JP2000330244A - Processing method for silver halide color reversal photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a developing method by which a sufficiently high density of a reverse image is attained, stable processing is carried out and problem on health and environmental safety is not caused by using a color developing solution of a specified pH containing a specified compound. SOLUTION: A silver halide color reversal photographic sensitive material is subjected to 2nd development with a color developing solution of pH 9.0-11.0 containing a compound of formula I after 1st black-and-white development and washing. The developing solution may further contain a substituted hydroxylamine of formula II. In the formula I, R1-R5 are each H or a substituent, A is a group which is adsorbed on the surface of silver halide, L is a combining group, (m) is an integer of 0-4 and (n) is 0 or 1. In the formula II, L1 is optionally substituted alkylene, A1 is carboxyl, sulfo or the like, R is H or optionally substituted alkyl and L1 and R may form a ring by combination.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the processing of a silver halide reversal color photographic light-sensitive material, and more specifically, to a color in which the image quality of a color reversal image is maintained even if a reversal bath is omitted. It relates to an inversion processing method.

[0002]

2. Description of the Related Art At present, there are two most common forms of color photography, one of which is performed by photographing on a color negative film, developing the film, and printing the resulting negative image on a color paper. A so-called negative / paper system (N / P system) for obtaining prints, and a color reversal system (R / P system) for directly photographing on a color reversal film (hereinafter referred to as a color reversal film) to obtain a positive image by reversal processing. Also called).

The color reversal system has disadvantages such as limited processing quality control elements and complicated processes as compared with the N / P system, but has the advantage that a positive image can be obtained directly and that it is suitable for photolithography. For this reason, it is widely used like the N / P system.

General color reversal film processing includes first (black and white) development, washing with water, reversal bath (also called reversal bath), second (color) development, conditioning bath (conditioner), bleaching, fixing, washing with water, It consists of each step of an image stabilizing bath. For details of this processing method, see Photo by LFA Mason.
ographic Processing Chemistry (1966, Focal Press)
257-266, Modern Photographic P by GMHaist
rocessing (1982), Vol. 2, Chapter 10 (pp. 523-527).

[0005] In order to form a positive dye image by color development, it is necessary to make it possible to develop an undeveloped part, that is, a part which has not been exposed to the image, at the stage of completing the first development. The method includes a light fogging method for irradiating the entire surface of the film with light, and a chemical processing method in which a reversal bath (reversal bath) containing a fogging agent for developing the silver halide is provided to process the film. There is a fogging method. The chemical fogging method is easier to maintain than the light fogging method, and effectively foggs the portion of the film surface where the degree of blackening by the first development is large, and furthermore, the fogging function. Are less susceptible to fluctuations in the temperature and composition of the developing solution and have been widely used. At the beginning of the chemical fogging system, US Patent No. 3
The method disclosed in Japanese Patent No. 246987 uses an alkali borohydride as a fogging agent, but has a drawback in that the processing solution has poor temporal stability.

[0006] Thereafter, a treatment bath using a tin (II) compound, which is known as an inorganic compound having an extremely strong reducing power like an alkali borohydride, as a fogging agent was disclosed in US Pat. No. 3,617,282. The fogging agent has the advantages of the above-mentioned chemical fogging method and also has a much better stability of the reversal bath over time than alkali borohydride, and is currently most commonly used in the processing of color reversal films. ing. However, the reversal bath using a tin (II) compound, although improved, has the disadvantage that it is still susceptible to air oxidation and consequently tends to precipitate insolubles in the form of tin hydroxide and the like. are doing.

Therefore, a reversal bath containing a tin (II) compound is desired to have stability against air oxidation, and a reversal bath using a chelating agent suitable for the purpose in combination with a tin (II) compound is desired. It has been disclosed. For example, while the above-mentioned U.S. Pat. No. 3,617,282 uses an organic phosphonate as a chelating agent, British Patent No. 1,209,050 using an aminopolycarboxylate, and Japanese Patent Publication No. 56-32616 using a phosphonocarboxylate. There have been many proposals to use chelating agents for many tin (II) ions. Inversion baths using these chelating agents have shown progress in terms of a strong and uniform fogging action and the stability over time of the processing solution, but nonetheless, the stability over time was still insufficient.

