JPH1055052A - Photographic processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable a rapid processing and to stabilize a photographic performance by processing a specified silver halide color photographic sensitive material using a processing bath having specified slit-formed passages in the section and developing it with an activator solution replenished countercurrently in a direction reverse to a progress of the material. SOLUTION: The silver halide color photographic sensitive material containing a color developing reducing agent represented by the formula is developed with the activator solution replenished countercurrently in a direction reverse to a forward movement of the material by using the processing bath having a slit form in the section having a gap 5-100 times as mush as a thickness of the photosensitive material. In the formula, L is an electron withdrawing group releasable in the course of development processing; D is a group derived by removing nH from Hn D having a developing activity and (n) is 1, 2, or 3. Consequently, the volume of the processing bath is made smaller than usual tank type processing baths and an exchange rate can be enhanced by replenishing the developing solution.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic processing method for activating silver halide color photographic light-sensitive materials (hereinafter, also referred to as "light-sensitive materials" and "light-sensitive materials").

[0002]

2. Description of the Related Art Activator processing is generally known as a method in which a black-and-white developing agent is preliminarily incorporated in a photosensitive material and then processed with an alkaline activator solution which is a processing solution containing no hydroquinone developing agent. (1
965 Fuji Photo Film Quick Copy). Applying this to color development is more effective. That is, when a normal developer containing a color developing agent is used, it takes much time for the color developing agent having a high molecular weight to diffuse into the light-sensitive material film, and the developing time is longer than that of black-and-white development. Become. On the other hand, alkali has a small molecular weight and thus penetrates into the film quickly, so that color activator development in which a color developing agent is incorporated has a large effect that the development time is reduced because diffusion of the color developing agent is unnecessary. Therefore, the quick effect of the built-in color is greater for the color. Thus, compared to the case of using a normal developer, the time required for the color developing agent having a large molecular weight to diffuse into the light-sensitive material is unnecessary, and the alkali component, which is the main component of the activator solution, is easily diffused. Suitable for rapid processing. In addition, a normal color developing solution has a higher pH than a black-and-white developing solution, and the oxidative deterioration of a developing agent is large.
If replenishment can be performed stably and the alkali concentration can be kept constant, low replenishment becomes possible.

As described above, the activator processing can satisfy the demand for photographic processing, which has been increasing recently, such as rapid processing and low replenishment.

However, since the activator solution is generally a high pH solution, it absorbs oxides such as carbon dioxide in the air to make it difficult to maintain the pH, which causes fluctuations in photographic performance. . Further, since the development of the sensitizing material does not proceed sufficiently with only the color-forming reducing agent (color-forming developer), the photographic material usually contains an auxiliary developing agent such as pyrazolidones. Organic substances such as sensitizing dyes elute from the light-sensitive material into the activator liquid and dye or color the light-sensitive material, which causes stains or deterioration of the storage stability of the color image, resulting in discoloration. Or In particular, if the auxiliary developing agent used is hydrophilic, if it is incorporated in the photographic material, it must be made hydrophobic so that it moves in the layer and foggs the silver halide. Must be completely dissolved in the activator solution, and do not remain in the light-sensitive material even when dyeing or the like occurs. Due to such properties, it is not eluted from the light-sensitive material in the following neutral bleach-fixing or washing with water. On the other hand, if the auxiliary developing agent remains in the light-sensitive material, it is considered that the auxiliary developing agent remains in the oil because it is an oil-soluble compound, and interacts with the color image formed thereby to cause discoloration.

Therefore, it is necessary to solve such a problem in order to put the activator processing into practical use.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an activator process that can speed up the process, obtain stable photographic performance, does not generate stains, and preserves a color image. An object of the present invention is to provide a photographic processing method with good performance.

[0007]

This and other objects are attained by the present invention which is defined below as (1), (2) and (5).
The following (3) and (4) are preferable. (1) A silver halide color photographic light-sensitive material containing a color-forming reducing agent represented by the following formula (1) is used as a silver halide color photographic light-sensitive material. Using a processing tank having a processing path having a slit-shaped cross section having a gap of 5 to 100 times the thickness, developing by an activator solution by countercurrent replenishment from the side opposite to the transport direction of the silver halide color photographic light-sensitive material Do photo processing method. Formula (1) (L) _n -D [In Formula (1), L is an electron-withdrawing group that can be removed during the development process, and D is _n from H _n D having development activity.
N is a residue derived except for one hydrogen atom, and n is 1 to
It is an integer of 3. (2) A silver halide color photographic light-sensitive material containing a color-forming reducing agent represented by the following formula (1) is not passed through a processing path of the silver halide color photographic light-sensitive material. Occasionally, there is substantially no liquid flow, and a processing tank provided with a partitioning means so that the silver halide color photographic light-sensitive material can pass through, from the side opposite to the transport direction of the silver halide color photographic light-sensitive material. A photographic processing method in which development is performed using an activator solution with countercurrent replenishment. Formula (1) (L) _n -D [In Formula (1), L is an electron-withdrawing group that can be removed during the development process, and D is _n from H _n D having development activity.
N is a residue derived except for one hydrogen atom, and n is 1 to
It is an integer of 3. (3) The photographic processing method according to the above (2), wherein the dividing means uses a processing tank provided in the latter half of the processing path. (4) The above-mentioned (1) to (5) using a processing tank having a temperature control means for maintaining the temperature of the activator liquid in the processing path.
The photographic processing method according to any one of (3). (5) The photographic processing method according to any one of (1) to (4), wherein the silver halide color photographic light-sensitive material contains an auxiliary developing agent.

[0008]

Embodiments of the present invention will be described below in detail. The photographic processing method of the present invention uses the formula (1)
A silver halide color photographic light-sensitive material containing a color-forming reducing agent represented by
At this time, a counter processing replenishment is performed from the side opposite to the transport direction of the photosensitive material using a slit processing tank having a processing path having a slit-shaped cross section, or a multi-chamber processing tank in which a partitioning means is provided in the processing path and a plurality of processing chambers are arranged. Processing.

When the slit treatment tank is used, the amount of the activator liquid to be filled in the treatment tank is smaller than that of a normal tank-type treatment tank, so that replenishment increases the liquid exchange rate. In addition, fresh activator liquid can always be brought into contact with the light-sensitive material during processing. For this reason, a decrease in pH which is a problem in the activator solution is prevented, and stable photographic performance can be obtained. Further, since organic substances such as auxiliary developing agents and sensitizing dyes eluted from the light-sensitive material are prevented from being stored in the activator solution, dyeing or coloring to the light-sensitive material is prevented, and generation of stain can be prevented. . Moreover, auxiliary developing agents such as pyrazolidones increase the exchange rate of the activator solution,
It is easier to elute into the activator solution, and furthermore, it flows out of the activator solution by overflow, so that the residue in the activator solution is reduced. Therefore,
Incorporation into the photosensitive material due to dyeing is reduced, and the preservability of the color image is remarkably improved. And since the replenishment is countercurrent replenishment, it comes into contact with fresh activator liquid on the unloading side of the photographic material in the processing path, and a good processing environment is obtained at the stage of finishing the photographic performance, so that good photographic performance is obtained. Is obtained. Further, in the slit treatment tank, the contact between the activator liquid and the air is reduced, so that the pH of the activator liquid is less fluctuated.

On the other hand, when a multi-chamber processing tank is used, the liquid does not flow between the processing chambers when the photosensitive material does not pass through, so that the processing liquid having a lowered pH, the auxiliary developing agent eluted in the preceding processing chamber, etc. The organic matter is prevented from being brought into the subsequent processing chamber, and is supplemented by countercurrent. Therefore, the organic substance comes into contact with a fresh activator solution in the subsequent processing chamber, and good photographic performance can be obtained. Further, the auxiliary developing agent is easily eluted from the light-sensitive material, and the storage stability of the color image is also improved.

In particular, in the present invention, it is preferable to form a processing chamber by providing a partitioning means in the processing path of the slit processing tank, particularly in the processing path in the rear half portion, whereby the replenishing amount can be reduced.

Further, in order to further improve the photographic performance, it is preferable to process the activator solution while keeping it at a constant temperature.

As described above, the present invention relates to the problem of pH reduction of the activator solution generated in the activator treatment of a light-sensitive material containing a color-forming reducing agent, dyeing due to the eluate of the light-sensitive material, and the use of an auxiliary developer in the light-sensitive material. This problem is solved by using a slit treatment tank or a multi-chamber treatment tank and performing countercurrent replenishment.

The present invention will be described in more detail. FIG. 1 shows a processing apparatus used in the photographic processing method of the present invention.
The configuration shown in FIG. The processing apparatus of FIG. 1 uses a slit processing tank as an activator processing tank.

As shown in FIG. 1, a processing apparatus 1 comprises a photosensitive material storage section 2 for storing a photosensitive material A, an exposure section 3 for exposing the photosensitive material A, and an activator process for exposing the photosensitive material A to bleach-fixing. Processing section 4 for processing → stabilization processing, drying section 5 for drying photosensitive material A after these processing, photosensitive material A after drying
And a photosensitive material take-out section 6 for taking out the photosensitive material.

The processing section 4 is provided with an activator processing tank 6 filled with the activator liquid P1, a bleach-fix tank 8 filled with the bleach-fixing liquid P2, and a stabilizing tank 9 filled with the stabilizing liquid P3. Each of these processing tanks 7 to 9 is a slit processing tank. In each of the processing tanks 7 to 9, drums 10 to 12 for transporting the photosensitive material A are provided. Each of the processing tanks 7 to 9 is provided with a replenishing tank 13 to 15, and each of the replenishing solutions P1, P2, and P3 is appropriately filled with each of the processing tanks 7 to 9.
Refilling is performed in the pump 9 through pumps 16-18. Each of these replenishment tanks 13 to 15 contains a replenisher P1
Replenisher storage sections 13A, 14A, 15A for storing ~ P3
And each of the overflows OF1, OF2, OF3. It is composed of overflow storage sections 13B, 14B and 15B. These replenishment tanks are disclosed in
No. 259,575 (the numbers of 60, 62, 64 in FIG. 2) and the like.
Has a structure in which the volume of each part is variable according to the respective volumes of the replenishers P1 to P3 and the overflows OF1 to OF3.
When only the tank is replaced, the tank is replaced.

In each of the processing tanks 7 to 9, replenishment is countercurrent replenishment performed from the side opposite to the conveying direction of the photosensitive material A.

The activator treatment tank 7 installed in the treatment apparatus 1 is preferably provided with a temperature control means for keeping the activator liquid at a constant temperature, such as the one shown in FIG. . The activator treatment tank 7 of FIG. 2 is provided with a water tank 20 for temperature control.
The water tank 20 is filled with water W, and the liquid temperature is kept constant by the heater 21 and the temperature sensor 22. A rotator 23 for stirring the water W is disposed in the water tank 20. In this case, the material of the water tank 20 and the activator processing tank 7 on the water tank 20 side is made of a heat conductive material (for example, stainless steel) so that the temperature of the water in the water tank 20 becomes substantially the same. Further, such a water tank 20 may be fixed in the drum 10 of FIG. 1 and installed so as to conduct heat to the processing tank 7.

Further, the processing tank 7 is provided with a carry-in roller 25 for carrying the photosensitive material A into the processing tank 7 and a carry-out roller 26 for carrying the photosensitive material A out of the processing tank 7. The activator liquid P1 is replenished from the discharge side of the photosensitive material A, and the overflow OF1 is discharged from the transfer side.

In FIG. 2, the heater 21 is a normal heater. However, a planar heater (for example, Japanese Patent Application Laid-Open No. 3-119846) that partially or entirely covers the bottom surface of the water tank 20 may be used. Further, in FIG. 2, at least a part of a replenishing pipe for replenishing the activator solution P1 is put in water for temperature control, and the temperature of the replenisher activator solution P1 is substantially equal to that in the activator processing tank 7. It may be the same. Further, the roller 25 on the loading side of the photosensitive material A may be used as a heat roller to preheat the photosensitive material A before processing. This prevents the liquid temperature from dropping due to the loading of the photosensitive material A.

Furthermore, without using water for temperature control,
A sheet heater provided on the opposite side to the liquid contact surface of one stainless steel sheet forming the slit treatment path, and a sheet heater provided with a temperature sensor on the opposite side of the liquid contact surface of the other stainless steel sheet is provided. A planar sensor may be used to control the temperature of the activator liquid by a combination of the planar heater and the planar sensor.

In the processing path of the slit processing tank 7,
As shown in FIG. 3, a partitioning means 71 may be provided to form a multi-chamber processing tank composed of processing chambers 7A and 7B. Such a dividing means 71 is disclosed in, for example, Japanese Patent Application Laid-Open No. 1-267648.
Or the blades disclosed in JP-A Nos. 2-130548 and 2-310557. Although the partitioning means 71 is provided at approximately ／ of the entire processing path in FIG. 3, it is preferably provided at the latter half (１ ／) or later, for example, 、 ２, ／, ／, One location or two or more locations may be selected from 7/8 and 15/16 and installed.

Although the above has been described with reference to the illustrated examples, the slit processing tank and the multi-chamber processing tank are not limited to these.

