufficiently prevented. I can't.

Here, the chlorine ion and the bromine ion may be directly added to the color developing solution, or may be eluted from the light-sensitive material into the color developing solution during the development processing. When added directly to the color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developing solution. Examples of the bromide ion supplying substance include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When it is eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

The color developing solution used in the present invention preferably has a pH of 9 to 13, more preferably 9 to 12.5, and the color developing solution contains other compounds of known developing solution components. be able to. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt,
3,4-dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-
Propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. Particularly, carbonates, phosphates, tetraborates, and hydroxybenzoates have excellent solubility and buffering ability in a high pH range of pH 9.0 or more, and even when added to a color developing solution, they have excellent photographic performance. It is particularly preferable to use these buffers, since they have the advantages of being free from adverse effects (fogging, etc.) and being inexpensive.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Examples thereof include potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate). The amount of the buffer added to the color developer is preferably 0.1 mol / liter or more, and particularly 0.1 mol / liter to 0.1.
It is particularly preferably 4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, trans-silohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2
-Hydroxybenzyl) ethylenediamine-N, N'-
Examples thereof include hydroxyethyliminodiacetic acid diacetate.
Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution. For example, it is about 0.1 g to 10 g per liter.

Any development accelerator can be added to the color developing solution, if necessary. As a development accelerator, Japanese Patent Publication No. 37
-16088, 37-5987, 38-782.
No. 6, No. 44-12380, No. 45-9019, and thioether compounds represented by US Pat. No. 3,813,247;
P-phenylenediamine compounds represented by JP-A-15554, JP-A-50-137726, and JP-B-44-3.
No. 0074, JP-A Nos. 56-156826 and 52-
Quaternary ammonium salts represented by U.S. Pat. No. 4,434,29, US Pat. Nos. 2,494,903 and 3,128,182.
No. 4,230,796, 3,253,919
No. 4, Japanese Patent Publication No. 41-11431, US Pat. No. 2,48
2,546, 2,596,926 and 3,58
Amine compounds described in 2,346, etc., JP-B-37-
16088, 42-25201, U.S. Pat.
128,183, Japanese Patent Publication Nos. 41-11431, 42
-23883 and U.S. Pat. No. 3,532,501 and the like, polyalkylene oxides, other 1-phenyl-3-pyrazolidones, imidazoles, and the like can be added as necessary.

In the present invention, any antifoggant can be added, if desired. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 Typical examples include nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adanine.

After color development, desilvering processing is performed. In the desilvering process, the bleaching process and the fixing process may be performed separately,
It may be performed at the same time (bleach-fixing process). In the mode of the desilvering process in the present invention, a bleach-fixing process is preferable for the purpose of simplifying the process and shortening the time. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose.

Examples of the bleaching solution used in the bleaching solution or the bleach-fixing solution include iron salts; compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II); peracids. Quinones; nitro compounds and the like. Typical bleaching agents are iron chloride; ferricyanide; dichromate; iron (I
II) organic complex salts (for example, metal complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid) Persulfate; bromate; permanganate; nitrobenzenes and the like. Of these, iron ethylenediamine tetraacetate
(III) Complex salt, and iron 1,3-diaminopropane tetraacetate (I
II) Complexing salts and other iron (III) aminopolycarboxylic acid complex salts are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. A bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is used at a pH of 3-8.

Known additives such as rehalogenating agents such as ammonium bromide and ammonium chloride; pH buffering agents such as ammonium nitrate; metal corrosion inhibitors such as ammonium sulfate are added to the bleaching solution and the bleach-fixing solution. be able to. In the bleaching solution and bleach-fixing solution, in addition to the above compounds,
It is preferable to contain an organic acid for the purpose of preventing bleach stain. A particularly preferred organic acid has an acid dissociation constant (pK
a) is a compound of 2 to 5.5, and specifically, acetic acid, propionic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. It is also preferable to use a combination of a thiosulfate and a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, in the fixing solution and the bleach-fixing solution, various aminopolycarboxylic acids and organic phosphonic acids (for example, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N ', N') are used for the purpose of stabilizing the solution. -Ethylenediaminetetraphosphonic acid) is preferred.

The fixing solution and the bleach-fixing solution may further contain various fluorescent whitening agents, defoaming agents, surfactants, polyvinylpyrrolidone, methanol and the like. Bleach,
If necessary, a bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof. Specific examples of useful bleaching accelerators include U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
And Research Disclosure No. 17129 (July 1978) and the like having a mercapto group or a disulfide bond;
Thiazolidine derivatives described in No. 29; US Pat. No. 3,7
Thiourea derivatives described in JP-A No. 06,561;
Iodide salt described in 16235; West German Patent No. 2,74
The polyoxyethylene compounds described in No. 8,430; the polyamine compounds described in JP-B-45-8836; the bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
Compounds described in US Pat. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material.

The total time of the bleaching / fixing step in the present invention is preferably as short as possible in order not to cause defective desilvering for the purpose of shortening the processing time. The preferred time is 5 seconds to 1 minute, more preferably 5 seconds to 25 seconds. The processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the generation of stains after the processing is effectively prevented. Further, in the treatment step of the present invention, the stirring method in each step may be applied by any known method, but it is preferable that the stirring is strengthened as much as possible. As a concrete method for strengthening stirring, JP-A-62-183460,
No. 62-183461, a method of colliding a jet of a processing liquid with the emulsion surface of a light-sensitive material, and JP-A-62-18343.
A method of increasing the stirring effect by using the rotating means of No. 61, and further moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface to make the emulsion surface turbulent, thereby further improving the stirring effect. There are a method of improving the method and a method of increasing the circulation flow rate of the whole processing solution. Such a stirring improving means is effective in any of a developing solution, a bleaching solution, a bleach-fixing solution, a fixing solution, a washing solution and / or a stabilizing solution. Further, in each of the above processing liquids used in the present invention, for example, JP-A-62-183460, specification 3
The method described in the lower right column of page to the lower right column of page 4 in which the liquid pumped by a pump is discharged from a slit or nozzle provided facing the emulsion surface can be applied. Further, the treatment of the present invention has a relatively excellent performance in any state of the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] as compared with the combinations other than the present invention,
From the viewpoint of stability of liquid components, the liquid opening ratio is 0 to 0.1 cm.
^-1 is preferred. In continuous processing, practically 0.0
The range of 01 cm ^{-1 to} 0.05 cm ^-1 is preferable, and 0.002 to 0.03 cm ^-1 is more preferable.

The color light-sensitive material of the present invention generally undergoes a washing step after desilvering. A stable process may be performed instead of the water washing process. In such stabilization treatment, JP-A-57-8543, JP-A-58-14834,
All the known methods described in JP-A-60-220345 can be used. In addition, a washing process-stabilizing process may be performed in which a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. For the washing and stabilizing solutions,
A water softening agent such as inorganic phosphoric acid, polyaminocarboxylic acid or organic aminophosphonic acid; a metal salt such as Mg salt, Al salt or Bi salt; a surfactant; a hardener and the like can be contained.