For this reason, p-aminophenol is used as an antioxidant for the tin (II) chelate in the reversal bath, but its effect is not sufficient. Also, ascorbic acid and the like are effective in preventing oxidation, but when brought into the color development step following the reversal bath, they act as black-and-white developing agents, resulting in impaired color image quality. Hydroxylamine also has similar defects and cannot be used practically.

As described above, even a reversal bath containing a tin (II) chelate is insufficient in stability against oxidative deterioration, and as a result, there is a problem that photographic characteristics vary greatly. The tin (II) compound and the chelating agent in the inside also need to consider the environment. Therefore, there is a strong demand for a reversal color developing method that has sufficient and stable reversal development quality and that is environmentally friendly.

[0010]

The problem to be solved by the present invention is to solve the above-mentioned problem relating to the reversal bath in the processing of the color reversal film. Is to find a reversal color developing method that has a sufficiently high density, is stable in processing, and is environmentally friendly.

[0011]

In order to achieve the above object, the present inventors have developed an undeveloped halogen after the first development without being particular about a fogging method such as a reversal bath or a light fogging method. As a result of extensive studies on means for effectively developing silver grains, it was discovered that a 3-pyrazolidone compound having enhanced adsorption to silver halide grains has a strong reducing property on silver salts. As a result of the research, the present invention has been achieved. That is, the present invention is as follows.

1. In the method for processing a silver halide color reversal photographic light-sensitive material, wherein the color developing solution has a pH of 9.
0 to 11.0, and at least one compound represented by the following general formula (I). General formula (I)

[0013]

Embedded image

In the general formula (I), R ¹ , R ² ,
R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent. A represents a group adsorbed on the silver halide surface. L represents a linking group. m represents an integer of 0 to 4.
n represents 0 or 1. 2. 2. The method for processing a color reversal photographic light-sensitive material as described in 1 above, wherein the color developer contains at least one kind of substituted hydroxylamine represented by the following general formula (II).

[0015]

Embedded image

In the general formula (II), L ¹ represents an alkylene group which may be substituted, and A ¹ represents a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid residue, a hydroxyl group, or an amino group which may be substituted with an alkyl. Group, an ammonio group which may be alkyl-substituted, a carbamoyl group which may be alkyl-substituted, a sulfamoyl group which may be alkyl-substituted or an alkylsulfonyl group which may be substituted, wherein R is a hydrogen atom or may be substituted Represents an alkyl group. Further, L ¹ and R may be linked to form a ring.

3. A color developer for a color reversal photographic light-sensitive material, characterized in that it contains at least one compound represented by the general formula (I) as described in 1 above and has a pH of 9 to 11.

In the present invention, the color developing solution of the formula (I)
Is added. The structural feature of this compound is that 1-phenyl-3 which is known as a strong black-and-white developing agent
-Having a pyrazolidone derivative and an adsorptive group A to silver halide grains as partial structures, respectively, and by this combination structure, undeveloped silver halide grains after the first development can be effectively developed. To be found. Due to this effect, which can be called self-fogging development, not only color development can be sufficiently performed without providing a reversal bath, but also a conventionally high pH, for example, described in JP-A-8-262668. 11.
Color development is sufficiently advanced even if the pH of the developer for reversal color development, which is performed at a high pH of 0 or more, in many cases, 11.7 to 13.5, is lowered to a range of 9.0 to 11.0. I also knew it could be done. The preferred pH is
9.5 to 10.5, more preferably 10.0 to 1
0.3. Since the stability over time of the developer is significantly affected by the pH, the ability to lower the pH significantly improves the stability of the developer in the developing tank and the replenishing tank over time. In addition, because it is stable, it is possible to reduce the amount of replenisher used to compensate for air oxidation during pauses called overnight correction and over-weekend correction. Environment addition to processing is also reduced. Furthermore, since the Sn (II) compound does not need to be used, the environmental load is also small in this aspect.

In a preferred embodiment of the present invention, the compound represented by the general formula (I)
In addition to the compound of formula (II), a compound of formula (II) is also added to the color developer. The color reversal developers commonly used in the current color lab market use only sulfite ions as preservatives. By using a substituted hydroxylamine as a preservative, the preservative properties are improved, the stability over time of the developer is further improved, and stable development can be performed stably. It can be even easier.