In the present invention, the term "slit processing tank" means a processing tank having a slit-shaped processing path having a gap of 5 to 100 times the thickness of the light-sensitive material (the total thickness of the support and the photographic layer). At least 70% or more of the processing path has such a cross-sectional slit shape.

For details of such a slit treatment tank, see US Pat. Nos. 2,428,681 and 3,610,029.
No., French Patent No. 1185411, Japanese Patent Publication No. 43-154
No. 9, JP-A-62-8905, JP-A-62-6754
No. 3, JP-A-61-7785 and JP-A-64-4493.
No. 8, JP-A-63-131138, JP-A-63-21
No. 6050, Japanese Unexamined Patent Publication No.
148944, JP-A-63-259661, JP-A-63-259662, and JP-A-63-148945.
And JP-A-64-26855.

In such a slit processing tank, when countercurrent replenishment is performed from the side opposite to the direction of transport of the light-sensitive material, the flow of liquid between the emulsion surface of the light-sensitive material and the wall surface of the slit processing path is increased. The flow is opposed to.

By forming such a liquid stream, in the activator processing of the present invention, the elution rate of the auxiliary developing agent such as a pyrazolidone derivative eluted from the light-sensitive material is increased, and at the same time, these are dyed and remain on the light-sensitive material. To prevent For this reason, the storage stability of the color image is improved. Further, dyeing due to elution of organic substances such as sensitizing dyes and dyes from the photosensitive material can be prevented.

On the other hand, the multi-chamber processing tank according to the present invention is a multi-chamber processing tank having a partitioning means for preventing the liquid from flowing substantially through the processing path of the light-sensitive material and allowing the light-sensitive material to pass therethrough. The flow rate of the liquid when the photosensitive material is not passed between the processing chambers formed by the partition means is about 2 ml / min or less. Also,
When passing through the light-sensitive material, the flow rate is about 2 to 20 ml / min.

Such a multi-chamber processing layer is disclosed in JP-A-1-267648, JP-A-2-67554, US Pat. Nos. 4,980,714 and 5,066,570, and JP-A-2,066,570.
JP-A-130548, JP-A-2-186340, JP-A-2-205846, JP-A-2-205847, JP-A-2-230145, JP-A-2-240651, JP-A-2-242249, JP-A-2-242 No. 267549,
JP-A-2-269335, JP-A-2-280149
JP-A-2-310557, JP-A-3-23445
And JP-A-3-39960 and JP-A-3-43733.

Among the multi-chamber processing tanks, in the present invention, it is preferable that a partitioning means is provided in the processing path of the slit processing tank as shown in the illustrated example.

The activator treatment tank of the present invention preferably has a liquid volume of about 100 to 3000 ml.
m ² per replenishment rate 15～800Ml, more 25-4
It is preferably 00 ml, especially 35-200 ml.
In addition, the liquid exchange rate is about 7 to 600 times that in the case of using a tank type processing tank having a capacity of 10 to 60 liters.

In FIG. 1, the bleach-fixing tank and the stabilizing tank are also slit processing tanks. However, if the activator processing tank is a slit or a multi-chamber processing tank, the present invention is not limited thereto. Tank type processing tank. Further, the configuration of the processing tank can be variously changed according to the processing steps.

The light-sensitive material of the present invention contains a color-forming reducing agent. The color-forming reducing agent used in the present invention will be described. Generally, a developing agent used for a silver halide color photographic light-sensitive material reduces silver halide imagewise, directly or via another electron transfer agent, to produce an oxidized developer corresponding to the exposure amount. The oxidized developing agent further reacts with a color forming agent (coupler) to form a dye. In this ordinary color photographic system, a developer is contained in a developer, and the developer permeates a photosensitive material during a development process, and development proceeds. That is, a developing agent having high reactivity (which is a reducing agent and thus easily decomposed by being oxidized by air) is always supplied in a fresh form in the developing process.

However, since the color-forming reducing agent corresponding to the developing agent used in the present invention is contained in the light-sensitive material, it has excellent storage stability before and after development and exhibits high development activity in the development process. It must have seemingly contradictory characteristics. In other words, the developer used in normal photographic processing cannot be used as it is (in terms of storage stability), and a developer designed to raise the oxidation potential for the purpose of satisfying storage stability cannot be processed. Sometimes, sufficient development activity cannot be exhibited. As one method for solving this problem, there is a method in which a group capable of being released in a color developing process is introduced into a compound having a developing activity and used as a developing agent. This developer, that is, the color-forming reducing agent is represented by the following formula (1). Formula (1) (L) _n -D In the formula (1), L is an electron-withdrawing group capable of leaving during the development process, and D is a compound H _n D having a development activity.
And n is an integer of 1 to 3.

The developer represented by the formula (1) is represented by the following formula (2)
Is preferable. Formula (2) L ¹ L ² N- (NH) _p- (X = Y) _q -Z In the formula (2), L ¹ and L ² are a hydrogen atom or an electron-withdrawing group which can be separated during the color developing process. And L ¹ and L ² are not hydrogen atoms at the same time, X and Y independently represent methine or azomethine, Z represents a hydrogen atom, a hydroxyl group, an amino group or —NHL ³ , and L ³ represents an electron Represents an attractive group, p is an integer of 0 or 1, q is an integer of 1 to 3, L ¹ , L ² , X, Y
And any two of Z and Z may combine to form a ring.

The preferred range of the developer represented by the formula (2) will be described in detail. In the formula (2), the electron-withdrawing groups represented by L ¹ and L ² are preferably an acyl group, a sulfinyl group, a sulfonyl group and a sulfolyl group, and particularly preferably an acyl group and a sulfonyl group. L
¹ and L ² are released during the color development process, but may be released after the developer represented by the formula (2) is oxidized, or may be released before being oxidized. However, from the viewpoint that it is preferable that development does not proceed in the unexposed area (fogging suppression), and that the developing active species generated in the developing process remain unreacted in the light-sensitive material, and this generates a colored substance. From the viewpoint of prevention (stain suppression),
Developing agent used in the present invention is a silver halide developing imagewise under basic conditions, whereby the resulting developer oxidant L ¹ and L ² are detached from the coupling of the coupler, generates a dye Is preferred. The form of elimination of L ¹ and L ² may be eliminated as an anion or a radical, or the action of a nucleophilic species or a base (water, hydroxide ion, hydrogen peroxide, sulfite ion, hydroxylamine, etc.) in the developer. May be withdrawn, especially in the latter case.
By actively adding a nucleophilic species to the developer, L ¹
Or or facilitate separation of L ^2, compounds that promote silver development (particularly preferably hydrogen peroxide) may utilize this nucleophilic case of adding facilitate separation of L ¹ or L ² .

In the formula (2), (X = Y) _q represents a π-electron conjugated system by a carbon atom or a nitrogen atom.
Are preferably linked to form a ring, q is preferably 2 or 3, and the number of nitrogen atoms contained is preferably 0 to 3. (X = Y) When _q forms a ring, the number of ring members is preferably 5 or 6, and a hetero atom may be contained as a constituent atom of the ring. In this case, a preferable hetero atom is a nitrogen atom or an oxygen atom. And a sulfur atom, and particularly preferably a nitrogen atom. (X = Y) _q may have a condensed ring, and the condensed ring is preferably a benzene ring.

When p is 0, X bonded to L ¹ L ² N may be either a carbon atom or a nitrogen atom. When p is 1, X bonded to NH is preferably a carbon atom. .

In the formula (2), when q is 0, Z is preferably a hydroxyl group, an amino group or NHL ³ ;
When p is 1, Z is preferably a hydrogen atom or NHL ³ . When Z is represented by NHL ³ , L ³ is preferably an acyl group, a sulfinyl group, a sulfonyl group and a phorphoryl group, and particularly preferably an acyl group and a sulfonyl group.

The developing agent represented by the formula (2) is preferably introduced into the photosensitive material by a method of dissolving and dispersing in a high boiling point organic solvent, that is, a so-called oil protection method.
Therefore, in order to be easily dissolved in a high-boiling organic solvent and to stably maintain the photosensitive material, the developer preferably has a relatively large lipophilic group generally called a ballast group. Therefore, this ballast group preferably contains one or more linear or branched alkyl groups of a certain size, and the total number of carbon atoms of these alkyl groups is preferably from 3 to 32, more preferably 6-22, particularly preferably 8-18. The substitution position of the ballast group may be on L ¹ , L ² , (X = Y) or Z, but is preferably on L ¹ or L ² .

Developing agent represented by [0041] formula (2) in order to impart development processing solution, i.e. preferably pKa corresponding to the pH of the activator solution (acid dissociation constant) is used, the absorption wavelength of the formed dye, L ¹ or L ^It may have a substituent for adjusting the rate of departure of ^2, the rate of coupling with the coupler, or the oxidation potential to a desired range. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an amino group, a carboxyl group, a sulfo group, an acyl group, an acylamino group,
Carbamoyl group, sulfonyl group, sulfonylamino group,
Examples include a sulfamoyl group, an alkyl group, an aryl group, an alkoxy group, a heterocyclic group, and an aryloxy group.

Among the developing agents represented by the formula (2), particularly preferred are the developing agents represented by the following formulas (3) to (9). Formula (3) R ¹ SO ₂ NH-φ ¹ -NR ² R ³ Formula (4) R ⁴ SO ₂ NH-φ ² -OH Formula (5) R ⁵ CONH-φ ³ -NR ⁶ R ⁷ Formula (6) R ⁸ CONH-φ ⁴ -OH Formula (7) R ⁹ SO ₂ NHN = φ ⁵ Formula (8) R ¹⁰ CONNHN = φ ⁶ Formula (9) R ¹¹ -NHNH-X-R ¹²

First, formulas (3) to (8) will be described. In formulas (3) to (8), R ² , R ³ , R ⁶ and R ⁷ represent an alkyl group, an aryl group or a heterocyclic group; ^{R 1, R 4, R 5} , R 8, R 9 and R ¹⁰ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group or an amino group, phi ¹ to [phi]
⁴ represents an arylene group or a heteroarylene group;
⁵ and phi ⁶ represents a carbon hydrocarbon ring group or a heterocyclic group bonded to the nitrogen atom by a double bond.

In the formulas (3) to (8), preferred as the alkyl groups represented by R ^{1 to} R ¹⁰ are those having 1 to 30 carbon atoms.
Linear or branched, linear or cyclic alkyl group, and among them, preferred are linear or branched alkyl groups having 1 to 22 carbon atoms, for example, a methyl group, an ethyl group,
Isopropyl, n-butyl, 2-ethylhexyl, n-dodecyl, t-octyl, n-tetradecyl, n-hexadecyl and n-octadecyl.

Preferred as the aryl groups represented by R ^{1 to} R ¹⁰ in formulas (3) to (8) are those having 6 to 2 carbon atoms.
It is an aryl group having 0 and preferably has 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthracenyl group. Among them, a preferable one is a phenyl group.

In formulas (3) to (8), preferred as the heterocyclic group represented by R ^{1 to} R ¹⁰ is a 5- to 7-membered heterocyclic group, wherein the hetero atom is a nitrogen, oxygen or sulfur atom. Is preferably, and the number of carbon atoms is preferably 1 to 10,
Particularly preferred are 5- or 6-membered nitrogen-containing heterocyclic groups such as a 2-imidazolyl group, a 1,3-oxazol-2-yl group, a 1,3-thiazol-2-yl group and a 5-membered heterocyclic group.
-Tetrazolyl group, 3-indolinyl group, 1,3,4-
Thiadiazol-2-yl group, 1,2,4-thiadiazol-5-yl group, 1,3-benzoxazol-2-yl
Yl group, 1,3-benzothiazol-2-yl group, 1,
3-benzimidazol-2-yl group, 1,2,4-triazol-3-yl group, 3-pyrazolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidyl group, 4- Pyrimidyl group, 1,3,5-triazine-
2-yl group, 1,2,4-triazin-3-yl group, 4
-Quinazolyl group, 2-quinoxalyl group and the like.
Further, these rings may have a condensed ring, and a preferable condensed ring is a benzene ring.

In the formulas (3) to (8), R ¹ , R ⁴ , R
Preferred as the alkoxy group represented by ⁵ , R ⁸ , R ⁹ and R ¹⁰ are straight-chain or branched having 1 to 30 carbon atoms,
A chain or cyclic alkoxy group is preferable, and a particularly preferable one is a linear or branched alkoxy group having 1 to 22 carbon atoms, for example, methoxy group, ethoxy group, isopropoxy group, n-butoxy group, 2-ethylhexyl. Examples thereof include an oxy group, an n-dodecyloxy group, an n-tetradecyloxy group, an n-hexadecyloxy group, and an n-octadecyloxy group.

In the formulas (3) to (8), R ¹ , R ⁴ , R
Preferred as the aryloxy group represented by ⁵ , R ⁸ , R ⁹ and R ¹⁰ are aryloxy groups having 6 to 20 carbon atoms, more preferably 6 to 10 carbon atoms,
For example, a phenoxy group, a naphthoxy group, an anthracenoxy group and the like can be mentioned, and among them, a phenoxy group is preferable.