The amount of rinsing water in the rinsing step depends on the characteristics of the light-sensitive material (for example, depending on the material used such as the coupler), the application, and the temperature of the rinsing water, the number of rinsing tanks (number of stages), replenishment system such as countercurrent and forward flow, and various other types. It can be set in a wide range depending on the condition. Further, as a solution to the problems such as the propagation of bacteria and the adherence of the produced suspension to the light-sensitive material, which occurs when the amount of washing water is greatly reduced in the multi-stage countercurrent system, Japanese Patent Laid-Open Publication No. Sho 6-62 has been proposed.
The method of reducing calcium ion and magnesium ion described in 2-288838 can be used very effectively. Also, isothiazolone compounds, siabendazoles, chlorine-based bactericides such as chlorinated sodium isocyanurate described in JP-A-57-8542, and benzotriazole, etc., Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents"
(1986) Sankyo Publishing, edited by Hygiene Engineering Society, "Microbial sterilization, sterilization, antifungal technology" (1982) Industrial Technology Association, edited by Japan Society for Antibacterial and Antifungal, "Encyclopedia of Antibacterial and Antifungal Agents" (1986) The disinfectants described can also be used.

The washing water has a pH of 4 to 9, preferably 5 to 8. The washing water temperature and washing time can be set variously depending on the characteristics of the light-sensitive material, application, etc., but generally 15 to 45 ° C.
At 10 seconds to 5 minutes, preferably at 35 to 45 ° C. for 10 seconds to 9
A range of 0 seconds is selected. Examples of dye stabilizers that can be used in the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. In addition, other stabilizing agents include boric acid and pH adjusting buffers such as sodium hydroxide;
1-Hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid; an antisulfurizing agent such as an alkanolamine; an optical brightening agent; a mildewproofing agent and the like can be contained. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration. In the present invention, the washing and / or stabilizing water treated with a reverse osmosis membrane can be effectively used. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide,
Polyether, polysulfone, polyacrylic acid, polyvinylene carbonate, etc. can be used.

The liquid feeding pressure in the use of these membranes is preferably ^{2 to} 10 kg / cm ² , and particularly preferably ^{3 to} 7 kg / cm ² because of the stain-preventing effect and the reduction of permeated water amount.
It is cm ^2. The washing and / or stabilizing step is preferably connected in a multi-stage countercurrent system using a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks.

The treatment with the reverse osmosis membrane is preferably carried out on the water from the second tank onward of such multistage countercurrent washing and / or stabilization. Specifically, in the case of a two-tank configuration, the water in the second tank is treated and permeated with a reverse osmosis membrane in the second or third tank in the case of a three-tank configuration and the water in the third or fourth tank in a four-tank configuration. Same water tank (Tank for collecting water for reverse osmosis membrane treatment; hereinafter referred to as “collection tank”)
Alternatively, it is carried out by returning to a washing and / or stabilizing tank located thereafter. Furthermore, concentrated washing and /
Alternatively, one of the measures is to return the stabilizing solution to the bleach-fixing bath upstream of the sampling tank.

A color developing agent may be incorporated in the color light-sensitive material of the present invention for the purpose of simplifying and accelerating the processing, and it is preferable to use various precursors of the color developing agent for incorporation. For example, indoaniline compounds described in U.S. Pat. No. 3,342,597, and No. 3,342,59.
No. 9, RD magazine Nos. 14850 and 15159, Schiff base type compounds, Aldol compounds described in No. 13924, metal salt complexes described in US Pat. No. 3,719,492, JP The urethane compounds described in JP-A-53-135628 can be mentioned. The color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. A typical compound is JP-A-56-64339.
No. 57-144547 and No. 58-11543.
No. 8 etc.

Next, the photosensitive material relating to the present invention will be described in detail. Examples of the light-sensitive material relating to the present invention include color light-sensitive materials and black-and-white light-sensitive materials. Examples of the former include color photographic paper, direct positive color photosensitive material, color negative film and the like, and examples of the latter include photosensitive material for printing and film for X ray.
The present invention can achieve the above effects more remarkably in the case of a color light-sensitive material, particularly when using a light-sensitive material for printing such as color printing paper. Hereinafter, the color photosensitive material will be mainly described in detail.

In the color light-sensitive material of the present invention, at least one yellow color forming silver halide emulsion layer, magenta color forming silver halide emulsion layer and cyan color forming silver halide emulsion layer are coated on a reflective support. Can be configured. In general color photographic paper, color reproduction by the subtractive method can be carried out by using a color coupler which forms a dye having a complementary color to the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color-forming layers described above, and on the support in the order described above. It can be constructed by coating. However, the order may be different from this. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

The silver halide grains used in the light-sensitive material preferably contain substantially no silver iodide in order to shorten the development processing time. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less (including zero), preferably 0.2 mol% or less (including zero). On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing storage stability of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains,
The so-called uniform structure grains having the same composition in any part of the silver halide grains, or the cores inside the silver halide grains and the surrounding shells (single or multiple layers) have different halogen compositions. A so-called layered structure grain or a structure having a non-layered portion having a different halogen composition inside or on the surface of the grain (in the case of being on the grain surface, a structure in which a portion having a different composition is bonded to the edge, corner or face of the grain) Particles and the like can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion preferably has a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grain in a layered or non-layered manner as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and preferably 20 mol%.
It is more preferable that the number exceeds. The silver bromide content of the localized silver bromide phase is analyzed by using an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis” Maruzen). can do. And these localized phases can be inside the particle, on the edge of the particle surface, on the corner or on the surface, but as one preferable example,
One that can be cited is one that is epitaxially grown at the corner portion of the grain.

The average grain size of the silver halide grains contained in the silver halide emulsion used for the above-mentioned light-sensitive material (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. .1 μ to 2 μ is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is regular, such as cubic, tetradecahedral or octahedral.
Those having a (regular) crystal form, those having an irregular (eg regular) crystal form such as spheres and plates, or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% or more, preferably 7% or more of the particles having the above-mentioned regular crystal form are used in the present invention.
It is preferable to contain 0% or more, more preferably 90% or more. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P. Glafki.
des by Chimie et Phisique Photographique (Paul Mont
published by el, 1967), by GF Duffin Photographic Em
ulsion Chemistry (Focal Press, 1966), V.
Making and Coating Photographic by L. Zelikman et al
It can be adjusted using the method described in Emulsion (Focal Press, 1964) and the like. That is,
Any method such as an acidic method, a neutral method or an ammonia method may be used.As a method of reacting the soluble silver salt and the soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. Is also good. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