It should be noted that EP 896248 A2 discloses a reversal color containing a 3-pyrazolidone derivative having a silver halide-adsorbing group and a dinucleophile (compound having two nucleophilic groups). A processing solution for a photosensitive material is disclosed, and it is described that the processing solution includes a color developer. However, this publication discloses a preferable p when applying this technology to a reversal color developer.
Since there is no description about the H range, the pH of the developer is adjusted to 9.0.
No effect or idea of the present invention of 11.0 is suggested. Further, the pH of the reversal color developer actually shown in Examples of the publication is also 11.7. In this publication, hydroxylamine, hydrogen peroxide,
Hydrazine and substituted hydrazine are mentioned. In the present invention, hydrazine and substituted hydrazine cannot be used for lowering the color density due to black-and-white development, and hydrogen peroxide cannot be used for oxidizing the developing agent to impair the stability over time. On the other hand, hydroxylamine has a pH
Is in the range of 11.0 to 13.0, black-and-white development occurs and the color density is significantly reduced.
It could not be used for color reversal developers performed in areas. On the other hand, in the pH range of the color development of the present invention, although the decrease in color density is small even when hydroxylamine is used, it can be more preferably used because it is a compound of the general formula (II). There is almost no decrease in color density, and it hardly acts as a dinucleophile. The compound of the general formula (II) has no black-and-white developing action in the pH range of 9.0 to 11.0, and effectively exerts preservative properties with respect to the developing agent. This compound cannot be used in the pH range around 11.7 or even higher, because it affects photographic properties. That is, pH 9.0-
It can be used effectively in the pH range of the present invention of 11.0.

Accordingly, European Patent EP 896248 describes
A feature of the present invention with respect to the technology disclosed in the specification of A2 is that by selecting the pH of the developing solution, a high color density can be obtained by reversal development without using two nucleophiles, and That is, the problem that black-and-white development (non-color development) occurs in the ink is suppressed, and the stability of the developer is improved. Further, the effect can be enhanced by further adding the compound of the general formula (II).

Further, in color reversal development,
JP-A-8-262668 (page 43, left 43 to right 1)
It is customary to add a colorless coupler such as citrazic acid as described in line 6), but with the addition of a two nucleophile such as hydroxylamine, non-color developing (ie. (Black-and-white development) further proceeds to cause a reduction in color density. Therefore, it is preferred that hydroxylamine is not used in the present invention.

[0023]

Embodiments of the present invention will be described below in detail. In the color inversion processing of the present invention,
A reversal bath may be provided before the color development step, but preferably, the color development is performed following the first development step and the washing step.

General formula (I) to be contained in a color developer
Will be described. In the compound of the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent, A represents a group adsorbed on the silver halide surface, and , L represents a linking group. Further, m represents an integer of 0 to 4, and n represents 0 or 1. R ¹
And a substituent represented by R ² is a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 4; For example, methyl group, ethyl group, n-propyl group, is
o-propyl group, n-butyl group, iso-butyl group, t
tert-butyl groups. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 2 carbon atoms)
6, particularly preferably having 2 to 4 carbon atoms, for example, a vinyl group and an allyl group. ), An alkynyl group (preferably having 2 to 12 carbon atoms, more preferably having 2 to 6 carbon atoms, particularly preferably having 2 to 4 carbon atoms, for example, a propargyl group), and an aryl group (preferably having 6 carbon atoms).
-12, more preferably 6-10 carbon atoms, particularly preferably 6-8 carbon atoms, such as a phenyl group and a p-methylphenyl group. ).