In the formulas (3) to (8), R ¹ , R ⁴ , R
^5, R ^8, R ⁹ and preferred as the amino group represented by R ¹⁰ is an alkylamino group having 2 to 40 carbon atoms, a dialkylamino group, an arylamino group, diarylamino group, heteroarylamino group, diheterocyclic An arylamino group, an alkylarylamino group, an alkylheteroamino group and an arylheteroarylamino group, more preferably an alkylamino group having 1 to 20 carbon atoms, a dialkylamino group and an arylamino group, for example, a methylamino group, an ethylamino Groups, propylamino, diethylamino, di-n-octylamino, phenylamino, dodecylamino, hexadecylamino and the like.

In the formulas (3) to (6), preferred as the arylene group represented by φ ^{1 to} φ ⁴ are those having 6 to 2 carbon atoms.
It is preferably an arylene group of 0, and more preferably an arylene group having 6 to 10 carbon atoms. Examples thereof include a phenylene group, a naphthylene group, and an anthracenylene group. Among them, a phenylene group is particularly preferred. These may have a condensed ring, and a preferable condensed ring is a benzene ring.

In formulas (3) to (6), the hetero atoms constituting the heteroarylene groups represented by φ ^{1 to} φ ⁴ are preferably nitrogen, oxygen and sulfur atoms, and the number of hetero atoms is preferably 1 to 4. , More preferably 1-3, and 1 or 2 is particularly preferred. 2 to 8 carbon atoms
Is more preferably 3 to 5, and the number of ring members is 5
Or 6 is preferable, and may have a condensed ring,
Preferred as a condensed ring is a benzene ring. φ ¹ ~
As the φ ⁴ ring structure, a benzene ring is most preferred.

[0052] Preferred as formula (7) and the "hydrocarbon residue or heterocyclic group bonded to the nitrogen atom by a double bond" represented by phi ⁵ and phi ⁶ (8) 5-7
A membered carbocyclic ring group or a heterocyclic group, and the heteroatoms are preferably nitrogen, oxygen and sulfur atoms, and the number of heteroatoms contained is preferably 0 to 3, more preferably 0 to 2, The number of carbon atoms is preferably 2 to 8, more preferably 3 to 6, and particularly preferably 5 to 5.
A 6- or 6-membered nitrogen-containing unsaturated heterocyclic ring represented by the formula (7):
In (8) and (8), the carbocyclic ring and the heterocyclic ring are represented by R ⁹ SO ₂ NHN or R ¹⁰ CO
It is preferable to form a double bond with NHN, and it may have a condensed ring. A preferable condensed ring is a benzene ring.

In the formulas (3) and (5), R ² and R
^3, phi ¹ and R ^2, phi ¹ and R ^3, R ⁶ and R ^7, phi ³ and R
⁶ , φ ³ and R ⁷ may be linked to form a ring, and the number of ring members is preferably 5 or 6, and a hetero atom may be contained as a ring-forming atom, and a hetero atom is preferable. Things are oxygen atoms.

Next, preferred ranges of the developing agents represented by the formulas (3) to (8) will be described in more detail. Equation (3)-
In (8), R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R
Preferred as ¹⁰ are an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, an amino group and an anilino group. Among the amino group and the anilino group, those having a hydrogen atom bonded to a nitrogen atom are particularly preferred.

Preferred as R ¹ and R ^{4 in} formulas (3) and (4) are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an alkyl group and an aryl group. Preferred as R ⁵ and R ^{8 in the} formulas (5) and (6) are an aryl group, an alkyl group, an amino group and an anilino group, and particularly preferred are an amino group and an anilino group.

R ¹ , R ⁴ , R ⁵ , R ⁸ , R ⁹ and R ¹⁰
May further have a substituent, and a preferable substituent is a halogen atom (a fluorine atom, a chlorine atom,
A bromine atom), an alkyl group (1 to 22 carbon atoms), an acyl group (1 to 18 carbon atoms), a sulfonyl group (1 to 1 carbon atoms)
8), an alkoxy group (1 to 22 carbon atoms), an aryloxy group (6 to 23 carbon atoms), an alkoxycarbonyl group (2 to 23 carbon atoms), an aryloxycarbonyl group (7 to 23 carbon atoms), a carbamoyl group ( C2 to C23), sulfamoyl group (C0 to C22), acylamino group (C1 to C22), sulfonylamino group (C1 to C2)
2) an acyloxy group (having 1 to 22 carbon atoms), a carboxyl group, a sulfo group, an amino group (having 0 to 22 carbon atoms), a hydroxyl group, a cyano group, a polyfluoroalkyl group, and a nitro group.

In the formulas (3) and (5), R ² and R
^3, preferred as R ⁶ and R ⁷ are 1 to 8 carbon atoms
Preferred substituents are a hydroxyl group, an alkoxy group (1 to 12 carbon atoms), an acylamino group (1 to 12 carbon atoms), a sulfonylamino group (1 to 12 carbon atoms), and a cyano group. is there.

Next, equation (9) will be described. The compound of the formula (9) is a particularly preferred compound among the compounds of the formulas (3) to (9). In the formula (9), R ¹¹ is an aryl group or a heterocyclic group, and R ¹² is an alkyl group,
It is an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. X is _{-SO 2 -, - CO -,} - COCO
-, - CO-O -, - CO-N (R 13) -, - COCO
-O -, - COCO-N ( R 13) - or -SO ₂ -N
(R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² .

Hereinafter, the structure of the color-forming reducing agent represented by the formula (9) will be described in detail. In the formula (9), R ¹¹
Represents an aryl group or a heterocyclic group which may have a substituent. The aryl group represented by R ¹¹ preferably has 6 carbon atoms.
To 14, for example, a phenyl group and a naphthyl group. The heterocyclic group for R ¹¹ is preferably nitrogen,
It is a saturated or unsaturated 5-, 6- or 7-membered ring containing at least one of oxygen, sulfur and selenium. These may be condensed with a benzene ring or a hetero ring. Examples of the heterocyclic group for R ¹¹ include a furanyl group, a thienyl group, an oxazolyl group, a thiazolyl group, an imidazolyl group, a triazolyl group, a pyrrolidinyl group, a benzoxazolyl group, a benzothiazolyl group, a pyridyl group, a pyridazyl group, a pyrimidinyl group, Examples include a pyrazinyl group, a triazinyl group, a quinolinyl group, an isoquinolinyl group, a phthalazinyl group, a quinoxalinyl group, a quinazolinyl group, a purinyl group, a pteridinyl group, an azepinyl group, and a benzooxepinyl group.

Examples of the substituent of R ¹¹ include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group and a heterocyclic thio group. , Acyloxy group, acylthio group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, amino group, alkylamino group, arylamino group, amide group, alkoxycarbonylamino group An aryloxycarbonylamino group, a ureido group, a sulfonamide group, a sulfamoylamino group,
Acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acylcarbamoyl group,
Carbamoylcarbamoyl group, sulfonylcarbamoyl group, sulfamoylcarbamoyl group, alkylsulfonyl group, arylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, alkoxysulfonyl group, aryloxysulfonyl group, sulfamoyl group,
Examples include acylsulfamoyl, carbamoylsulfamoyl, halogen, nitro, cyano, carboxyl, sulfo, phosphono, hydroxyl, mercapto, imide, and azo groups.

R ¹² represents an optionally substituted alkyl group, alkenyl group, alkynyl group, aryl group or heterocyclic group.

The alkyl group represented by R ¹² is preferably a straight-chain, branched or cyclic alkyl group having 1 to 16 carbon atoms, for example, methyl, ethyl, hexyl, dodecyl, 2-octyl, t-butyl. Group, cyclopentyl group, cyclooctyl group and the like.

The alkenyl group for R ¹² is preferably a linear or cyclic one having 2 to 16 carbon atoms, and examples thereof include a vinyl group, a 1-octenyl group and a cyclohexenyl group.

The alkynyl group for R ¹² preferably has 2 to 16 carbon atoms, and examples thereof include a 1-butynyl group and a phenylethynyl group. As the aryl group and heterocyclic group for R ¹² , those described for R ¹¹ can be mentioned. Examples of the substituent of R ¹² include those described for the substituent of R ¹¹ .

X represents -SO _2- , -CO-, -CO
CO -, - CO-O - , - CO-N (R 13) -, - CO
CO-O -, - COCO- N (R 13) - or -SO ₂
—N (R ¹³ ) —. Here, R ¹³ is a hydrogen atom or a group described for R ¹² .

Among these groups, -CO- and -CON (R
¹³⁾ -, - CO-O- are preferable, -CON in that coloring property is particularly excellent (R ¹³⁾ - is particularly preferred.

Among the compounds represented by the formula (9), the compounds represented by the following formulas (10) and (11) are preferable.
Compounds represented by the following formulas (12) and (13) are more preferred, and compounds represented by the following formulas (14) and (15) are even more preferred.

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In the formulas (10) and (11), Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and Z ² represents a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. , X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. However, the sum of the Hammett's substituent constant σp value of X ¹ , X ³ and X ^{5 and} the Hammett's substituent constant σm value of X ² and X ⁴ is 0.80 or more and 3.80 or less. R ²³ represents a heterocyclic group.

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In the formulas (12) and (13), R ²¹ and R ²² each represent a hydrogen atom or a substituent, and X ¹ , X ² , X ³ , X ⁴ ,
X ⁵ represents a hydrogen atom or a substituent. Where X ¹ , X
³ , the sum of the Hammett's substituent constant σp value of X ^{5 and} the Hammett's substituent constant σm value of X ² and X ⁴ is 0.80 or more and 3.8.
0 or less. R ²³ represents a heterocyclic group.

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In the formulas (14) and (15), R ²⁴ and R ²⁵ each represent a hydrogen atom or a substituent, and X ⁶ , X ⁷ , X ⁸ , X ⁹ ,
X ¹⁰ is a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group or a heterocyclic group Represents Where X
⁶ , Hammett's substituent constant σp value of X ⁸ , X ¹⁰ and X ⁷ ,
The sum of Hammett's substituent constant σm value of X ⁹ is 1.20 or more and 3.80 or less. Q ¹ and 5-8 of nitrogen-containing with C
Represents a group of nonmetallic atoms necessary to form a membered heterocycle.

Hereinafter, the compounds represented by formulas (10) to (15) will be described in detail. Equation (10) and Equation (1)
In 1), Z ¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Z ² represents a carbamoyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. As the acyl group, an acyl group having 1 to 50 carbon atoms is preferable,
More preferably, it has 2 to 40 carbon atoms. Specific examples include acetyl, 2-methylpropanoyl, cyclohexylcarbonyl, n-octanoyl, 2-hexyldecanoyl, dodecanoyl, chloroacetyl, trifluoroacetyl, benzoyl, A dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and a 3- (N-hydroxy-N-methylaminocarbonyl) propanoyl group.

The case where Z ¹ and Z ² are carbamoyl groups will be described in detail with formulas (14) to (15).

The alkoxycarbonyl group and the aryloxycarbonyl group are preferably an alkoxycarbonyl group and an aryloxycarbonyl group having 2 to 50 carbon atoms, more preferably 2 to 40 carbon atoms. Specific examples include methoxycarbonyl, ethoxycarbonyl, isobutyloxycarbonyl, cyclohexyloxycarbonyl, dodecyloxycarbonyl, benzyloxycarbonyl, phenoxycarbonyl, 4-octyloxyphenoxycarbonyl, 2-hydroxy Examples include a methylphenoxycarbonyl group and a 2-dodecyloxyphenoxycarbonyl group.

X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a hydrogen atom or a substituent. Here, examples of the substituent include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, trifluoromethyl, methyl, ethyl,
Propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl, etc.), linear or branched, linear or cyclic having 2 to 50 carbon atoms. Alkenyl group (for example, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), having 2 to 50 carbon atoms in total
(E.g., ethynyl, 1-propynyl, etc.), an aryl group having 6 to 50 carbon atoms (e.g., phenyl, naphthyl, anthryl, etc.), and an acyloxy group having 1 to 50 carbon atoms (e.g., acetoxy, tetradecanoyloxy) , Benzoyloxy, etc.), a carbamoyloxy group having 1 to 50 carbon atoms (eg, N, N-dimethylcarbamoyloxy), a carbonamide group having 1 to 50 carbon atoms (eg, formamide, N-methylacetamide, acetamide, N -Methylformamide, benzamide, etc.),
A C1-50 sulfonamide group (e.g., methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.); a C1-50 carbon atom carbamoyl group (e.g., N-methylcarbamoyl, N, N-diethylcarbamoyl, N-mesylcarbamoyl and the like, a sulfamoyl group having 0 to 50 carbon atoms (for example, N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4-methoxyphenyl) ) Sulfamoyl, etc.), C1-C50 alkoxy groups (for example, methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, dodecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy, etc. ), An aryloxy group having 6 to 50 carbon atoms (for example, phenoxy, 4 Methoxyphenoxy, naphthoxy, etc.), an aryloxycarbonyl group of 7 to 50 carbon atoms (e.g., phenoxycarbonyl, naphthoxycarbonyl, etc.),

An alkoxycarbonyl group having 2 to 50 carbon atoms (for example, methoxycarbonyl, t-butoxycarbonyl, etc.), an N-acylsulfamoyl group having 1 to 50 carbon atoms (for example, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino, etc.), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl , A hydroxy group, a sulfo group, a mercapto group, etc.), an alkylsulfinyl group having 1 to 50 carbon atoms (eg, methanesulfinyl, octanesulfinyl, etc.), an arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenyl) Sulfinyl, p-toluenesulfinyl, etc.), having 1 to 5 carbon atoms
0 alkylthio groups (eg, methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, etc.),
A ureido group having 1 to 50 carbon atoms (for example, 3-methylureide, 3,3-dimethylureide, 1,3-diphenylureide and the like), a heterocyclic group having 2 to 50 carbon atoms (for example, nitrogen, A 3- to 12-membered monocyclic or condensed ring containing at least one or more oxygen and sulfur atoms, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino,
-Quinolyl, 2-benzimidazolyl, 2-benzthiazolyl, 2-benzoxazolyl, etc.), having 1 to 50 carbon atoms
(E.g., acetyl, benzoyl, trifluoroacetyl, etc.) and a sulfamoylamino group having 0 to 50 carbon atoms (e.g., N-butylsulfamoylamino, N
-Phenylsulfamoylamino, etc.), having 3 to 50 carbon atoms
(E.g., trimethylsilyl, dimethyl-t
-Butylsilyl, triphenylsilyl and the like), and a halogen atom (for example, a fluorine atom, a chlorine atom and a bromine atom). The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here. X ¹ , X ² , X ³ , X ⁴ and X ⁵ may be bonded to each other to form a condensed ring. 5-7 as fused ring
Member rings are preferred, and 5- to 6-membered rings are more preferred.