The localized phase of the silver halide grain of the present invention or its substrate preferably contains a different metal ion or its complex ion. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Ions or their complex ions mainly selected from iridium, rhodium, iron etc. in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. as the substrate. Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of silver salt or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. It is contained in the localized phase and / or other particle portion (matrix). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion in the light-sensitive material according to the present invention is usually chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface. The silver halide emulsion used in the light-sensitive material according to the present invention contains various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. The body can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the photosensitive material according to the present invention,
Examples of spectral sensitizing dyes used for spectral sensitization in the blue, green, and red regions include Heterocyclic compounds- by FM Harmer.
Cyanine dyes and related compounds (John Wiley & S
Ons New York, London, Inc., 1964). Specific examples of compounds and the spectral sensitization method are described in the above-mentioned JP-A-62-215272.
The compounds described on page 22, right upper column to page 38 of the publication are preferable, and more preferable compounds among them are (S-1) to (S-19) and (S-21) in the specific compound examples.
(S-23) to (S-38), (S-40) to (S-4
4), (S-46) to (S-48), (S-51),
(S-53), (S-55) to (S-58), (S-6
0), (S-62), (S-63), (S-66),
(S-68), (S-71) to (S-83), (S-8
5) to (S-90) and the like, which do not have a carboxy group in the molecule. Further, as the red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, the spectral sensitizing dye described in JP-A-3-123340 is stable, has strong adsorption, and has an exposure temperature. It is very preferable from the viewpoint of dependency.

In the case of efficiently spectrally sensitizing the infrared region of the light-sensitive material of the present invention, JP-A-3-15049-1.
Page 2, upper left column to Page 21, lower left column, or JP-A-3-207
No. 30, page 4, lower left column, to page 15, lower left column, EP-0, 420,
011 page 4, line 21 to page 6, line 54, EP-0,420,
012, page 4, line 12 to page 10, line 33, EP-0,44
The sensitizing dyes described in 3,466 and US-4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-
As described in 22089 and the like, an acid or a base is allowed to coexist to prepare an aqueous solution, and as described in U.S. Pat. No. 3,822,135 and U.S. Pat. It may be added to the emulsion. Further, after being dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, it may be dispersed in water or a hydrophilic colloid and added to the emulsion. JP-A-53-102733, JP-A-58-105141
Alternatively, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before the application, but is described in US Pat.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A No. 628969 and No. 4225666.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. adding some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation, including the method taught in US Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the photosensitive material according to the present invention,
In particular, when using a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region, it is preferable to use the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column. By using these compounds, the storability of the light-sensitive material, the processing stability, and the supersensitizing effect can be specifically enhanced. Among them, the general formulas (IV), (V) and (V
It is particularly preferable to use the compound of I) in combination. These compounds are 0.5 × 10 ^-5 per mol of silver halide.
Mol to 5.0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵
The sensitizing dye 1 is used in an amount of mol to 5.0 × 10 ⁻³ mol.
0.1 times to 10,000 times, preferably 0.5 times per mol
There is an advantageous amount of use in the range of 2 times to 5000 times.

It is preferable that gelatin is used as a protective colloid in the photographic constituent layers of the light-sensitive material of the present invention. The gelatin may be either acid-treated or lime-treated. Details of the method for producing gelatin are described in Arthur Weiss, The Macromolecular Chemistry of Gelatin (Academic Press, 1964). In order to obtain the effects of the present invention, it is preferable to use lime-processed gelatin having an isoelectric point of 5.2 or less. In the light-sensitive material of the present invention, the amount of lime-processed gelatin as described above is 1.0 g / m ² or more, 8.0 g / m ² or more.
It is preferably ² or less, more preferably 4.0.
It is at least g / m ² and at most 7.0 g / m ² .

In one of the most preferable embodiments of the present invention, the non-photosensitive uppermost hydrophilic colloid has an isoelectric point of 6.
An acid-treated gelatin of 0 or more, more preferably 6.5 or more, a protective colloid of the other layer is a lime-treated gelatin having an isoelectric point of 5.2 or less, and a total gelatin coating amount of 5.0 g / m 2. ^{It is 2} or more and 7.0 g / m ² or less.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. A preferred gelatin has a calcium content of 800 pp in order to suppress the occurrence of pressure desensitizing streaks in continuous processing.
It is preferable to use low calcium gelatin of m or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

Upon exposure, US Pat. No. 4,880,7
It is preferable to use the band stop filter described in No. 26. As a result, light color mixture is removed, and color reproducibility is significantly improved. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing this light-sensitive material. As an additive,
The following patent publications, in particular European patent EP 0,355,660
Those described in the specification of A2 (JP-A-2-139544) are preferably used.

[0117]

[Table 11]

[0118]

[Table 12]

[0119]

[Table 13]

[0120]

[Table 14]

[0121]

[Table 15]

Cyan, magenta, or yellow couplers are impregnated into rollable latex polymers (eg, US Pat. No. 4,203,716) in the presence (or absence) of high boiling organic solvents described in the table above. Then, it is preferable to dissolve in a polymer soluble in an organic solvent and to emulsify and disperse in a hydrophilic colloid aqueous solution. The water-insoluble and organic solvent-soluble polymers which can be preferably used are, for example, columns 7 to 15 of US Pat. No. 4,857,449 and page 12 of WO88 / 00723.
The homopolymer or copolymer described on page 30 can be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, particularly acrylamide-based polymer, from the viewpoint of color image stability and the like.

In the light-sensitive material of the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0277589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler or a pyrrolotriazole coupler. That is, by chemically bonding with the aromatic amine-based developing agent remaining after color development processing,
A compound chemically bonded to the compound in the above-mentioned patent specification which produces a substantially colorless compound and / or an oxidant of an aromatic amine color developing agent remaining after the color developing treatment It is possible to use the compounds in the above-mentioned patent specification, which form an inactive and substantially colorless compound, simultaneously or alone, for example, the reaction of the coupler with the residual color developing agent in the film or its oxidant and the coupler during storage after processing. It is preferable for preventing the occurrence of stains and other side effects due to the formation of the coloring pigment.

As the cyan coupler, in addition to the compounds shown in the above table, diphenylimidazole type cyan couplers described in JP-A-2-33144 and 3-hydroxypyridine type cyanides described in European Patent EP0333185A2. Couplers and JP-A-64-32260
Cyclic active methylene type cyan couplers described in Japanese Patent Publication No. EP 0456226A1 and pyrrolopyrazole type cyan couplers described in European Patent No. EP 0456226A1.
Pyrroloimidazole type cyan couplers described in 84909, European Patent Nos. EP0488248 and EP0.
The use of pyrrolotriazole type cyan couplers described in 491197A1 is preferred. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969 may be used.
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, US Pat. The acylacetamide type yellow coupler having a dioxane structure described in 118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group, or a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

As the magenta couplers, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the above-mentioned publicly known documents are used. JP-A-61-65245, wherein a pyrazolotriazole coupler having a secondary or tertiary alkyl group directly bonded to the 2, 3 or 6 position of the pyrazolotriazole ring is disclosed in JP-A-61-65245.
Pyrazoloazole couplers containing sulfonamide groups in the molecule as described in JP-A-65246;
Pyrazoloazole couplers having an alkoxyphenyl sulfonamide ballast group as described in US Pat. No. 147,254, EP Patent Nos. 226,849A and 294,
It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No. 785.