These substituents may further have a substituent, for example, a linear, branched or cyclic alkyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom).
-10, particularly preferably 1-4, for example, methyl,
Ethyl, n-propyl group, iso-propyl, n-butyl, iso-butyl, tert-butyl. ), An aryl group (preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 12 carbon atoms)
And aryl groups such as phenyl and p-methylphenyl. ), An amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, such as an amino group, a methylamino group, a dimethylamino group, and a diethylamino group. ), An alkoxy group (preferably having 1 to 1 carbon atoms).
8, more preferably an alkoxy group having 1 to 6 carbon atoms, particularly preferably an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group and an ethoxy group. ), An aryloxy group (preferably having 6 to 12 carbon atoms, more preferably having 6 to 10 carbon atoms,
Particularly preferred is an aryloxy group having 6 to 8 carbon atoms, such as a phenyloxy group. ), An acyl group (preferably an acyl group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as acetyl), an alkoxycarbonyl group (preferably carbon atom). An alkoxycarbonyl group having a number of 2 to 12, more preferably 2 to 10 carbon atoms, and particularly preferably 2 to 8 carbon atoms, such as a methoxycarbonyl group; and an aryloxycarbonyl group (preferably 7 to 12 carbon atoms). 20, more preferably 7 to 15 carbon atoms, particularly preferably 7 to 10 carbon atoms, for example, a phenyloxycarbonyl group.), Acyloxy group (preferably 2 to 12 carbon atoms, more preferably 2 carbon atoms). ~ 1
0, particularly preferably 2 to 8 carbon atoms, for example, an acetoxy group. ), An acylamino group (preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms, particularly preferably having 2 to 4 carbon atoms, for example, an acetylamino group), and an alkoxycarbonylamino group (preferably, 2 to 12 carbon atoms, more preferably 2 to 1 carbon atoms
0, particularly preferably 2 to 8 carbon atoms, such as a methoxycarbonylamino group. ), An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 12 carbon atoms, and particularly preferably having 7 carbon atoms)
To 10, for example, a phenyloxycarbonylamino group. ), A sulfonylamino group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, such as a methanesulfonylamino group), and a sulfamoyl group (preferably, It has 0 to 10 carbon atoms, more preferably 0 to 6 carbon atoms, particularly preferably 0 to 4 carbon atoms, for example, a sulfamoyl group,
And a methylsulfamoyl group. ), A carbamoyl group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, such as a carbamoyl group and a methylcarbamoyl group), and an alkylthio group (preferably). Has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 1 carbon atoms.
4, and examples thereof include a methylthio group, an ethylthio group, and a carboxymethylthio group. ), An arylthio group (preferably having 6 to 20 carbon atoms, more preferably having 6 carbon atoms)
10 to 10, particularly preferably 6 to 8 carbon atoms, such as a phenylthio group. ), A sulfonyl group (preferably having 1 to 8 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, such as a methanesulfinyl group), and a ureido group (preferably having a carbon number of 1). 1 to 8, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, for example, a ureido group and a methylureido group.), A hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom, A chlorine atom, a bromine atom, an iodine atom), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, and a heterocyclic group (eg, imidazolyl, pyridyl). R ¹ and R
Preferred as a substituent of the substituent represented by ² , an alkoxy group, an aryloxy group, an acyloxy group, a hydroxy group, an amino group, more preferably an alkoxy group,
It is an acyloxy group or a hydroxy group, particularly preferably a hydroxy group.

At least one of R ¹ and R ² is an alkyl group or an aryl group, more preferably at least one is an alkyl group, particularly preferably both are alkyl groups. Particularly preferred combinations of groups as R ¹ and R ² are (R ¹ , R ² ) = (methyl group, methyl group), (methyl group, hydroxymethyl group), (methyl group, hydroxyethyl group), (hydroxymethyl group) Group, hydroxymethyl group) and (hydroxyethyl group, hydroxyethyl group). As the substituent represented by R ³ ,
Those wherein a substituent of R ¹ and R ² are exemplified as the substituent which may be possessed by applicable. Among these substituents, preferred are an alkyl group, an aryl group, a carboxyl group, and an acyloxy group, more preferred are an alkyl group and an aryl group, and particularly preferred is an aryl group. These substituents may further have a substituent. However, R ³ is most preferably a hydrogen atom.

As the substituent represented by R ⁴ , those mentioned as the substituent which the substituents of R ¹ and R ² may have can be applied. Among these substituents, an alkyl group and an acyl group are preferable, and an alkyl group is more preferable. These substituents may further have a substituent. However, R ⁴ is most preferably a hydrogen atom.

As the substituent represented by R ⁵ , those exemplified as the substituent which the substituents of R ¹ and R ² may have can be applied. Of those substituents, an alkyl group, an alkoxy group, a sulfamoyl group, a sulfonylamino group, an acylamino group, a halogen atom, a sulfo group, and an amino group are preferable, and an alkyl group and a halogen atom are more preferable. These substituents may further have a substituent. When n is 2 or more, each substituent may be the same or different. m is preferably 0 or 1, and more preferably 0. n is preferably 1.