The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 34 or less. Also, one or more is preferable.

X ¹ , X in formulas (10) and (11)
^{As for 2} , X ³ , X ⁴ , and X ⁵ , the sum of the Hammett's substituent constants of X ¹ , X ³ , and X ^{5 and} the Hammett's substituent constant σm of X ² , X ⁴ is 0.80. Not less than 3.80. Further, X ⁶ , X ⁷ , X ⁸ , X
⁹ , X ¹⁰ represents a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group or a hetero atom. Represents a ring group, which may further have a substituent and may be bonded to each other to form a condensed ring. X ¹ ,
This is the same as that described for X ² , X ³ , X ⁴ , and X ⁵ . However, in the formula (11), the sum of the Hammett's substituent constant σp value of X ⁶ , X ⁸ and X ^{10 and} the Hammett's substituent constant σm value of X ⁷ and X ⁹ is 1.20 or more and 3.80 or less. Yes, 1.
It is preferably 50 or more and 3.80 or less, more preferably 1.
70 or more and 3.80 or less.

Here, the sum of the σp value and the σm value is 0.8
If it is less than 0, there are problems such as insufficient color development,
On the other hand, when it exceeds 3.80, it becomes difficult to synthesize and obtain the compound itself.

The Hammett's substituent constants σp and σm are described, for example, by Naoki Inamoto, “Hammet's Rule—Structure and Reactivity—” (Maruzen), “New Experimental Chemistry Course 14, Synthesis and Reaction of Organic Compounds V” 2605 (Chemical Society of Japan, Maruzen), Tadao Nakaya, "Explanation of Theoretical Organic Chemistry", 217 pages (Tokyo Kagaku Dojin), Chemical Review (91), 165-195
The book is described in detail in pages (1991).

In the formulas (12) and (13), R ²¹ ,
R ²⁴ and R ²⁵ in R ²² , (14) and (15) represent a hydrogen atom or a substituent, and specific examples of the substituent include X
¹ , X ² , X ³ , X ⁴ and X ⁵ have the same meaning as described above, but are preferably a hydrogen atom or a carbon atom having 1 to 5 carbon atoms.
0 substituted or unsubstituted alkyl group, 6 to 50 carbon atoms
A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group having 1 to 50 carbon atoms, and more preferably at least one of R ²¹ and R ²² and at least one of R ²⁴ and R ²⁵ are hydrogen atoms. is there.

In the formulas (11) and (13), R ²³ represents a heterocyclic group. The preferred heterocyclic group here has 1 to 1 carbon atoms.
50 heterocyclic groups, each of which contains at least one or more nitrogen, oxygen and sulfur atoms, and is a saturated or unsaturated 3- to 12-membered ring (preferably 3 or more).
-8-membered ring) or a condensed ring, and specific examples of the hetero ring include furan, pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2, 4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole, pyridazine, indole, pyrazole, triazole, quinoxaline and the like. These heterocyclic groups may have a substituent, and preferably have at least one electron-withdrawing group. Here, the electron-withdrawing group means a group having a positive Hammett σp value.

When the color-forming reducing agent of the present invention is incorporated in a light-sensitive material, Z in the structural formula of each compound used.
¹ , Z ² , R ^{21 to} R ²⁵ , X ^{1 to} X ¹⁰ , at least one of which is a ballast group (a reducing agent for color formation (in a high boiling organic solvent)
It is preferable to have a group having 5 to 50, preferably 8 to 40 carbon atoms for solubilization and immobilization.

Next, the color-forming reducing agents used in the present invention will be specifically described, but the scope of the present invention is not limited to these specific examples.

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The color-forming reducing agent of the present invention is used in an amount of 0.01 to 10 mmol / mol / color-forming layer in order to obtain a sufficient color-forming density.
Preferably, m ^{2 is} used. A more preferred amount is 0.05 to 5 mmol / m ² , and a particularly preferred amount is 0.1 to 1 mmol / m ² .

As the coupler preferably used in the present invention, compounds known in the art can be used. These are compounds generally called active methylene, pyrazolone, pyrazoloazole, phenol, naphthol and pyrrolotriazole, respectively. As the yellow coupler, a coupler called an active methylene coupler can be used. As the magenta coupler, a 5-pyrazolone coupler or a pyrazoloazole coupler can be used. As the cyan coupler, a phenol coupler, a naphthol coupler, and a pyrrolothrazole coupler can be used.

The amount of the coupler in the color-forming layer in which the color-forming reducing agent of the invention is used is preferably 0.05 to 20 times, more preferably 0.1 to 20 times the molar amount of the color-forming reducing agent.
It is 10 to 10 times, particularly preferably 0.2 to 5 times.

The color light-sensitive material of the present invention is basically obtained by coating a support with a photographic constituent layer comprising at least one hydrophilic colloid layer, and any of the photographic constituent layers is provided with a light-sensitive silver halide. , A dye-forming coupler and a color-forming reducing agent, preferably an auxiliary developing agent.

In the most general mode, the dye-forming coupler and the color-forming reducing agent used in the present invention are added to the same layer. it can. These components are preferably added to a silver halide emulsion layer or a layer adjacent to the silver halide emulsion layer in the light-sensitive material, and particularly preferably added together to a silver halide emulsion layer.

The color-forming reducing agent and coupler of the present invention can be introduced into a light-sensitive material by various known dispersion methods, dissolved in a high-boiling organic solvent (optionally using a low-boiling organic solvent in combination), and emulsified in an aqueous gelatin solution. An oil-in-water dispersion method of dispersing and adding to a silver halide emulsion is preferred. The high boiling organic solvent that can be used in the present invention has a melting point of 100 ° C. or less and a boiling point of 140 ° C.
Any compound that is immiscible with water at a temperature of not less than ° C and is a good solvent for the color-forming reducing agent and coupler can be used. The melting point of the high boiling organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher. Details of these high-boiling organic solvents are described in JP-A-62-215272, page 137, lower right column to page 144, upper right column. In the present invention, when using a high-boiling organic solvent, the amount of the high-boiling organic solvent used may be any amount,
Preferably, the ratio of the high-boiling organic solvent / color-forming reducing agent to the color-forming reducing agent is 20 or less by weight, preferably 0.02 or less.
To 5 are more preferable, and 0.2 to 4 are particularly preferable.

In the present invention, a known polymer dispersion method may be used. As one of the polymer dispersion methods, the steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 25.
No. 41274, No. 2541230, JP-B-53-4
No. 1091 and European Patent Publication No. 029104, and a more preferable method is a dispersion method using a water-insoluble and organic solvent-soluble polymer.
It is described in CT International Publication No. WO 88/00723.

The average particle size of the lipophilic fine particles containing the color-forming reducing agent of the present invention is not particularly limited, but is preferably from 0.05 to 0.3 μm from the viewpoint of color-forming properties. Further, the thickness is more preferably 0.05 to 0.2 μm.

Generally, in order to reduce the average particle size of the lipophilic fine particles, it is necessary to select the type of the surfactant, increase the amount of the surfactant used, increase the viscosity of the hydrophilic colloid solution, This can be achieved by lowering the viscosity of the organic layer by using a low-boiling organic solvent in combination, increasing the shearing force such as increasing the rotation of the stirring blades of the emulsifier, or increasing the emulsification time.

The particle size of the lipophilic fine particles can be measured by, for example, an apparatus such as Nanosizer manufactured by Coulter, UK.

In the present invention, when the dye formed from the color-forming reducing agent and the dye-forming coupler is a diffusible dye, it is preferable to add a mordant to the light-sensitive material. When the present invention is applied to such an embodiment, it is not necessary to immerse the color in an alkali after washing with water or stabilizing treatment, so that the image stability after the treatment is remarkably improved.
The mordant of the present invention may be used in any of the layers, but when added to a layer containing the color-forming reducing agent of the present invention, the stability of the color-forming reducing agent deteriorates. It is preferable to use the layer containing no reducing agent. Furthermore, the dye formed from the color-forming reducing agent and the coupler diffuses through the swollen gelatin film during the treatment and dyes the mordant. for that reason,
In order to obtain good sharpness, it is preferable that the diffusion distance is short. Therefore, the layer to which the mordant is added is preferably added to the layer adjacent to the layer containing the color-forming reducing agent.

Since the coloring agent of the present invention and the dye formed from the coupler of the present invention are water-soluble dyes, they may flow out into the processing solution. Therefore, the layer to which the mordant is added to prevent this is preferably on the side opposite to the support with respect to the layer containing the color-forming reducing agent. However, when a barrier layer as described in JP-A-7-168335 is provided on the side opposite to the support with respect to the layer to which the mordant is added, the layer to which the mordant is added contains a color-forming reducing agent. It is also preferably on the same side as the support with respect to the layer being made.

The mordant of the present invention may be added to a plurality of layers. In particular, when a plurality of layers contain a color-forming reducing agent, the mordant is added to each adjacent layer. Is also preferred.

The coupler forming the diffusible dye may be any coupler as long as the diffusible dye formed by coupling with the reducing agent of the present invention reaches the mordant. The dye preferably has at least one dissociating group having a pKa (acid dissociation constant) of 12 or less, more preferably has one or more dissociating groups having a pKa of 8 or less, and particularly preferably has a dissociating group having a pKa of 6 or less. The molecular weight of the diffusible dye formed is 200 or more and 200
0 or less is preferable. In addition, the molecular weight of the dye formed /
The number of dissociating groups having a pKa of 12 or less is preferably from 100 to 2,000, and more preferably from 100 to 1,000. Here, as the value of pKa, a value measured using dimethylformamide: water = 1: 1 as a solvent is used.

The coupler forming the diffusible dye is soluble in the alkaline solution having a solubility of 1 × 10 ⁻⁶ mol / l or more at pH 11 at 25 ° C. in a diffusible dye formed by coupling with the color-forming reducing agent of the present invention. More preferably, it is more preferably 1 × 10 ⁻⁵ mol / liter or more, and more preferably 1 × 10 ⁻⁵ mol / l.
It is particularly preferable to dissolve at least ^-4 mol / l. The coupler forming the diffusible dye is dissolved in an alkaline solution having a diffusion constant of 25 ° C. and a pH of 11 at a concentration of 10 ^-4 mol / l in an alkaline solution having a diffusion constant of 25 ° C., which is formed by coupling with the color-forming reducing agent of the present invention. In this case, it is preferably 1 × 10 ⁻⁸ m ² / s ⁻¹ or more, more preferably 1 × 10 ⁻⁷ m ² / s ⁻¹ or more, and 1 × 10 ⁻⁶ m ² / s ^−. It is particularly preferred that it is ¹ or more.

The mordant which can be used in the present invention can be arbitrarily selected from mordants usually used.
Among them, a polymer mordant is particularly preferable. Here, the polymer mordant is a polymer having a tertiary amino group,
Polymers having a nitrogen-containing heterocyclic moiety;
And a polymer containing a class cationic group.

Specific examples of homopolymers and copolymers containing a vinyl monomer unit having a tertiary imidazole group are described in US Pat. Nos. 4,282,305 and 4,115,124.
No. 3,148,061 and JP-A-60-118834.
No. 60-122941, No. 62-244043
And No. 62-244036.

Preferred specific examples of homopolymers and copolymers containing a vinyl monomer unit having a quaternary imidazolium salt include British Patent Nos. 2056101 and 20.
Nos. 93041 and 1594961, U.S. Pat.
No. 24386, No. 4115124, No. 44502
No. 24, JP-A-48-28325 and the like.

Other preferred specific examples of homopolymers and copolymers having a vinyl monomer unit having a quaternary ammonium salt include US Pat. No. 3,709,690;
Nos. 3,988,088 and 3,598,995, JP-A-60-57836, JP-A-60-60643, and JP-A-60-60643.
122940, 60-122942, 60-2
No. 35134 and the like.