As the processing method of the present invention, in addition to the methods described in the above table, page 26, lower right column, line 1 to page 34, upper right column, line 9 of JP-A-2-207250 and JP-A-4-973.
The processing materials and processing methods described in No. 55, page 5, upper left column, line 17 to line 18, lower right column, line 20 are preferable. As the developing agent, compounds (I-1) to (I described in JP-A-4-443 are used.
It is also preferable to use -13). The bleach-fix solution used in the present invention preferably has a pH of 4 to 7, and more preferably pH 4.5 to 5.5. A pH of 4.5 or less is not preferable because the liquid stability tends to be poor, and a pH of 5.5 or more is not preferable because the desilvering property tends to be poor.

The supply form of the treating agent used in the present invention is as follows:
It may be in any form such as a concentrated or concentrated liquid preparation, a granule, a powder, a tablet, a paste or an emulsion. As an example of such a treating agent, JP-A-63-1
7453 describes a liquid agent stored in a container with low oxygen permeability.
No. 4-19655 and No. 4-230748, vacuum packed powders or granules, No. 4-211951 include granules containing a water-soluble polymer, JP-A-51-61837 and JP-A-6-102628. Is a tablet,
Japanese Laid-Open Patent Publication No. 57-500485 discloses a paste-type treatment agent, and any of them can be preferably used. However, from the viewpoint of ease of use, use a liquid that has been adjusted in advance according to the concentration at the time of use. It is preferable. Containers containing these treatment agents include polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, etc.
Used alone or as a composite material. These are selected according to the level of oxygen permeability required. For a liquid such as a color developing solution which is easily oxidized, a material having low oxygen permeability is preferable, and specifically, polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. It is preferable that these materials have a thickness of 500 to 1500 μm, are used in a container, and have an oxygen permeability of 20 ml / m ² · 24 hrs · atm or less.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer, but also in a solid state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as an excitation light source and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high density light such as a second harmonic generation light source (SHG) combined with an optical crystal. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus which is compact, inexpensive, has a long life and high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser with a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three regions of blue, green and red. In order to use a semiconductor laser as a light source in order to make the device inexpensive, highly stable and compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. This is because currently available inexpensive and stable III-V semiconductor lasers have emission wavelengths only in the red to infrared regions. However, at the laboratory level, the oscillation of II-VI group semiconductor lasers in the green and blue regions has been confirmed, and if semiconductor laser manufacturing technology is developed, these semiconductor lasers can be used inexpensively and stably. It is fully expected. In such a case, it is less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

An embodiment of a silver salt photographic color paper processor which can be used for carrying out the method of the present invention will be described below with reference to the drawings, but the present invention is limited to this embodiment. It is not something that will be done. FIG. 1 is an explanatory view showing an example of this silver salt photographic color paper processing machine. This processor is for developing an image on a color paper by developing, bleach-fixing, washing with water and drying (omitted in FIG. 1) a web-shaped color paper exposed based on a positive original. A color paper (hereinafter referred to as a light-sensitive material) processed by this processing machine is a color photographic light-sensitive material having at least one layer of a silver halide emulsion containing 95 mol% or more of a silver chloride salt on a support. Color development is performed with a color developing solution containing a group 1 primary amine color developing agent.

FIG. 1 shows a light-sensitive emulsion layer of a light-sensitive material which can be adapted to the upper side. The processor main body 10 is provided with a developing tank 12, a bleach-fixing tank 14, and washing tanks 16a to 16e. The exposed light-sensitive material 20 is developed, bleach-fixed, washed with water, and then carried out of the main body 10 (not shown in FIG. 1, but subsequently dried in a drying section). The light-sensitive material 20 is processed by being dipped in the processing liquid for a predetermined time while being nipped and carried by the carrying roller pair 24 with the emulsion surface facing down. In the present invention, the development processing time is preferably 30 seconds or less. Further, it is preferable that the time from the start of development to the end of drying is 100 seconds or less, and the conveying speed of the photosensitive material is 13 to 55 mm / second.

The wall of each tank and the block 29 are provided with a circulating liquid spray nozzle (circle having a diameter of 1 mm) for stirring the photosensitive material. In the developing tank 12 and the bleach-fixing tank (desilvering tank 14), as shown in FIG. 1, the developing solution for circulation is extracted from the developing tank 12 and separated into the first half and the second half of the apparatus via a pump 31. The liquid is sent to the blowing nozzle 32, and the developing liquid is sprayed from a direction perpendicular to the emulsion surface of the photosensitive material 20 being conveyed. The blowing nozzle 32 is a circle having a diameter of 1 mm, and for example, a nozzle having a total of 18 per 1 cm is used. Similarly, in the washing tanks 16b to 16e, a spray nozzle is provided between the blade outlet and the roller. In the developing tank 12 and the bleach-fixing tank 14, it is necessary that at least one of the blowing nozzles blows from the upper side or the lower side, but the blowing nozzles may blow from both. In addition, it is preferable that the washing tanks 16b, 16c, 16d and 16e are basically blown from both upper and lower sides.

The washing tanks 16a to 16e are transferred in the liquid through a blade 28 provided on the wall of the tank. Although various plastic materials can be used for this submerged blade, polyurethane rubber is particularly preferable from the viewpoint of elasticity and durability for liquid sealing. Blocks 29 are arranged at various places in each tank in order to prevent the photosensitive material 20 from being clogged. Five washing tanks 16a to 16e are arranged, and each layer is cascade-piped, and the last-stage tank 16e
From this point, the cleanliness of the wash water gradually decreases from the frontmost tank 16a. Reverse osmosis membrane (RO membrane) device 26 is used for the washing layer
The pump 30 pumps the water in the fourth washing tank 16d to the reverse osmosis membrane device 26, and the clean permeated water that has passed through the reverse osmosis membrane device 26 is supplied to the fifth washing tank 16e.
The concentrated water that has not passed through the reverse osmosis membrane device 26 is supplied to the fourth washing tank 16d. The same reference numerals are used for the respective tanks in FIG. The effects of the present invention are particularly remarkable for small and medium-sized automatic processors. In that case, for example, the width of the photosensitive material to be processed is 20 cm or less, and even if holes are made at intervals of 1 cm, a maximum of about 18 outlets will be formed. If the blowing area is too large, the blowing speed will decrease, but in the above machine for processing the width of the photosensitive material, a water flow having a sufficient strength is formed.

FIG. 2 shows another mode of the liquid spraying section of the processor to which the present invention is applied. In FIG. 2, a spray nozzle 40 having a blowout port 41 is incorporated in a rack in which the sensitive material 20 is conveyed, and the developing solution is perpendicular to the emulsion surface of the sensitive material from the blowout ports 41 arranged on both sides of the spray nozzle 40. Spray the circulating fluid of. The photosensitive material 20 is conveyed in the direction of the arrow shown. Although the shape of the air outlet 41 is elliptical in FIG. 2, a plurality of small circles may be laid out. Here, the nozzle in the first half of the developing tank is the one in the front of the drawing.