The linking group represented by L is an alkylene group,
A arylene group, -CO-, -CO-O-, -O-CO-,
-CO-NR⁶, -NR⁷-CO-, -SO_Two-NR⁸
-, NR⁹-SO_Two-, -O-, -S-, NR^Ten-And
And a linking group consisting of a combination thereof,
Is an alkylene group, -CO-, -CO-O-, -O-CO
-, -CO-NR⁶, -NR⁷-CO-, -SO_Two-N
R⁸-, NR⁹-SO _Two-, -O- and combinations thereof
A linking group consisting of
Group, -CO-O-, O-CO-, -CO-NR⁶, -N
R⁷—CO—. R⁶, R⁷, R⁸, R⁹And R^Ten
Represents a hydrogen atom or a substituent, and the substituent is R¹Passing
And R^TwoWhat is mentioned as a substituent which the substituent of may have
Can be applied. When n is 2 or more, L is the same
It may be a linking group or may be different.

A represents a group which can be adsorbed on the silver halide surface. For example, heterocycles (eg, imidazoles, benzimidazoles, triazoles, benzotriazoles, thiazoles, benzothiazoles, mercaptotetrazole, mercaptoimidazoles, mercaptothiazoles, mercaptooxazoles, mercaptotriazoles, indazoles) , Thioethers, thioureas, thiols, and selenoureas, which may have a substituent. As the substituent, those exemplified as the substituent which the substituents of R ¹ and R ² may have can be applied. A is preferably benzimidazoles, benzotriazoles, benzothiazoles, mercaptotetrazole, mercaptothiazoles, mercaptotriazoles, more preferably benzotriazoles, benzothiazoles, mercaptotetrazole, and particularly preferably Is a benzotriazole.

Among the compounds represented by the general formula (I), a compound represented by the following general formula (Ia) is preferable, and a compound represented by the following general formula (Ib) is more preferable. General formula (Ia)

[0032]

Embedded image

In the general formula (Ia), R ¹ , R ² ,
R ⁵ , A, L and n have the same meanings as those in formula (I), and the preferred ranges are also the same. General formula (Ib)

[0034]

Embedded image

In the general formula (Ib), R ¹ , R ² , A and L have the same meanings as those in the general formula (I), and their preferred ranges are also the same. Specific examples of the compound represented by formula (I) are shown below, but the invention is not limited thereto.

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

Among the compounds represented by the above general formula (I), preferred compounds are I-3, I-4, I-5 and I-
6 and I-14, among which the preferred compound is I-4
And I-5.

The amount of the compound of the formula (I) to be added to the color developing solution is 0.1 g to 20 g, preferably 0.5 g to 10 g per liter as a composition of the tank solution in the developing tank. Is 1.0 to 1.8 times, preferably 1.0 to 1.3 times.

The compound of the general formula (I) can be synthesized, for example, from a nitrobenzene derivative (1) and a compound (2) having a silver halide adsorbing group by the following reaction route. In the formula, X and Y are functional groups bonded to each other;
R ¹ , R ² , R ³ , A, L and n have the meaning described in the general formula (I). When R ⁴ is other than a hydrogen atom, it can be synthesized according to this scheme.

[0043]

Embedded image

Specifically, for example, the exemplified compound (I-
1) is synthesized by the following reaction route.

[0045]

Embedded image

Next, the compound represented by formula (II) will be described. In the formula (II), L ¹ represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. Specifically, methylene, ethylene, trimethylene, and propylene are preferred examples. As the substituent, a carboxyl group, a sulfo group,
Represents a phosphono group, a phosphinic acid residue, a hydroxyl group, an amino group which may be substituted with an alkyl (preferably having 1 to 5 carbon atoms), a carboxyl group, a sulfo group, a phosphono group,
Hydroxyl groups are mentioned as preferred examples.