In addition, US Pat. Nos. 2,548,564, 2,484,430, 3,148,161 and 37.
US Pat. Nos. 3,625,694 and 3,585,096, vinylpyridine polymers and vinylpyridinium cationic polymers disclosed in US Pat.
No. 4,128,538, British Patent No. 1,277,453.
Mordants capable of cross-linking with gelatin and the like disclosed in US Pat.
No. 21852, No. 2798063, JP-A-54-1
No. 15228, No. 54-145529, No. 54-26
Aqueous sol-type mordant disclosed in specification 027 and the like;
Water-insoluble mordant disclosed in U.S. Pat. No. 3,988,088; U.S. Pat.
No. 4-137333) Reactive mordant capable of forming a covalent bond with the dye disclosed in the specification, etc .;
No. 09690, No. 3788855, No. 36424
No. 82, No. 3488706, No. 355706
No. 3,271,147, JP-A-50-71332.
No. 53-30328, No. 52-155528,
Mordants disclosed in JP-A-53-125 and JP-A-53-1024 can be exemplified.

Other examples include mordants described in US Pat. Nos. 2,675,316 and 2,882,156.

The molecular weight of the polymer mordant of the present invention is 1,0.
100 to 1,000,000 is suitable, and especially 10,000
00 to 200,000 is preferred.

The above-mentioned polymer mordant is usually used as a mixture with a hydrophilic colloid. As the hydrophilic colloid, a hydrophilic colloid, a highly hygroscopic polymer or both of them can be used, and gelatin is most typical. The mixing ratio of the polymer mordant and the hydrophilic colloid, and the amount of the polymer mordant applied, are easily determined by those skilled in the art according to the amount of the dye to be morded, the type and composition of the polymer mordant, and the image forming process to be used. The mordant / hydrophilic colloid ratio is 20 / 80-80 / 20 (weight ratio), and the mordant application amount is suitably 0.2-15 g / m ² , preferably 0.5-8 g / m 2. Preferably used in ² .

In the present invention, it is preferable to use an auxiliary developing agent and its precursor in the light-sensitive material, and these compounds will be described below.

The auxiliary developing agent used in the present invention is a compound having an action of promoting electron transfer from a color-forming reducing agent to silver halide in the course of developing silver halide grains, and is preferably exposed. It is a compound capable of developing silver halide grains and oxidizing the same to oxidize a color-forming reducing agent (hereinafter referred to as cross-oxidation).

The auxiliary developing agent used in the present invention is preferably pyrazolidones, dihydroxybenzenes, reductones or aminophenols, and particularly preferably pyrazolidones. The lower the diffusivity of these compounds in the hydrophilic colloid layer, the better. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0% or less. 0.01% or less.

The precursor of the auxiliary developing agent used in the present invention is a compound which is stably present in the light-sensitive material, but which releases the auxiliary developing agent quickly once it is processed with a processing solution. Also when using, it is preferable that the diffusivity in the hydrophilic colloid layer is low. For example, the solubility in water (25 ° C.) is preferably 0.1% or less, more preferably 0.05% or less, and particularly preferably 0.01% or less. The solubility of the auxiliary developing agent released from the precursor is not particularly limited, but the auxiliary developing agent itself preferably has low solubility.

Specific examples of the auxiliary developing agent or its precursor are shown below, but the compounds used in the present invention are not limited to these specific examples.

[0124]

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[0125]

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These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer, and the protective layer. When the compound contains an auxiliary developing agent, it is preferably used by adding it to a non-photosensitive layer.

The method for incorporating these compounds into the light-sensitive material includes a method in which the compound is dissolved in a water-miscible organic solvent such as methanol and directly added to the hydrophilic colloid layer. A method of dissolving in a solvent or oil that is substantially immiscible with water and then adding a substance dispersed in water or a hydrophilic colloid or a method of adding a solid fine particle dispersion. Conventionally known methods can be applied alone or in combination. The method for preparing the solid fine particle dispersion is described in detail in page 20 of JP-A-2-23544.

The amount added to the light-sensitive material is from 1 mol% to 200 mol%, preferably from 5 mol% to 1 mol%, based on the color-forming reducing agent.
00 mol%, more preferably 10 mol% to 50 mol%.

The support used in the present invention includes glass,
Any support such as paper and plastic film which can be coated with a photographic emulsion layer can be used as long as it is a transmission or reflection support. As the plastic film used in the present invention, a polyester film such as polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate or cellulose nitrate, a polyamide film, a polycarbonate film, a polystyrene film and the like can be used.

The term "reflective support" which can be used in the present invention means a material which enhances reflectivity to sharpen a dye image formed on a silver halide emulsion layer. Is a support coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium oxide, or calcium sulfate, or a hydrophobic resin itself containing a light-reflecting substance dispersed therein. Included are those used as For example, polyethylene-coated paper, polyester-coated paper, polypropylene-based synthetic paper, a support provided with a reflective layer or combined with a reflective substance, for example, a glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, polyamide film , Polycarbonate film, polystyrene film, and vinyl chloride resin. As the polyester-coated paper, particularly, a polyester-coated paper containing polyethylene terephthalate as a main component described in European Patent EP 0507489 is preferably used.

The reflective support used in the present invention is preferably a paper support coated on both sides with a water-resistant resin layer, wherein at least one of the water-resistant resins contains fine white pigment particles. The white pigment particles are preferably contained at a density of 12% by weight or more, more preferably 14% by weight or more. As the light-reflective white pigment, it is preferable to sufficiently knead the white content in the presence of a surfactant, and it is preferable that the surface of the pigment particles is treated with a divalent to tetravalent alcohol.

In the present invention, a support having a second-class diffuse reflective surface can be preferably used. The second type diffuse reflectivity refers to diffuse reflectivity obtained by imparting irregularities to a surface having a mirror surface and dividing the mirror surface into minute mirror surfaces facing different directions. The unevenness of the surface of the second type diffuse reflection has a three-dimensional average roughness of 0.1 to 2 μm, preferably 0.1 to
1.2 μm. Details of such a support are described in JP-A-2-239244.

In order to obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. Can be For example, three layers of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, and three layers of a green-sensitive layer, a red-sensitive layer, and an infrared-sensitive layer are applied in combination on the support. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

The light-sensitive material can be provided with a photographic component layer comprising the above-described light-sensitive layer and various non-light-sensitive layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to the photographic component layer in order to improve color separation.

As the binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. The calcium content of gelatin is preferably 800 ppm or less, more preferably 200 ppm or less, and the iron content of gelatin is preferably 5 ppm or less, more preferably 3 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-2712
It is preferable to add a fungicide as described in JP-B-47.

When exposing the light-sensitive material of the present invention to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved.

The light-sensitive material of the present invention can be used not only in a printing system using a normal negative printer but also in a gas laser, a light-emitting diode, a semiconductor laser, or a solid-state laser using a semiconductor laser as an excitation light source. 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. The system is compact,
It is preferable to use a second harmonic generation light source (SHG) in which a semiconductor laser, a semiconductor laser or a solid-state laser and a nonlinear optical crystal are combined in order to reduce the cost. Particularly, in order to design a device which is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum of the light-sensitive material of the present invention can be arbitrarily set depending on the wavelength of the scanning exposure light source used. The semiconductor laser is a solid laser used as an excitation light source or SHG obtained by combining a semiconductor laser with a nonlinear optical crystal.
In the light source, the emission wavelength of the laser can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual 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 the available inexpensive and stable III-V semiconductor lasers currently have an emission wavelength range only from the red to the infrared region. However, at the laboratory level, oscillations of II-VI group semiconductor lasers in the green and blue regions have been confirmed, and if semiconductor laser manufacturing technology develops, these semiconductor lasers can be used stably at low cost. It is fully anticipated. In such a case, the necessity for at least two layers to have a spectral sensitivity maximum at 670 nm or more is reduced.

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

The silver halide grains used in the present invention include silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver bromoiodide,
It is silver chloroiodobromide. Other silver salts, such as rodin silver,
Silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains. When rapid development and desilvering (bleaching, fixing and bleach-fixing) steps are desired, so-called high silver chloride grains having a silver chloride content of 90 mol% or more are desirable. In order to appropriately suppress development, it is desirable to contain silver iodide. The preferred silver iodide content depends on the intended light-sensitive material.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in a layered or non-layered form inside and / or on the surface of silver halide grains.

It is also effective to further increase the silver chloride content of the silver halide emulsion in order to reduce the replenishment amount of the developing solution. In such a case, the silver chloride content is 9
Emulsions of substantially pure silver chloride, such as 8 mol% to 100 mol%, are also preferably used.

The silver halide emulsion of the present invention preferably has a distribution or structure with respect to the halogen composition in the grains. A typical example is JP-B-43-131.
No. 62, JP-A-61-215540 and JP-A-60-2
No. 22845, JP-A-60-143331, JP-A-6-143331
No. 1-75337 and JP-A-60-222844.

In order to provide a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. These examples are disclosed in
-133540, JP-A-58-108526, EP 199290A2, JP-B-58-24772.
And JP-A-59-16254.

In the case of a joint structure, a combination of silver halides is of course possible, but a silver salt compound having no rock salt structure such as silver rhodanate or silver carbonate can be combined with silver halide to form a joint structure.

It is important to suppress the halogen composition near the surface of the grains. Increase the silver iodide content near the surface,
Alternatively, increasing the silver chloride content can be selected according to the purpose because the adsorption property of the dye and the developing speed are changed.

Even if the silver halide grains used in the present invention are normal crystals that do not contain twin planes, they can be edited by the Photographic Society of Japan, “Basics of the Photographic Industry, Silver Salt Photography” (Corona), page 163 (Showa 54). Example, two parallel twin planes
It can be selected and used according to the purpose from parallel multiple twins including two or more non-parallel twins including two or more non-parallel twin planes. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964. In the case of a normal crystal, a cube consisting of (100) planes, an octahedron consisting of (111) planes, Japanese Patent Publication No. 55-42737,
A dodecahedral particle having a (110) plane disclosed in JP-A-222842 can be used. In addition, Jou
rnal of Imaging Science 3
Particles having (hlm) planes as reported in Vol. 0, page 247 (1986) can be selected and used according to the purpose. A tetrahedron in which (100) planes and (111) planes coexist in one particle Particles having two or many planes, such as particles, (100) and (110) planes, or (111) and (110) planes, may be selected according to the purpose. Can be used.

The value obtained by dividing the circle equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio greater than 1 can be used in the present invention. Tabular grains are described in Cleeve, "Theory and Practice of Photography" (Cleve, Photography Th.
eory and Practice (1930)),
131 pages; Photographic Science and Engineering by Gaft (Gutoff, Phot)
graphical Science and Engin
eering), Vol. 14, pp. 248-257 (197
0); U.S. Patent Nos. 4,434,226 and 4,441,431
No. 4,443,048, 4,439,520 and British Patent No. 2,121,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in color sensitization efficiency by a sensitizing dye, and the like. US Pat.
No. 26 describes this in detail. 8 of the total projected area of the grain
The average aspect ratio of 0% or more is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. The shape of the tabular grains can be selected from triangles, hexagons, and circles.
A regular hexagon having approximately equal lengths of six sides as described in U.S. Pat. No. 4,797,354 is a preferred form.

The silver halide emulsion used in the present invention may be prepared by subjecting grains to a rounding treatment as disclosed in European Patent Nos. 96727B1 and 64412B1, or by West German Patent No. 2306447C2, JP-A-60-2213.
The surface may be modified as disclosed in No. 20.

A structure having a flat particle surface is generally used.
It is preferable in some cases to form irregularities intentionally.
JP-A-58-106532, JP-A-60-22132
0 or U.S. Patent No. 4,643,966.

The emulsion used in the present invention may be a polydisperse emulsion having a wide grain size distribution, or a monodisperse emulsion having a narrow size distribution. As a scale representing the size distribution, a variation coefficient of a circle equivalent diameter of a projected area of a particle or a sphere equivalent diameter of a volume may be used. When a monodispersed emulsion is used, the coefficient of variation is 25% or less,
It is more preferable to use an emulsion having a size distribution of 20% or less, more preferably 15% or less.

In order to satisfy the desired gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes are mixed in the same layer in an emulsion layer having substantially the same color sensitivity. Alternatively, it can be applied in another layer. Further, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion can be used as a mixture or as a mixture.

The photographic emulsion used in the present invention is described in "Graphicde, Photographic Physics and Chemistry", published by Paul Mondell (P.G.
lafkides, Cheimie et Physi
que Photographique Paul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Che
Mistry (FocalPress, 1966), "Manufacture and Coating of Photographic Emulsion" by Zelikman et al., Published by Focal Press (VL Zelikman et al, M.
aking and Coating Photogr
aphic Emulsion, Focal Pres
s, 1964) and the like. A method of forming grains in the presence of excess silver ions (a so-called reverse mixing method) can also be used.
As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept 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.

A method of adding previously precipitated silver halide grains to a reaction vessel for preparing an emulsion, US Pat.
012, 4301241, and 4150994 are sometimes preferable. These can be used as seed crystals, and are also effective when supplied as silver halide for growth. It is also effective in some cases to add fine particles having various halogen compositions to modify the surface.