Further, in order to adjust the amount of the sprayed liquid, a blowing jam member 42 may be mounted on the entire surface of the blowing port 41 between the blowing port 41 and the conveyed photosensitive material 20. The mounting member 42 not only improves the amount of spraying and the uniformity, but also has a merit in terms of maintenance because it can be removed. The form of this blowing member 42 is
Any one may be used as long as the flow rate of the liquid flowing out can be adjusted, but as shown in FIGS. 2 and 3, a mesh-like one, a large number of small holes, and a large number of elliptical holes. Etc.

As another mode of this blowing member 42, as shown in FIG. 4, it is possible to install a vane-shaped guide 43. The arrow in FIG. 4 indicates the conveying direction of the photosensitive material. As such a blowing member 42, an organic compound, an inorganic compound, and a metal can be used, and it is preferable that the blowing member 42 be molded and processed into a mesh shape before use.

[0139]

【Example】

Example 1 (Preparation of Support) For low density polyethylene with MFR = 3,
Titanium dioxide was added at the ratio shown in Table 16, and zinc stearate was added at a ratio of 3.0% by weight based on the amount of titanium dioxide, and was added together with ultramarine blue (Daiichi Kasei Kogyo DV-1) in a Banbury mixer. After kneading, it was molded into pellets to form a masterbatch. The titanium dioxide used was 0.15 μm to 0.35 μm with an electron microscope, and the coating amount of hydrated aluminum oxide was 0.75 wt% based on titanium dioxide in terms of Al ₂ O ₃ . After a corona discharge treatment of 10 kVA on a paper substrate having a basis weight of 170 g / m ² , melt extrusion was performed at 320 ° C. using a multilayer extrusion coating die to form a polyethylene laminate layer having a film thickness shown in Table 16. The surface of this polyethylene layer was subjected to glow discharge treatment.

[0140]

[Table 16]

(Preparation of Photosensitive Material 100) Various photographic constituent layers were coated on the above reflective support (A) to prepare a multilayer color photographic paper (100) having the following layer constitution. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 153.0 g, color image stabilizer (Cpd-1) 15.0 g, color image stabilizer (Cpd-2)
7.5 g, color image stabilizer (Cpd-3) 16.0 g, solvent (Solv-1) 25 g, solvent (Solv-2) 25
g and 180 cc of ethyl acetate, and the solution is 10%
An emulsified dispersion A was prepared by emulsifying and dispersing in 60 cc of sodium dodecylbenzenesulfonate and 1000 cc of 10% gelatin aqueous solution containing 10% of citric acid.

On the other hand, silver chlorobromide emulsion A {cubic, 3: 7 mixture of large size emulsion A with average grain size 0.88 μm and small size emulsion A with 0.70 μm (silver molar ratio), grain size distribution The coefficient of variation was 0.08 and 0.10 respectively, and each size emulsion contained 0.3 mol% of silver bromide localized on a part of the grain surface}. In this emulsion, the blue-sensitive sensitizing dyes A, B, and C shown below were added in an amount of 1.4 × 10 ⁻⁴ mol per mol of silver, and 1.4 × 10 ⁻⁴ mol per mol of the large-sized emulsion A, respectively.
For small size emulsion A, 1.7 × 10 ⁻⁴ for each.
Mol is added. The chemical ripening of this emulsion was performed by adding a sulfur sensitizer and a gold sensitizer. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the following composition. The emulsion coating amount was expressed in terms of silver amount. Preparation of Second Layer to Seventh Layer Coating Liquid The coating liquids for the second to seventh layers were also prepared in the same manner as the first layer coating liquid. The coating liquid for each layer described above was applied onto a support to prepare a sample of a light-sensitive material having the latter layer structure. Further, Cpd-14 and Cpd-15 were added to each layer so that the total amounts were 25.0 mg / m ² and 50.0 mg / m ² , respectively. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0144]

[Chemical 12]

(1.4 × 10 ^-4 mol each was added to the large-sized emulsion or 1.7 × 10 ^-4 mol each to the small-sized emulsion, per mol of silver halide) Sensitive emulsion layer

[0146]

[Chemical 13]

(Sensitizing dye D per mol of silver halide was 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide was 4.0 × 10 ⁻⁵ mol for large size emulsion and 7.0 for small size emulsion.
^{X10 -5} mol, and sensitizing dye F per mol of silver halide was 2.0 x 10 ^-4 mol for a large size emulsion and 2.8 x 10 ^-4 for a small size emulsion. Mol added. ) Red-sensitive emulsion layer

[0148]

Embedded image

(Sensitizing dye G per mol of silver halide was 5.0 × 10 ⁻⁵ mol for large size emulsion, 6.0 × 10 ⁻⁵ mol for small size emulsion, and Sensitizing dye H was added per mol of silver halide in an amount of 5.0 × 10 ^-5 mol for the large-sized emulsion and 6.0 × 10 ^-5 mol for the small-sized emulsion.) 1. The compound of 1 is used per mol of silver halide.
6 × 10 ⁻³ mol was added.

[0150]

[Chemical 15]

For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
8.5 × 10 ⁻⁵ moles, 9.0 × 10 ⁻⁴ moles per mole,
2.5 × 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.

(Layer Constitution) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper (A) [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First layer (blue-sensitive emulsion layer) Blue-sensitive silver chlorobromide emulsion 0.27 Gelatin 1.36 Yellow coupler (ExY) 0.79 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image Stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-5) 0.04 Solvent (Solv-1) 0.13 Solvent (Solv-2) 0.13

Second Layer (Color Mixing Prevention Layer) Gelatin 1.00 Color mixing inhibitor (Cpd-16) 0.08 Solvent (Solv-1) 0.10 Solvent (Solv-2) 0.15 Solvent (Solv-3) 0.25 Solvent (Solv-8) 0.03

Third Layer (Green Sensitive Emulsion Layer) Silver Chlorobromide Emulsion B-1 (cubic, 1: 3 mixture of large size emulsion having average grain size 0.55 μm and small size emulsion 0.39 μm (silver) The molar coefficient of variation of the particle size distribution is 0.
08 and 0.06, silver bromide 0.8 mol% for each size emulsion
Was locally contained in a part of the surface of the grain based on silver chloride. Furthermore, potassium hexachloroiridium (IV) acid was added to the inside of the grain and the silver bromide localized phase in an amount of 0.
1 mg and 1 mg of potassium ferrocyanide were combined. ) 0.13 Gelatin 1.45 Magenta coupler (ExM) 0.16 UV absorber (UV-2) 0.16 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-5) 0.10 Color image stabilizer (Cpd-6) 0.01 color Image stabilizer (Cpd-17) 0.01 Color image stabilizer (Cpd-8) 0.08 Color image stabilizer (Cpd-19) 0.02 Solvent (Solv-3) 0.13 Solvent (Solv-8) 0.39 Solvent (Solv-9) 0.26

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.70 Color mixing inhibitor (Cpd-16) 0.06 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.11 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.02