A¹Is carboxyl, sulfo, phospho
Group, phosphinic acid residue, hydroxyl group, alkyl
An amino group (preferably having 1 to 5 carbon atoms) which may be substituted,
Alkyl (preferably having 1 to 5 carbon atoms)
Nummonio group, alkyl (preferably having 1 to 5 carbon atoms)
Carbamoyl group, alkyl (preferably carbon
Formulas 1 to 5) Sulfamoyl group which may be substituted,
Represents a good alkylsulfonyl group, carboxyl
Group, sulfo group, hydroxyl group, phosphono group, alkyl
A carbamoyl group which may be substituted is mentioned as a preferred example.
Can be A¹Is a general formula (II) when represents an ammonium group
The compound of the formula
, P-toluenesulfonic acid ion, chlorine ion, sulfurous acid
It may be accompanied by an acid ion or the like. Also, L¹And A¹Mosquito
Ruboxyl group, sulfo group, phosphono group, phosphinic acid residue
With a substituent having an acid group such as a hydroxyl group or a hydroxyl group
If the hydrogen is an alkali metal atom,
You may replace the corps. -L ¹-A¹As an example of
Carboxymethyl group, carboxyethyl group, carboxy
Propyl, sulfoethyl, sulfopropyl, sulfo
Hobutyl, phosphonomethyl, phosphonoethyl,
A droxyethyl group is a preferred example.
Carboxymethyl group, carboxyethyl group, sulfo
Ethyl group, sulfopropyl group, phosphonomethyl group, phos
Phonoethyl group is a particularly preferred example.
You.

R represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms which may be substituted, and preferably has 1 to 5 carbon atoms. As the substituent, a carboxyl group,
Sulfo group, phosphono group, phosphinic acid residue, hydroxyl group, amino group which may be substituted with alkyl, carbamoyl group which may be substituted with alkyl, sulfamoyl group which may be substituted with alkyl, alkylsulfonyl group which may be substituted, Acylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkoxycarbonyl group,
It represents an amino group, an arylsulfonyl group, a nitro group, a cyano group, or a halogen atom which may be alkyl-substituted. There may be two or more substituents. Among them, preferred R includes a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. Particularly preferred examples include a hydrogen atom. Carboxymethyl group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group and phosphonoethyl group.

L ¹ and R may be linked to form a ring.
When L ¹ and R form a ring, L ¹ and R directly form a ring to have A ¹ as a substituent, or A ¹ represents an amino group which may be alkyl-substituted; L ¹ and R can form a ring (eg, a piperazine ring) via an atom. Next, specific compounds of the present invention are described, but are not limited thereto.

[0050]

Embedded image

[0051]

Embedded image

[0052]

Embedded image

The compound represented by the general formula (II) can be synthesized by subjecting commercially available hydroxylamines to an alkylation reaction (nucleophilic substitution reaction, addition reaction, Mannich reaction, etc.). Also, West German Patent 115963
No. 4, `` Inorganica Chemica Actor '' (Inorg
anica Chimica Acta), 93, (1984) 101-108, and the like. A synthesis method for a more specific compound is also described in JP-A-3-266837.

These substituted hydroxylamine compounds can prevent the color developer from oxidatively deteriorating in the air, maintain the activity of the developer, and continue the development process for a long time without replacing the solution in the developing tank. The amount of the hydroxylamine derivative of the general formula (II) to be added to the color developing solution is 0.1 g to 20 g, preferably 0.5 g to 10 g per liter as a composition of the tank solution in the developing tank. The amount of addition is 1.0 to 1.8 times, preferably 1.0 to 1.3 times.

Next, the general silver halide reversal color processing method of the present invention using a color developer containing the compound of the above general formula (I) and also the compound of the general formula (II) will be described. Known developing agents can be used for the first black-and-white developer and the replenisher thereof of the present invention. Developing agents include dihydroxybenzenes (eg, hydroquinone, hydroquinone monosulfonate), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), aminophenols, ascorbic acid and US Pat. No. 4,067, No. 872, a heterocyclic compound in which a 1,2,3,4-tetrahydroquinoline ring and an indole ring are condensed can be used alone or in combination. A preferred developing agent is potassium hydroquinone monosulfonate or hydroquinone It is sodium monosulfonate. The preservative used in the first black-and-white developer / replenisher of the present invention is preferably a sulfite, a bisulfite or the like, and the sulfurous acid concentration in the developer is preferably 0.01 to 10 mol / l, and more preferably 0.1 to 1 mol / liter. Further, hydroxylamines of the general formula (I) described in JP-A-3-144446 can also be used.