A silver halide solvent is useful for the purpose of accelerating ripening. For example, it is known to have an excess of halogen ions in the reactor to promote ripening. Other ripening agents can also be used. These ripening agents can be incorporated in their entirety in a dispersion medium in a reactor before adding a silver salt and a halide salt,
A halide salt, silver salt or peptizer may be provided and introduced into the reactor.

Examples of these compounds include ammonia, thiocyanate (rhodancali, rhodanammonium, etc.), and organic thioether compounds (for example, US Pat. No. 3,574,462).
No. 8, No. 3021215, No. 3057724, No. 3
No. 388805, No. 4276374, No. 429743
No. 9, 3704130, 4782013 and JP-A-57-104926. ), Thione compounds (for example, JP-A-53-82408,
No. 77737, U.S. Pat. No. 4,221,863, etc .;
No. 19) and JP-A-57-20
And mercapto compounds and amine compounds (for example, JP-A-54-100717) capable of promoting the growth of silver halide grains described in JP-A No. 2531.

Gelatin is advantageously used as a protective colloid used in preparing the emulsion of the present invention and as a binder for other hydrophilic colloid layers.
Other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other macromolecules, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugars such as sodium alginate and starch derivatives Derivatives: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide,
Various kinds of synthetic hydrophilic high molecular substances such as a single or copolymer such as polyvinylimidazole and polyvinylpyrazole can be used.

Examples of gelatin include coal-treated gelatin, acid-treated gelatin and Bull. Soc. Sci. Ph
oto. Japan, No. 16, P308 (196
Enzyme-treated gelatin as described in 6) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used. Use of low molecular weight gelatin described in JP-A-1-158426 is preferred for preparing tabular grains.

The silver halide emulsion was washed with water for desalting,
It is preferable to use a newly prepared protective colloid dispersion. The temperature for water washing can be selected according to the purpose, but is preferably selected in the range of 5 to 50 ° C. The pH at the time of washing can be selected according to the purpose, but is preferably selected from 2 to 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing can be selected according to the purpose, but is preferably selected from 5 to 10.
The method for washing can be selected from noodle washing, dialysis using a semipermeable membrane, centrifugal separation, coagulation sedimentation, and ion exchange. In the case of the coagulation sedimentation method, a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative, and the like can be selected.

The preparation of a silver halide emulsion, for example, at the time of grain formation, at the desalting step, at the time of chemical sensitization, or before the coating is preferably carried out in the presence of a metal ion salt depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain and a method of doping only the core portion, only the shell portion, only the epitaxial portion, or only the base grain of the grain can be selected. Mg, Ca, Sr, Ba, A
1, Sc, Y, La, Cr, Mn, Fe, Co, Ni,
Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, I
r, Pt, Au, Cd, Hg, Tl, In, Sn, P
b, Bi, etc. can be used. These metals can be added as long as they can be dissolved at the time of particle formation, such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides, hexacoordinate complex salts, and tetracoordinate complex salts.

In some cases, a method of adding a chalcogen compound during preparation of an emulsion as described in US Pat. No. 3,770,203 is useful. In addition to S, Se, and Te, cyanide, thiocyanate, selenocyanate, carbonate, phosphate, and acetate may be present.

The silver halide grains used in the present invention are at least one of sulfur sensitization, selenium sensitization, tellurium sensitization (these three are collectively referred to as chalcogen sensitization), noble metal sensitization, and reduction sensitization. Can be applied in any step of the production process of the silver halide emulsion. It is preferable to combine two or more sensitization methods. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion used in the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose.

Chemical sensitization which can be preferably carried out in the present invention is chalcogen sensitization and noble metal sensitization alone or in combination thereof, and is described by TH (James), The Photographic Process, Fourth Edition. , Macmillan, 1977, (TH James, The Th
eory of the PhotographicP
loss, 4th ed, Macmillan, 1
977) pp. 67-76, and can be performed using active gelatin, and can also be performed using Research Disclosure Item 12008 (Apr. 1974).
Month); Item 13452 (June 1975);
tem 307105 (November 1989), U.S. Patent Nos. 2,642,361, 3,297,446 and 3,772.
No. 031, No. 3857711, No. 3901714,
Nos. 4,266,018 and 3,904,415 and p.
Ag 5 to 10, pH 5 to 8 and temperature 30 to 80 ° C. can be carried out with sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers.

In the sulfur sensitization, an unstable sulfur compound is used, specifically, thiosulfate (eg, hypo),
Thioureas (eg, diphenylthiourea, triethylthiourea, allylthiourea, etc.), rhodanines, mercaptos, thioamides, thiohydantoins, 4-oxo-oxozolidine-2-thiones, di- or polysulfides, polythioic acid Salts and elemental sulfur, as well as known sulfur-containing compounds described in U.S. Patent Nos. 3,857,711, 4,266,018 and 4,054,457 can be used. Sulfur sensitization is often used in combination with noble metal sensitization.

The preferred amount of sulfur sensitizer to be used for silver halide grains is 1 × 10 ^-7 per mol of silver halide.
１1 × 10 ⁻³ mol, more preferably 5 × 10 ^-3 mol.
^-7 to 1 × 10 ^-4 mol.

In the selenium sensitization, a known unstable selenium compound is used, for example, US Pat. No. 3,297,446.
And selenium compounds described in Nos. 3,297,447 and the like, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, tetramethylselenourea, etc.), selenoketones (Eg, selenoacetone), selenoamides (eg, selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (eg,
Diethyl selenide, triphenylphosphine selenide), selenophosphates (for example, tri-p-
Selenium compounds such as tolyl selenophosphate) can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

[0168] The amount of the selenium sensitizer, the kind of selenium compounds and silver halide grains to be used will vary with the chemical ripening condition and the like, generally, per mol of silver halide 10 ^-8 to
^10-4 mol, preferably about ^10-7 to ^10-5 mol is used.

The tellurium sensitizers used in the present invention include Canadian Patent No. 800958 and British Patent No. 1295.
No. 462, No. 1396696, Japanese Patent Application No. 2-33381
Compounds described in Nos. 9 and 3-131598 can be used.

In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide,
Known compounds such as gold selenide can be used.
The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are R ₂ PdX ₆
Or represented by R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group.
X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

The emulsion used in the present invention is preferably used in combination with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-7 to 1 × 10 ^-3 mol, and more preferably 5 × 10 ^{-7 to} 5 × 10 ^-4 mol, per mol of silver halide. The preferred range of the palladium compound is from 5 × 10 ^-7 to
It is 1 × 10 ^-3 mol. The preferable range of the thiocyan compound or the selenocyan compound is 1 × 10 ^{−6 to} 5 × 10
^-2 moles.

It is preferable that the silver halide emulsion is subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization refers to a method in which a reduction sensitizer is added to a silver halide emulsion, or a pAg 1 called silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening. Also, two or more methods can be used in combination.

As the reduction sensitizer, known reduction sensitizers such as stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine and its derivatives, formamidine sulfinic acid, dilan compounds and borane compounds are selected. And two or more compounds can be used in combination. Stannous chloride as reduction sensitizer,
Aminoiminomethanesulfinic acid (common name: thiourea dioxide), dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds.

Chemical sensitization can be carried out in the presence of a so-called chemical sensitization aid. As useful chemical sensitization aids, compounds such as azaindene, azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the course of chemical sensitization are used. Examples of chemical sensitization aids are described in U.S. Pat. Nos. 2,131,038 and 3,411,914.
No. 3,554,575, JP-A-58-126526, and the aforementioned "Photographic Emulsion Chemistry" by Duffin, 138-1.
It is described on page 43.

It is preferable to use an oxidizing agent for silver during the emulsion production process. The oxidizing agent for silver refers to a compound having an action of converting metallic silver into silver ions. In particular, a compound that converts very fine silver particles by-produced in the process of forming silver halide grains and in the step of chemical sensitization into silver ions is effective. The silver ions generated here may form a silver salt that is hardly soluble in water such as silver halide, silver sulfide, and silver selenide, or may form a silver salt that is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be inorganic or organic.

It is a preferred embodiment to use the above-mentioned reduction sensitization and an oxidizing agent for silver together.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. . That is, thiazoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, and aminotriazoles , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazole, (1-phenyl-5-mercaptotetrazole,
-(5-methylureidophenyl) -5-mercaptotetrazole, etc .; mercaptopyrimidines; mercaptotriazines, such as thioketo compounds such as oxadolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly Many compounds known as antifoggants or stabilizers can be added, such as, 4-hydroxy-6-methyl (1,3,3a, 7) tetraazaindene), pentaazaindenes and the like. For example, US Pat.
No. 982947 and JP-B No. 52-28660 can be used. One of the preferred compounds is a compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before, during and after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added according to the purpose.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like. The dyes used include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes are included. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thioazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus,
A benzimidazole nucleus, a quinoline nucleus and the like can be applied.
These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, nuclei having a ketomethylene structure include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidin-2,4-dione nucleus, and a thiazolidine-2,4-nucleus.
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for supersensitization. Representative examples are U.S. Pat. Nos. 2,688,545 and 2,977,229.
No. 3397060, No. 3522052, No. 35
No. 27641, No. 3617293, No. 3628964
Nos. 3666480, 3672898, 36
No. 79428, No. 3703377, No. 3769301
Nos. 3814609, 3837862, 40
No. 26707, British Patent Nos. 1344281 and 150
No. 7803, JP-B-43-4936, JP-B-53-123
No. 75, JP-A Nos. 52-110618 and 52-109
925.

Along with the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. It is most usually carried out after completion of chemical sensitization but before coating, but US Pat.
JP-A-58-113928 discloses that a chemical sensitizer is added simultaneously with a chemical sensitizer to carry out spectral sensitization simultaneously with chemical sensitization as described in JP-A Nos. Can be performed prior to chemical sensitization,
It can also be added before the completion of silver halide grain precipitation to start spectral sensitization. No. 42
As taught in US Pat. No. 25666, it is also possible to add these compounds separately, that is, to add some of these compounds prior to chemical sensitization and the remainder after chemical sensitization. It is possible at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 parts per mole of silver halide.
It can be used in an amount of from × 10 ^-6 to 8 × 10 ^-3 mol, but a more preferable silver halide grain size is from 0.2 to 1.2 μm.
In this case, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective.

The above-mentioned various additives are used in the light-sensitive material according to the present technology, and other various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978) and Item 18716 (November 1979).
Mon) and Item 307105 (November 1989)
Month).

The total amount of silver coated on the light-sensitive material of the present invention is preferably 0.003 to 12 g per m ^{2 in} terms of silver. In the case of a transparent material such as a color negative film, the amount is preferably 1 to 12 g, more preferably 3 to 10 g.
0.003-1 g for reflective materials such as color paper
Is preferred in terms of rapid processing and low replenishment. In this case, the amount of each layer is preferably 0.001 to 0.4 g per photosensitive layer. In particular, when intensifying the light-sensitive material of the present invention, the amount is preferably from 0.003 to 0.3 g, more preferably from 0.01 to 0.1 g, and particularly preferably from 0.015 to 0.1 g.
05 g. In this case, 0.001 per photosensitive layer
0.1 g, more preferably 0.003 g
0.03 g.

In the present invention, when the coated silver amount of each photosensitive layer is less than 0.001 g per 1 m ² , the dissolution of the silver salt proceeds,
When sufficient color density cannot be obtained and when intensification processing is performed.
When the amount exceeds 1 g, D _min increases and bubbles are generated, which makes it difficult to appreciate the view.

The total amount of gelatin in the light-sensitive material of the present invention is 1 m ²
1.0 to 30 g, preferably 2.0 to 20 g
g. In the swelling of the light-sensitive material of the present invention using an alkaline solution having a pH of 12, the time required to reach a swelled film thickness of 1/2 of its saturated swelled film thickness (90% of the maximum swelled film thickness) is preferably 15 seconds or less, Further, it is preferably 10 seconds or less. The swelling ratio ((maximum swollen film thickness−film thickness) / film thickness × 100) is 50
-300% is preferable, and 100-200% is particularly preferable.

The processing material and processing method used in the present invention will be described in detail. In the present invention, the photosensitive material is subjected to development using an activator solution, that is, activator processing, desilvering, and washing or stabilizing processing.
After the washing or stabilizing treatment, a treatment for enhancing color development such as alkali addition may be performed.

The activator process is a process in which a color-forming reducing agent is incorporated in a light-sensitive material, more preferably an auxiliary developing agent is incorporated, and development is performed with a processing solution containing no color-forming developing agent. Method. In the present invention, the "activator liquid" is characterized in that it does not substantially contain a p-phenylenediamine-based color developing agent as conventionally used, and other components (eg, alkali, halogen, chelating agent, etc.) ) May be included. In order to maintain the processing stability, it may be preferable that a reducing agent is not contained in some cases, and it is preferable that the auxiliary developing agent and the hydroxyamines contain substantially no sulfite or the like.

Here, “substantially not contained” means preferably 0.5 mmol / liter or less, more preferably 0.1 mmol / liter or less. In particular, it is preferable not to contain at all.

The pH of the alkaline solution is preferably from 9 to 14, and particularly preferably from 10 to 13.

To maintain the above pH, it is preferable to use various buffers. Preference is given to using carbonates, phosphates, tetraborates and hydroxybenzoates.