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C-1 (cubic, 1: 4 mixture of a large size emulsion having an average grain size of 0.50 μm and a small size emulsion of 0.41 μm (silver) The molar coefficient of variation of the particle size distribution is 0.
09 and 0.11, silver bromide 0.8 mol% for each size emulsion
Was locally contained in a part of the surface of the grain based on silver chloride. Furthermore, potassium hexachloroiridium (IV) acid was added to the inside of the grain and the silver bromide localized phase in an amount of 0.
1.5 mg including 3 mg and potassium ferrocyanide
It was included in mg. ) 0.18 Gelatin 0.85 Cyan coupler (ExC) 0.33 UV absorber (UV-4) 0.18 Color image stabilizer (Cpd-1) 0.33 Color image stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 color Image stabilizer (Cpd-18) 0.02 Color image stabilizer (Cpd-19) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0.22

Sixth layer (UV absorbing layer) Gelatin 0.60 UV absorbing agent (UV-3) 0.39 Color image stabilizer (Cpd-5) 0.01 Color image stabilizer (Cpd-17) 0.05 Solvent (Solv-10) 0.05

Seventh layer (protective layer) Gelatin 1.0 Acrylic modified copolymer of polyvinyl alcohol (degree of modification
17%) 0.05 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0160]

Embedded image

[0161]

[Chemical 17]

[0162]

Embedded image

[0163]

[Chemical 19]

[0164]

Embedded image

[0165]

[Chemical 21]

[0166]

[Chemical formula 22]

[0167]

[Chemical formula 23]

Further, in the color photographic paper (100), the photographic papers (101) to (1) having the same constitution except that the irradiation preventing dye is added to the sixth layer as shown in Table 17.
08) was produced. However, the following dyes were used for comparison.

[0169]

[Table 17]

[0170]

[Chemical formula 24]

Using the following processing steps and color developing solution, continuous processing was carried out using the exposed printing paper (101) until the tank volume of the color developing solution was replenished.

Processing process Temperature Time Replenishment amount Tank capacity (liter) Color development 45 ° C 30 seconds 35 ml 2 Bleach fixing 40 ° C 15 seconds 35 ml 1 Rinse 35-40 ° C 4.2 seconds-0.5 Rinse 35-40 ° C 2.6 seconds-0.5 Rinse 35-40 ° C 2.6 seconds − 0.5 Rinse 35-40 ° C 2.6 seconds − 0.5 Rinse 35-40 ° C 4.2 seconds 60 ml 0.5 Dry 80 ° C 13 seconds (Rinse → 5 tank countercurrent method)

The above processing time was determined by using the processing apparatus shown in FIG. 1 and determining the transport speed from the transport distance of each layer. However, in the bleach-fixing process, a carrying rack having a carrying distance of 1/2 of the developing process was used. In the above treatment, the rinse water was pumped through the reverse osmosis membrane, the permeated water was supplied to the rinse, and the concentrated water that did not pass through the reverse osmosis membrane was returned to the rinse for use. In addition, in order to shorten the crossover time between each rinse,
A blade was installed between the tanks, and the photosensitive material was passed between them.
In each step, the circulating liquid was sprayed by using the apparatus shown in the above embodiment and setting the spraying rate to 4 to 6 liters / min per tank.

Color developing solution (CD-1) Tank solution Replenishing solution Water 700 ml 700 ml Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6 -Disulphonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 15.8 g-Potassium bromide 0.04 g-Potassium carbonate 27.0 g 27.0 g Sodium sulfite 0.1 g 0.1 g (organic preservatives Table 31 ) 18.0 g 35.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 7.0 g 21.0 g Optical brightener (SR-1) 5.0 g 6.0 g Water was added. 1000 ml 1000 ml pH (25 ℃) 10.35 12.8

(For each processing solution, the pH of the processing solution was set in the same manner as the tank solution of the color developing solution or the replenishing solution)

[0176]

[Chemical 25]

Bleach-fixing solution (a replenishing solution prepared by separating the components into two solutions was used.) [First replenishing solution] Water 150 ml Ethylenebisguanidine nitrate 30 g Ammonium sulfite monohydrate 226 g Ethylenediaminetetraacetic acid 7.5 g Fluorescence enhancement Whitening agent (SR-1) 1.0 g Ammonium bromide 30 g Ammonium thiosulfate (700 g / liter) 340 ml Water was added 1000 ml pH (25 ° C.) 5.82

[Second Replenisher] Water 140 ml Ethylenediaminetetraacetic acid 11.0 g Ethylenediaminetetraacetic acid iron (III) ammonium 384 g Acetic acid (50%) 230 ml Water is added 1000 ml pH (25 ° C.) 3.35 Tank for bleach-fixing solution Solution 1st replenisher 260ml 2nd replenisher 290ml Water is added 1000ml pH (25 ° C) 5.0 Replenishing amount of bleach-fixing solution (38ml per m ^{2 in the following} amount) 1st replenisher 18ml 2nd replenisher 20ml

Rinsing solution Ion-exchanged water (3 ppm each for calcium and magnesium)
Less than)

A3 size printing paper (10
The process of processing with 1) the imagewise exposure using a stretcher was repeated (this is referred to as a running process), and the total amount of the replenisher added to the developing step was used for each processing tank of the developing machine. 1 times the capacity (this is called 1 round)
Continued until. The running test was conducted with the above replenishment amount and color developer, and the processing amount of the light-sensitive material (m
² ) The replenishment amount per day is 0.5 to the developing tank capacity.
It was set to be within the range of 5%. By the above method, the running process is continuously performed for 25 days, and the average replenishment amount per day during that time is 1.7% of the developing tank capacity.
(This value is referred to as the replenishment volume ratio). In this test, the amount of waste liquid per 1 m ² of light-sensitive material was 4 m in the developing process.
1, the desilvering step was 33 ml, and the rinse step was 56 ml. (Evaluation of Minimum Density) The reflection density of yellow, magenta, and cyan of the processed photographic paper was measured immediately after the start of the running process and at the end of one round to obtain a characteristic curve to obtain the minimum density (D _min ). Further, the photographic sensitivity (S) was determined at the exposure amount at which the density on the characteristic curve was 0.5.
The D _min value and the S value were represented by ΔD _min and ΔS, which were obtained by subtracting the value immediately after the start of running from the value after the completion of one round. The ΔD _min value represents the amount of increase in stain during continuous processing, and the ΔS value represents the amount of change in photographic sensitivity during continuous processing (in the case of this embodiment, decreased sensitivity), both of which are preferably small.

Next, in the above running test, the photographic paper used was changed to (102) to (108), or the preservatives used for the developing solution and the developing replenisher were changed as shown in Table 18. I did a running test.
For comparison, the same running test was performed except that the spraying and stirring of the treatment liquid in all steps was changed as shown in Table 19. The above results are shown in Tables 18 and 19.

[0182]

[Table 18]

[0183]

[Table 19]

From the results shown in Table 18, when the color photographic paper of the present invention was used, ΔD _min in the running test was small, and the dye having the structure having an alkyl group in the pentamethine chain used in the photographic paper of the present invention and the dye The combination with the preservative of the invention showed particularly good results. Further, the combination of the color photographic paper of the present invention and the preservative had a small ΔS and was at a level capable of sensitivity correction by exposure, but the photographic paper of the present invention was not used or a preservative for comparison was used. In this case, since ΔS is large, the correction suitability due to exposure was insufficient. Further, from the results of Table 20, the effect becomes more remarkable by performing the spray stirring in the photographic printing paper and the treatment of the present invention, but it is difficult to obtain the remarkable effect of the spray stirring in the configuration for comparison. However, also in the constitution of the present invention, ΔS tends to increase when the circulation rate exceeds 10 liters / minute, and a preferable result is 10 liters / minute or less. From the above, by the simple and rapid processing method of the constitution of the present invention, a color print in which the stain is reduced and the fluctuation of the photographic sensitivity is smaller than in the conventional case can be obtained.

Example 2 The same running test as in Example 1 was carried out except that the preservative concentration of the replenishing solution for development and the average replenishing amount per day (replenishing volume ratio) were changed as shown in Table 20. However, the processing amount and the replenishing amount per day are controlled to be within ± 10%, and the total replenishing amount of the color developing solution is expressed as the average replenishing amount per day with respect to the developing solution volume. Defined as rate. The compound (II-5) was used as the preservative. Running tests and evaluations were performed in the same manner as in Example 1. The above results are shown in Table 20.

[0186]

[Table 20]

As is clear from the results shown in Table 20, the variation of D _min and sensitivity depending on the combination of the light-sensitive material of the present invention and the preservative is within the range of the preservative concentration in the replenisher of 40 to 150 mmol / liter. 20 to 20 indicates a preferable result.
On the contrary, when the concentration was outside the range of 0 mmol / liter, the tendency was worse. Furthermore, the combination of the photographic paper of the present invention and the preservative has an average replenishment amount (replenishment volume ratio) of 0.2 per day.
The improvement effect was most obtained within the range of 5 to 10%, but the performance was inferior under any condition in the comparative photographic paper.

Example 3 Table of Example 2 except that the fluorescent whitening agent (SR-1) used in the color developing solution was changed to the fluorescent whitening agents (SR-2) and (SR-4) for comparison. 20, a running test similar to Test 11 was performed. As a result, when the fluorescent whitening agent for comparison (SR-2) was used, ΔD _min was twice larger than the result of Test 11, and the effect of the present invention was not obtained. Further, when the comparative fluorescent whitening agent (SR-3) was used, ΔD _min was deteriorated, and the fluorescent whitening agent (SR-1) of the present invention was the best result.

[0189]

[Chemical formula 26]

Example 4 Using the reflective supports B and C described in Table 16, the coating amount of gelatin was changed (the coating amounts of the second layer, the fourth layer and the sixth layer described in Example 1 were coated). Table 17 except that
Photographic paper (40) similar to the photographic paper (105)
1) to (406) were produced.

[0191]

[Table 21]

Table 2 of Example 2 for these printing papers
The same running test as 0 and test 11 was performed.
However, the photographic paper was exposed by the following method. (Exposure) YAG solid-state laser (oscillation wavelength, 946 nm) with semiconductor laser GaAlAs (oscillation wavelength, 808.5 nm) as excitation light source was wavelength-converted by KNbO ₃ SHG crystal and extracted 473 nm, semiconductor laser GaAlAs (oscillation) YVO ₄ solid-state laser (oscillation wavelength, 1064 nm) with a pumping light source having a wavelength of 808.7 nm)
532 nm, AlGaInP (oscillation wavelength, about 670 nm: Toshiba No. TOLD9211 manufactured by Toshiba) was used after wavelength conversion with SHG crystal of KTP. The laser light is an apparatus capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. Using this apparatus, the light amount is changed to change the relationship between the density (D) of the photosensitive material and the light amount (E) D-1.
ogE was determined. At this time, the laser light of three wavelengths was modulated in light quantity using an external modulator to control the exposure quantity. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 5 × 10 ⁻⁸ seconds. The semiconductor laser uses a Peltier device to keep the temperature constant in order to suppress the fluctuation of the light quantity due to the temperature.

As a result of the running test, the same effects as in Example 2 were confirmed when the reflective supports B and C were used. Further, the smaller the gelatin coating amount was, the smaller ΔD _min and ΔS were, and good results were obtained.

Example 5 A color negative film (501) was prepared according to the method described in Example 4 of JP-A-6-329936. Further, color negative films (502) and (503) similar to (501) were prepared except that the support (cellulose triacetate) of the color negative film (501) was changed to polyethylene terephthalate and polyethylene naphtherate. After the color negative film (501) and the color paper (105) were imagewise exposed, continuous processing was performed in the following processing steps. In the color development processing, the film and the paper were processed separately, and a processing machine was prepared so that they could be processed in a common processing bath after the desilvering step. The average daily throughput was 0.2 m ² for the color negative film and 1.6 m ² for the color paper. Under these conditions, a running test was conducted until the tank was replenished with 1 times the capacity of the color developing tank (2 liters below). Next, the same running process was carried out except that the color negative film (501) was changed to (502) and (503), and the image of the obtained color paper was evaluated. As a result, when the color negative films (502) and (503) were used, there was less uneven stain on the processed photosensitive material, and the ΔD _min value of the color paper was low.

Treatment process Temperature Time Replenishment amount (ml) * Negative paper Negative paper Negative paper Color development 40 ℃ ---- 3'15 "---- 260 ---- Color development ---- 40 ℃- --30 "---- 40 Bleach fixing 38 ℃ 38 ℃ 3'00" 30 "520 50 Rinse ** 38 ℃ 38 ℃ 15" 10 "---- ---- Rinse 38 ℃ 38 ℃ 15" 10 "---- ---- Rinse 38 ℃ 38 ℃ 15" 10 "260 150 Dry 60 ℃ 70 ℃ 60" 60 "* Per square meter of photosensitive material ** Rinsing is a three-tank countercurrent method The carryover amount per square meter of the light-sensitive material was 60 ml in the case of color negative film and 40 ml in the case of color paper in each bath.