The amount of the buffer added to the activator solution was as follows:
It is preferably at least 0.05 mol / l, particularly preferably from 0.1 mol / l to 0.4 mol / l.

The activator treatment requires an auxiliary developing agent as a mediator for silver development of silver halide since the color-forming reducing agent is a compound that is very hydrophobic and hard to move in the emulsion layer. As the auxiliary developing agent, one which is easily broken by an alkali is used, and as described above, it is preferable to incorporate the auxiliary developing agent into the light-sensitive material. In this manner, the exposed silver halide is reduced by the auxiliary developing agent, and becomes an oxidized substance, diffuses into other layers, and cross-oxidizes a hard-to-move color reducing agent in the emulsion.

As such an auxiliary developing agent, pyrazolidones, dihydroxybenzenes, reductones and aminophenols are preferably used, and pyrazolidones are particularly preferably used.

The pyrazolidones include 1-phenyl-3
-Pyrazolidones are preferred, and 1-phenyl-3-pyrazolidone (phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-
4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone,
1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl -3-pyrazolidone, 1-p-chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl -3-pyrazolidone,
1-phenyl-2-hydroxymethyl-5-phenyl-
3-pyrazolidone and the like.

Examples of the dihydroxybenzenes include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone,
And potassium hydroquinone monosulfonate.

As the reductones, ascorbic acid or a derivative thereof is preferable, and the compounds described in JP-A-6-148822, pp. 3-10 can be used. Particularly, sodium L-ascorbate and sodium erythorbate are preferred.

Examples of p-aminophenols include N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, and 2-methyl-p-aminophenol. Aminophenol, and the like.

These compounds are usually used alone, but it is also preferable to use two or more of them in order to enhance development and cross-oxidation activity.

It is preferable that these compounds be incorporated in the light-sensitive material, but in some cases, they may be contained in the activator solution.
× 10 ^-4 mol / L to 0.2 mol / L, preferably 0.0025 mol / L to 0.1 mol / L, more preferably 0.001 mol / L to 0.1 mol / L.
05 mol / l.

Preservatives that can be used in the activator solution include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde bisulfite, hydroxylamine sulfate, and the like. When used, the amount used is generally 0.1 mol / l or less, preferably in the range of 0.001 to 0.02 mol / l. When a high silver chloride emulsion is used for the light-sensitive material, the amount of the compound is generally 0.001 mol / l or less, and it is preferable that the compound is not contained at all.

The activator liquid preferably contains an organic preservative such as diethylhydroxylamine or dialkylhydroxylamines described in JP-A-4-97355 in place of the above-mentioned hydroxylamine and sulfite ions.

The activator solution may contain halogen ions such as chlorine ions, bromine ions and iodine ions.

Here, the halide may be directly added to the activator solution, or may be eluted from the photosensitive material into the activator solution during the activator processing.

In addition, various chelating agents can be used in the activator solution as an agent for preventing precipitation of calcium or magnesium, or for improving the stability of the developing solution.

The addition amount of these chelating agents may be an amount sufficient to mask metal ions in the activator solution, and is, for example, about 0.1 g to 10 g per liter.

In the present invention, an optional antifoggant can be added as required. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds are used.

The addition amount of the nitrogen-containing heterocyclic compound was 1 × 1
0 ^-5 to 1 × 10 ^-2 mol / l, preferably 2.5 ×
It is 10 ^-5 to 1 × 10 ^-3 mol / l.

Any development accelerator can be added to the activator solution, if necessary.

The activator solution preferably contains a fluorescent whitening agent. In particular, 4,4'-diamino-2,
It is preferable to use a 2'-disulfostilbene compound.

The treatment temperature with the activator solution applied to the present invention is 20 to 70 ° C., preferably 35 to 55 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. It is preferable that the replenishment amount is small, but 1 m ²
The volume is 15 to 800 ml, preferably 25 to 400 ml, more preferably 35 to 200 ml.

After development with the activator solution, desilvering treatment is performed. The desilvering process includes a fixing process and a bleaching and fixing process. When performing the bleaching and fixing processes, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). Further, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose.

In some cases, it is also preferable to stabilize silver salts or color images without carrying out desilvering after development, in some cases.

After development, West German Patent (OLS) 18
No. 13920, No. 2044993, No. 2735262
No., JP-A-48-9728, JP-A-49-84240,
No. 49-102314, No. 51-53826, No. 5
An image reinforcement treatment (intensification) using a peroxide, a halogenous acid, an iodoso compound and a cobalt (III) complex compound described in JP-A Nos. 2-3336 and 52-73731 can be performed. In order to further enhance the image reinforcement, the above-mentioned oxidizing agent for reinforcing the image may be added to the activator liquid, and development and image intensification may be simultaneously performed in one bath.
In particular, hydrogen peroxide is preferable because of its high amplification factor. These image intensification methods can significantly reduce the amount of silver in the photosensitive material, so that bleaching is not required, and it is possible to eliminate the need to discharge silver (or silver salts) for stabilization, etc. This is a preferable treatment method.

Examples of the bleaching agent used in the bleaching solution or the bleach-fixing solution include compounds of polyvalent metals such as iron (III), cobalt (III), chromium (IV) and copper (II), peracids and quinones. And nitro compounds. Among them, iron (III) aminopolycarboxylate such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetic acid (III) complex, hydrogen peroxide, persulfate and the like are promptly treated and prevent environmental pollution. It is preferable from the viewpoint of.

The iron (III) aminopolycarboxylates
The pH of the bleaching solution or the bleach-fixing solution using a complex salt is used at 3 to 8, preferably 5 to 7. The pH of the bleaching solution using persulfate or hydrogen peroxide is 4 to 11, preferably 5 to 10.

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.

In the bleaching solution, the bleach-fixing solution and the fixing solution, conventionally known additives such as a rehalogenating agent, a pH buffer and a metal corrosion inhibitor can be used. Particularly, in order to prevent bleaching stain, the acid dissociation constant (pKa) is 2-7.
It is preferable that the organic acid is contained.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, a large amount of iodide salts and JP-A-4-365037, pages 11 to 2.
Examples thereof include a nitrogen-containing heterocyclic compound having a sulfide group, a mesoionic compound, and a thioether compound described on page 1 and 5-66540, pages 1088 to 1092.

As a preservative for the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable.

The fixing solution or the bleach-fixing solution may further contain various fluorescent whitening agents; antifoaming agents; surfactants; polyvinylpyrrolidone;

The processing temperature in the desilvering step is from 20 to 50 ° C., preferably from 30 to 45 ° C. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. The replenishment amount is preferably smaller, but is preferably 15 to 600 ml, preferably 25 to 200 ml, more preferably 35 to 100 ml per m ^{2 of} the light-sensitive material. It is also preferable to perform the treatment without replenishment, as the amount of evaporation is also made up with water.

The light-sensitive material of the present invention generally undergoes a washing step after desilvering. When the stabilization treatment is performed, the washing step may be omitted. In such a stabilization process, JP-A-57-8543 and JP-A-58-1483 are used.
Nos. 4 and 60-220345, and JP-A-5-220345.
8-127926, 58-13837, 58
All known methods described in JP-A-140741 can be used. Further, a washing step and a stabilizing step in which a stabilizing bath containing a dye stabilizing agent and a surfactant represented by processing of a color light-sensitive material for photography is used as a final bath may be performed.

Water washing and stabilizing solutions include sulfites; hard water softeners such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminosulfonic acid; metal salts such as Mg salt, Al salt and Bi salt; Agents; hardening agents; pH buffering agents; fluorescent whitening agents; silver salt-forming agents such as nitrogen-containing heterocyclic compounds;

Examples of the dye stabilizer for the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde sulfite adducts.

The pH of the washing or stabilizing solution is 4 to 9, preferably 5 to 8. The processing temperature is generally from 15 to 45 ° C, preferably from 25 to 40 ° C. The processing time is generally from 5 seconds to 2 minutes, preferably from 10 seconds to 40 seconds.

The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The amount of washing water and / or stabilizing solution can be set in a wide range depending on various conditions. The replenishing amount is preferably 15 to 360 ml, preferably 25 to 120 ml, per m ² of the light-sensitive material.
Is more preferred. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks and carry out the method in a multistage countercurrent system.

In the present invention, water obtained by treating an overflow liquid or a liquid in a tank with a reverse osmosis membrane to save water can be used. For example, the treatment by reverse osmosis is preferably performed on the water after the second tank for multi-stage countercurrent washing and / or stabilization.

In the present invention, it is preferable that the stirring is strengthened as much as possible. Specific methods of strengthening the stirring are described in JP-A-62-183460 and JP-A-62-1834.
No. 61, a method of impinging a jet jet of a processing liquid on an emulsion surface of a light-sensitive material, a method of increasing a stirring effect by using a rotating means of JP-A-62-183461, and a wiper blade provided in a liquid A method in which the photosensitive material is moved while bringing the emulsion surface into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Such stirring improving means include a developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution, a stabilizing solution,
It is useful in any washing. These methods are effective in that the supply of the effective component in the liquid into the photosensitive material and the diffusion of the unnecessary component of the photosensitive material are promoted.

In the present invention, the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )] of any bath shows excellent performance in any state, but from the viewpoint of the stability of the liquid components. The liquid aperture ratio is preferably from ⁰ to 0.1 cm ^-1 . In the continuous treatment, the practical range is preferably 0.001 cm ^{-1 to} 0.05 cm ^-1 , more preferably 0.002 to 0.0 cm ^-1.
3 cm ^-1 .

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. Such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing solution from deteriorating. Such an effect is particularly effective for shortening the processing time of each step and reducing the replenishing amount of the processing solution. In order to shorten the processing time, it is preferable to shorten the crossover time (air time).
For example, Japanese Patent Application Laid-Open No. 4-86659, FIG.
Also, a method in which each processing time described in FIG. 4 or FIG. 5 of JP-A-5-66540 is carried through a blade having a shielding effect is preferable.

In the case where each processing solution is concentrated by evaporation in the continuous processing, it is preferable to correct the concentration by adding water.

The processing time of the step in the present invention means the time required from the start of processing of the photosensitive material in one step to the start of processing in the next step. The actual processing time in an automatic developing machine is usually determined by the linear velocity and the capacity of the processing bath.
000 mm / min. In particular, in the case of a small developing machine, the speed is preferably 500 to 2500 mm / min.

The entire processing step, that is, the processing time from the developing step to the drying step is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying unit of the processor.

Various additives are used in the treatment applied to the present invention, and are described in more detail in Research Disclosure Item 36544 (September, 1994). The relevant portions are shown below. Processing agent type Page Developing agent 536 Preservative of developing agent 537 Left column Antifoggant 537 Chelating agent 537 Right column Buffer 537 Right column Surfactant 538 Left column and 539 Left column Bleaching agent 538 Bleaching accelerator 538 Right column- 539 left column chelating agent for bleaching 539 left column rehalogenating agent 539 left column fixing agent 539 right column preservative for fixing agent 539 right column chelating agent for fixing 540 left column surfactant for stabilization 540 left for stabilization Anti-scum agent 540 right Stabilizing chelating agent 540 right Antibacterial deodorant 540 right Color image stabilizer 540 right

The water saving technique applied to the present invention is described in detail in Research Disclosure Item 365.
44 (September 1994), page 540, right column to page 541, left column.

[0241]

The present invention will be described below in detail with reference to examples. However, the present invention is not limited to only these examples. Example 1 (Preparation of photosensitive material) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a subbing layer of a gelatin layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. Thus, a multilayer color photographic paper having the following layer configuration was produced. This is the sample (1
00).

A coating solution was prepared as follows. Preparation of First Layer Coating Solution 27.8 g of yellow color-forming coupler (ExY-1) and 20.5 g of color-forming reducing agent (I-32) were dissolved in a solvent (Solv-
4) The resulting solution was dissolved in 52 g and 73 cc of ethyl acetate, and this solution was emulsified and dispersed in 420 cc of a 12% aqueous solution of gelatin containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsion D.

On the other hand, silver chlorobromide emulsion D (cubic, 3: 7 mixture of a large-size emulsion having an average grain size of 0.88 μm and a small-size emulsion having an average grain size of 0.70 μm (silver molar ratio). Coefficient of variation in grain size distribution) Prepared 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide in each size emulsion was locally contained in a part of the surface of a grain having silver chloride as a base material). In this emulsion, blue-sensitive sensitizing dyes-1, 2 and 3 shown below were composed of silver 1
1.4 × 1 each for large size emulsions per mole
^0-4 moles, and for small size emulsions, 1.
7 × 10 ^-4 mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion D and this silver chlorobromide emulsion D were mixed and dissolved to prepare a first layer coating solution.