The composition of each processing liquid is as follows. [Color developer] Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 2.0 2.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 3.9 6.1 Potassium carbonate 37.5 39.0 Potassium bromide 2.0 --- Iodide Potassium 2.0 mg --- Hydroxylamine sulfate 2.4 4.0 2-Methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 4.5 11.0 Add water 1.0 liter 1.0 liter pH (hydroxylation Adjusted with potassium and sulfuric acid) 10.05 10.25

[Color developer] [Tank solution] [Replenisher] water 800 ml 800 ml ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g triethanol Amine 12.0 g 12.0 g Potassium chloride 11.5 g-Potassium bromide 0.03 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (SR-1) 2.0 g 5.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis ( Sulfonatoethyl) hydroxylamine 17.0 g 30.0 g Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline 3/2 Sulfuric acid monohydrate 6.3 g 22.0 g Water was added 1000 ml 1000 ml pH (25 ° C Potassium hydroxide and adjusted with sulfuric acid) 10.50 12.50

(Bleach-fixing solution) Tank solution (g) Replenishing solution (g) 1,2-cyclohexanediamine tetraammonium ferric ammonium monohydrate 130 195 Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / l) 200 ml 400 ml Imidazole 15 45 Ethylenediaminetetraacetic acid 5 5 Add water 1.0 liter 1.0 liter pH [Prepared with ammonia water and acetic acid] 6.0 5.45

(Rinse Solution) Tank Solution and Replenisher Solution (Unit: g) Tap water is used as H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas Co.) and OH-type strongly basic anion exchange resin ( Same amber light IR-40
0) packed in a mixed bed column to treat calcium and magnesium ions at a concentration of 3 mg / liter or less, and then 20 mg of sodium diisocyanurate dichloride /
L and 150 mg / L of sodium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5.

Example 6 A light-sensitive material (600) similar to (403) was prepared except that the following yellow coupler was used in the light-sensitive material described in Example 4. The same test as in Example 1 was carried out except that the following processing steps and processing solutions were used, and as a result, the effects of the present invention were obtained as in Example 1.

[0201]

[Chemical 27]

Treatment process Temperature Time Replenishment amount Tank capacity (liter) Color development 47 ° C 23 seconds 40 ml 2 Bleaching fixing 40 ° C 23 seconds 30 ml 1 Rinse 40-45 ° C 3.2 seconds-0.5 Rinse 40-45 ° C 2.0 seconds-0.5 Rinse 40-45 ° C 2.0 seconds −0.5 Rinse 40-45 ° C 2.0 seconds −0.5 Rinse 40-45 ° C 3.2 seconds 80 ml 0.5 Dry 80 ° C 10 seconds (Rinse → 5 tank countercurrent method)

For the above processing time, the processing speed shown in FIG. 1 was used to determine the transfer speed from the transfer distance of each tank. However, the transporting rack used in the bleach-fixing process had the same transporting distance as in the developing process. In each step, the circulating liquid was sprayed by using the apparatus shown in the above embodiment and setting the spraying amount to 4 to 5 liters / min per tank.

Color developing solution (CD-2) Tank solution Replenishing solution Water 700 ml 700 ml Sodium triisopropylnaphthalene (β) sulfonate 0.1 g 0.1 g Ethylenediaminetetraacetic acid 3.0 g 3.0 g 1,2-dihydroxybenzene-4,6 -Disulphonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 15.8 g-Potassium bromide 0.04 g-Potassium carbonate 27.0 g 27.0 g Sodium sulfite 0.1 g 0.1 g Organic preservative I-5 18.0 g 35.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 8.0 g 23.0 g Optical brightener (SR-1) 5.0 g 6.0 g Water was added to 1000 ml 1000 ml pH (25 ℃) 10.35 12.80

(For each processing solution, the pH of the processing solution was set in the same manner as the tank solution of the color developing solution or the replenishing solution)

Bleach-fixing solution Tank solution Replenishing solution Water 800 ml 600 ml Ammonium thiosulfate (750 g / l) 120 ml 240 ml Ammonium sulfite 30 g 65 g Ethylenediaminetetraacetic acid Ferric ammonium salt 0.11 mol 0.24 mol Ethylenediaminetetraacetic acid 0.01 mol 0.024 mol 3-Carboxyphenylsulfinic acid 0.1 mol 0.2 mol Maleic acid 0.1 mol 0.2 mol pH (at 25 ° C./nitric acid and ammonium water) 6.5 5.8

Rinsing solution Ion-exchanged water (calcium and magnesium 3 ppm each
Less than)

[0208]

EFFECTS OF THE INVENTION According to the present invention, in a simple and rapid continuous development process of a color photographic light-sensitive material, D
_It is possible to form a color image in which the increase of _min and the fluctuation of photographic sensitivity are reduced.

[Brief description of drawings]

FIG. 1 is an explanatory view showing one embodiment of a silver salt photographic color paper processor used for carrying out the present invention.

FIG. 2 is a perspective view of another example of the liquid spraying unit used in the processing machine of FIG.

FIG. 3 is a perspective view of another example of a baffle member attached to the liquid spraying portion of FIG.

4 is a cross-sectional view of another example of the liquid spraying unit used in the processing machine of FIG.

[Explanation of symbols]

 10 Processor Main Body 12 Development Tank 14 Bleach-Fixing Tank 16a, 16b, 16c, 16d, 16e Water Washing Tank 20 Photosensitive Material after Exposure 24 Conveying Roller Pair 26 Reverse Osmosis Membrane Device 28 Blade 29 Block 30, 31 Pump 32 Blowing Nozzle

Claims (4)

[Claims] 1. An image forming method comprising the steps of exposing a silver halide color photographic light-sensitive material to an image, and then subjecting it to color development, desilvering, stabilization and / or washing, followed by drying. At least one photosensitive silver halide emulsion layer containing silver halide having a silver chloride content of 95 mol% or more on one side, and at least one compound represented by the following general formula [Ia] And a compound of the following general formula [II]
It is carried out by processing with a color developing solution using a replenishing solution containing a concentration of 0 mmol / liter or more and 200 mmol / liter or less, and at least one step is 1 liter / liter.
A method for forming a color image, characterized in that the circulating processing solution is sprayed onto the emulsion layer coating side of the light-sensitive material at a rate of not less than 10 minutes and not more than 10 l / min. General formula [Ia] In the formula, R ₁ and R ₂ are Hammett's substituent constants σ _p, respectively.
Represents an electron-withdrawing group of 0.3 or more and 0.6 or less, and R ₃ , R
₄ represents a hydrogen atom, a halogen atom, a hydroxyl group, a methyl group or a methoxy group, respectively, and A is a carbon number of 1 to 1.
8 represents an alkyl group or an aryl group having 6 to 10 carbon atoms, M ¹ and M ² each represent a hydrogen atom or an atomic group or a metal atom that becomes a monovalent cation, and p and q each represent 1 to
Represents an integer of 5. General formula [II] In the formula, L represents an alkylene group, B is a carboxyl group,
Sulfo group, phosphono group, phosphinic acid residue, hydroxy group, amino group which may be alkyl substituted, ammonio group which may be alkyl substituted, sulfamoyl group which may be alkyl substituted, or alkylsulfonyl group which may be alkyl substituted Represents R represents a hydrogen atom or an alkyl group. 2. The color image forming method according to claim 1, wherein the replenishing amount of the color developing solution is 10 ml / m ² or more and 45 ml / m ² or less per 1 m ^{2 of the} light-sensitive material. 3. The color image forming method according to claim 1, wherein the color development time is 10 to 30 seconds and the processing from the beginning of the developing step to the end of the drying step is 50 to 90 seconds. . 4. The color according to claim 1, 2 or 3, wherein the replenishing amount of the color developing replenishing solution per day is 0.1% or more and 20% or less of the capacity of the color developing tank. Image forming method.