[0244]

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The coating solutions for the third and fifth layers were prepared in the same manner as the coating solution for the first layer by the following method. That is, silver chlorobromide emulsion E for the third layer (cubic, 1: 4 mixture of large size emulsion having an average grain size of 0.50 μm and small size emulsion of 0.41 μm (silver molar ratio), fluctuation of grain size distribution) Coefficients were 0.09 and 0.11, respectively, and silver bromide of each size emulsion was 0.8.
Mol% was partially contained on the surface of the silver chloride-based grain). This emulsion contains the following green-sensitive sensitizing dye-1 per mol of silver: 3.0 × 10 ^-4 mol for a large-sized emulsion and 3.6 for a small-sized emulsion.
× 10 ⁻⁴ mol, and green-sensitizing sensitizing dye-2 per mol of silver, 4.0 × 10 ⁻⁵ mol for large-size emulsion, and 7.0 × 10 ⁻⁵ for small-size emulsion. Mole is added. Further, 2.0 × 10 ^-4 mol of green-sensitive sensitizing dye-3 was added per mol of silver, and 2.8 × 10 ^-4 mol was added per mol of silver. I have. Emulsion E containing magenta color coupler (ExM-1) prepared in the same manner as silver chlorobromide emulsion E and emulsion D
Were mixed and dissolved to prepare a third layer coating solution.

[0246]

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Silver chlorobromide emulsion F for the fifth layer (cubic, 1: 4 mixture (larger silver ratio) of a large emulsion having an average grain size of 0.50 μm and a small emulsion having a mean grain size of 0.41 μm, silver mole ratio). Coefficients of variation were 0.09 and 0.11, respectively, and 0.8 mol% of silver bromide was locally contained in a part of the surface of silver chloride-based grains in each size emulsion). This emulsion contains the following red-sensitive sensitizing dye-1 per mol of silver, 5.0 × 10 ⁻⁵ mol for a large-sized emulsion and 6.0 × 10 ⁻⁵ mol for a small-sized emulsion. Moles of red-sensitizing sensitizing dye-2 per mole of silver, 5.0 × 10 ⁻⁵ moles for large-size emulsions and 6.0 for small-size emulsions.
× 10 ^-5 mol is added.

[0248]

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Further, the compound A-2 was added to the fifth layer in an amount of 2.6 × 10 ⁻³ mol per mol of silver.

This silver chlorobromide emulsion F and an emulsion F containing a coupler for cyan coloring (ExC-1) prepared in the same manner as the emulsion D were mixed and dissolved to prepare a coating solution for a fifth layer. .

The coupler and A-2 used in the above are shown below.

[0252]

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[0253]

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The second, sixth and seventh layers were also prepared so as to have the compositions described below.

An auxiliary developing agent (ETA-6) was added to the intermediate layer of the second layer and the fourth layer in an amount of 1.4 × 10 ⁻⁴ mol in a state of solid dispersion of fine particles.

The following compounds were used as the solvent, color image stabilizer, ultraviolet absorber, color mixing inhibitor, surfactant and the like.

As the gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

In each layer, Cpd-4 and Cpd-4 shown below are shown.
Total amount -5 respectively, was added to a 25 mg / m ² and 50 mg / m ^2.

The blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer were treated with 1- (5-methylureidophenyl)-
5-mercaptotetrazole was replaced by silver halide 1
8.5 × 10 ^-5 mol, 9.0 × 10 ^-4 mol per mol,
2.5 × 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.

For the purpose of preventing irradiation, the following dyes were added to the emulsion layers (the coating amount is shown in parentheses).

[0261]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). It represents the amount of silver halide emulsion and silver equivalent.

[0263]

[Table 1]

[0264]

[Table 2]

In addition to those already described, the drugs and the like used above are as follows.

[0266]

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[0267]

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[0268]

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After cutting the sample prepared as described above,
A sensitometer (Fuji Photo Film Co., FW type,
A light source color temperature of 3200 ° K) was used to provide a gradation exposure of a three-color separation filter for sensitometry.

The exposed samples were processed in the steps of development, bleach-fix, stabilization, and drying using a processing solution having the following composition. The following treatments A to F were performed according to the treatment conditions, and the treatment performance was evaluated as follows.

<Treatment liquid composition> Activator liquid (alkaline activation bath) Tank liquid (common to replenisher) Water 800 ml 29 g 5-sodium sulfosalicylate (or 30 g of tripotassium phosphate may be used, in this case 30 g) Potassium 10 g Hydroxyethylidene-1,1-diphosphonic acid (30% solution) 4 ml Add water 1 liter pH 12.0 Bleaching fixer Tank solution Replenisher water 600 ml 150 ml Ammonium thiosulfate (700 g / l) 100 ml 250 ml ammonium sulfite / 1 water Salt 40g 40g Ammonium iron (III) ethylenediaminetetraacetate 77g 154g Ethylenediaminetetraacetic acid 5g 10g Ammonium bromide 10g 20g Acetic acid (50%) 70ml 140ml Add water 1000ml 1000ml Stabilizing solution Tank solution (common replenisher) Water 900ml Citric acid 4 2g-hydroxyethylidene-1,1-diphosphonic acid 1.0 ml (30% solution) 5-chloro-2-methyl-4-isothiazolin-3-one 0.02g Water to make 1 liter pH6.0

<Evaluation of Photographic Performance> Gradation: Maximum density (D _max ) −0.2 of blue-sensitive layer and D
_The gradient connecting the points of _max- 1.0 was used. Stain: The value of the minimum density (D _min ) of the green sensitive layer is D =
It was evaluated by how much it increased with respect to 0.10. 0.0
If it is 2 or more, it becomes a practical problem. Preservability of color image: Evaluation was made based on a decrease in _Dmax of the red-sensitive layer when the processed photosensitive material was allowed to stand at 60 ° C. and 70% RH for 7 days.
Discoloration and discoloration are practically unknown at 0.2 or less.

(Processing A) Processing Step Temperature Time Replenishment Volume Tank Capacity Development 40 ° C. 30 seconds 300 ml / m ² (sensitive material) 10 liters Bleaching and fixing 40 ° C. 15 seconds 200 ml / m ² (sensitive material) 5 liters Stabilizing 40 ° C. 10 seconds 200 ml / m ² (sensitive material) 5 liter drying 80 ° C 10 seconds −

In the processing A according to the above-mentioned processing steps, a running was performed for 10 days at a processing amount of 4 pieces (about 0.3 m ² ) cut into four pieces a day.

On the first day, the desired photographic performance was obtained, but in the first week, the increase in D _min of the green-sensitive layer was 0.12, the stain was increased, and the gradation was softened to 1.34, and printing was performed. As it did not stand to see. In addition, the storage stability of the color image was such that the reduction in _Dmax of the red-sensitive layer was 0.68 and the discoloration was large.

It is considered that the increase in stain is caused by the residual color of the auxiliary developing agent and the residual color of the dye and the pigment eluted from the light-sensitive material in the activator solution. The softening of the gradation is considered to be caused by the fact that the activator solution has a high pH and the pH is lowered by CO ₂ in the air. The poor preservability of the color image is considered to be due to the fact that the auxiliary developing agent is not sufficiently eluted in the activator processing and remains in the light-sensitive material.

(Process B) The process was performed in the same manner as in process A except that the activator processing tank was replaced with a countercurrent replenishment type slit processing tank as shown in FIG. The slit gap of the slit treatment tank was 1 mm, the width was 260 mm, and the treatment path length was 400 mm. The tank capacity was about 100 ml. However, the heater used was a planar heater, and was mounted so as to cover the entire upper surface of the slit treatment tank. The temperature control range was 40 ± 1 ° C. The treatment was performed in the same manner as in the treatment A, but the treatment B showed good performance without increasing the stain and softening even in the second week. In the first week, the increase in D _min of the green-sensitive layer was 0.01 and no stain was generated, and the gradation was almost unchanged at 2.11. . In addition, the storage stability of the color image was such that the reduction in _Dmax of the red-sensitive layer was 0.15 and practically no discoloration was observed.

(Process C) In the slit processing tank used in process B, as shown in FIG.
The processing was carried out in the same manner except that a processing tank provided with a blade at the processing path length corresponding to the above was used, and the replenishing rate was 150 ml / m ² (sensitive material). In the treatment C, no performance deterioration (stain increase, softening) occurred even in the second week. Further, the storage stability of the color image was good.

(Process D) In process C, the process was performed in the same manner as in process C, except that the blade installation position of the slit processing tank was set at a processing path length of 、 ３ and ／. In Treatment D, no performance deterioration (stain increase, softening) was observed in the second week even when the replenishment rate was 120 ml / m ² . Further, the storage stability of the color image was good.

(Treatment E) In treatment B,
A processing tank provided with a shielding means provided with a slit for allowing passage of a photosensitive material and for covering a processing liquid when immersed in a processing bath in a rack on which a photosensitive material guide roller disclosed in FIG. Treatment was carried out in the same manner, except that a tank volume of 780 ml) was used. However, although the temperature control is not shown in FIG. 1 of the above publication, it is performed by a combination of a sheet heater attached to the processing path and a temperature sensor installed near the rotary blade 40, and the temperature control range is 40 ± 2 ° C. there were. In processing E, the control range was ± 2 ° C., but no change in photographic performance was observed. Moreover, as in the case of the process B, the photographic performance did not deteriorate even one week after the process. Further, the storage stability of the color image was good.

(Process F) In process B, the process was performed in the same manner as in process B, except that the replenishment was performed in the same direction as the photosensitive material in the forward direction instead of the countercurrent replenishment. In process F,
When the increase in D _min of the green-sensitive layer was 0.04, the increase in stain was at a level at which practical problems occurred, and it was found that the gradation was softened to 1.73. Further, regarding the preservation of the color image, the reduction in _Dmax of the red-sensitive layer was 0.37, and it was found that discoloration occurred. Thus, it was found that the use of the slit treatment tank for forward flow replenishment improved the performance compared with the normal type treatment tank, but was inferior to the countercurrent replenishment and did not provide a practical level of performance.

Example 2 Example 1 was repeated except that the sample of Example 1 was used and the following exposure was performed.
The same processing and evaluation as described above were performed. (Exposure) semiconductor laser GaAlAs as a light source (oscillation wavelength, 808.5Nm) a YAG solid laser (oscillation wavelength, 946 nm) was an excitation light source 473nm was taken out by wavelength conversion by the SHG crystal of the KNb0 _3, a semiconductor laser GaAlAs (oscillation YVO ₄ solid-state laser (wavelength: 808.7 nm) as an excitation light source (oscillation wavelength: 1064 nm)
Was subjected to wavelength conversion by a KTP SHG crystal and was taken out 5
32 nm, AlGaInP (oscillation wavelength, about 670 nm: Type No. TOLD9211 manufactured by Toshiba) was used. Each of the laser beams is a device capable of sequentially scanning and exposing a color photographic paper moving in a direction perpendicular to a scanning direction by a rotating polyhedron. The relationship between the density (D) of the photosensitive material and the light amount (E) is changed by changing the light amount using this apparatus.
ogE was determined. At this time, the amount of the laser light of three wavelengths was modulated using an external modulator to control the exposure amount. 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 temperature of the semiconductor laser was kept constant by using a Peltier element in order to suppress fluctuations in light quantity due to temperature.

In the case where such exposure is performed, the first embodiment
Similar results were obtained according to the treatments A to F.

[0284]

According to the present invention, rapid processing can be performed in the activator processing, and stable photographic performance can be obtained. Further, there is no generation of stains and the like, and the storage stability of the color image is good and no discoloration occurs.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram illustrating an example of a processing apparatus used in the present invention.

FIG. 2 is a schematic configuration diagram showing an example of an activator processing tank used in the present invention.

FIG. 3 is a schematic configuration diagram showing another example of an activator processing tank used in the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Processing apparatus 2 Sensitive material storage part 3 Exposure part 4 Processing part 5 Drying part 6 Sensitive material take-out part 7 Activator processing tank 8 Bleaching and fixing tank 10-12 Drum 13-15 Replenishment tank 16-18 Pump A Photosensitive material P1 Activator Liquid P2 Bleach-fixing solution P3 Stabilizing solution OF1 to OF3 Overflow 20 Temperature control water tank 21 Heater 22 Temperature sensor 23 Rotor 24 Cover 25 Sensitive material carry-in roller 26 Sensitive material carry-out roller W Water

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G03D 3/08 G03D 3/08 GF

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material containing a color-forming reducing agent represented by the following formula (1): a cross section having a gap of 5 to 100 times the thickness of the silver halide color photographic light-sensitive material. Using a processing tank having a slit-like processing path,
A photographic processing method in which a silver halide color photographic light-sensitive material is countercurrently replenished from the side opposite to the transport direction and is developed with an activator solution. Formula (1) (L) _n -D [In Formula (1), L is an electron-withdrawing group that can be removed during the development process, and D is _n from H _n D having development activity.
N is a residue derived except for one hydrogen atom, and n is 1 to
It is an integer of 3. ] 2. A silver halide color photographic light-sensitive material containing a color-forming reducing agent represented by the following formula (1) is supplied to a processing path of the silver halide color photographic light-sensitive material. There is virtually no liquid flow when passing,
In addition, using a processing tank provided with a partitioning means so that the silver halide color photographic light-sensitive material can pass therethrough, the silver halide color photographic light-sensitive material is countercurrently replenished from a side opposite to the conveying direction, and is developed with an activator solution. Do photo processing method. Formula (1) (L) _n -D [In Formula (1), L is an electron-withdrawing group that can be removed during the development process, and D is _n from H _n D having development activity.
N is a residue derived except for one hydrogen atom, and n is 1 to
It is an integer of 3. ] 3. The photographic processing method according to claim 1, wherein the silver halide color photographic light-sensitive material contains an auxiliary developing agent.