In addition, the first black-and-white developer / replenisher of the present invention contains a buffer (eg, carbonate, borate, alkanolamine, sulfosalicylic acid), a hydroxide (eg, potassium hydroxide, sodium hydroxide), Dissolution aids (eg, polyethylene glycols), sensitizers (eg, quaternary ammonium salts), silver halide solvents (eg, KSCN, N
aSCN), a development accelerator, a surfactant, a hardener, and the like. The pH value of the first black-and-white developer / replenisher of the present invention is preferably from 8.0 to 11.0, more preferably from 9.0 to 10.5, and particularly preferably from 9.5 to 10. 0.

The standard processing time of the first black-and-white developing solution of the present invention is 6 minutes, and by appropriately changing the processing time, the increase / decrease sensation processing can be performed. Usually 3 minutes to 18
Change the processing time between minutes.

The replenishment amount to the first black-and-white developer of the present invention is generally 2 to 2.5 per square meter of the light-sensitive material to be processed.
Liter, and in recent years, 0.5 to
Processing with 1.5 liters is also practiced.

The smaller the contact area between the liquid and the air in the processing liquid tank and the replenishing liquid tank, it is preferable to prevent oxidation deterioration. The contact area between the photographic processing solution and air in the processing tank and the replenisher tank can be represented by the aperture ratio defined below.
That is, opening ratio = [contact area between processing solution and air (cm ² )] ÷ [capacity of processing solution (cm ³ )] The above opening ratio is preferably 0.1 or less, more preferably 0. 0.001 to 0.05. As a method of reducing the aperture ratio, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank and the replenisher tank, Japanese Patent Laid-Open No.
No. 2033, using a movable lid;
A slit developing method described in JP-A-3-216050 can be exemplified. The reduction of the aperture ratio is preferably applied not only to both the color development and the black-and-white development but also to the subsequent various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The reversal bath or light fogging step conventionally used after the first black and white development can be omitted in the present invention. However, when it is carried out, a known fogging agent, that is, stannous ion-organic phosphate complex (U.S. Pat. No. 3,617,282), stannous ion organophosphonocarboxylic acid complex (Japanese Patent Publication No. 56-3261
No. 6), stannous ion-complex salts such as stannous ion-aminopolycarboxylic acid complex salt (U.S. Pat. No. 1,209,050), and borohydride compounds (U.S. Pat.
No. 4,567) and a boron compound such as a heterocyclic amine borane compound (UK Patent No. 1,011,000). The pH of the reversal bath ranges from an acidic side to an alkaline side depending on the type of the fogging agent.
H2-12, often in the range 2.5-10, especially 3-9.

In the present invention, the color developer contains an aromatic primary amine color developing agent. The amount of the color developing agent used is 1 to 20 g per liter of the color developer,
Preferably it is 2 to 15 g.

These color developing agents may be used alone or in combination of two or more. Specific compounds are described below, but the compounds are not limited thereto. D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [ N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino-3-methyl -N-ethyl-N-
[Β- (methanesulfonamido) ethyl] -aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino -3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-Amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline These color developing agents are usually used in the form of a salt such as hydrochloride, sulfate, phosphate, p-toluenesulfonate or a hydrate of the salt. Preferred color developing agents in the present invention are D-4, D-5 and D-6.

In the present invention, the reversal color developer includes:
As a preservative, a sulfite such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite, or a carbonyl compound sulfite adduct can be added as necessary. The preferred amount of addition is 20 g or less, more preferably 10 g or less, and particularly preferably 0.05 to 5 g per liter of the color developer. If the addition amount is large, the color coupling is inhibited, so that the color density decreases. In this regard, the compound of the general formula (II) preferably used in the present invention does not have such an adverse effect.

In the present invention, a colorless competing coupler may be contained in order to adjust the gradation of the inverted color image. No-color competitive couplers are disclosed in U.S. Pat.
No. 2,832, No. 3,520,690, No. 3,6
No. 45,737, JP-B-44-9504, 44-9
Nos. 506 and 44-9507, particularly preferably used compounds include citrazic acid and J.
Acid, H acid, resorcin and the like. Among these, citrazic acid is particularly preferred. When a non-color-competitive coupler is added to the reversal color developer, the addition amount is 1 to
10 mmol / liter.

In the present invention, as described above, it is not preferable to use hydroxylamine. The reason is that, as described above, since there is a non-color developing activity, compatibility with the reversal color developing solution is poor, and desired photographic properties (gradation) cannot be obtained. In the present invention, the general formula (I
Since it contains the compound of I), no other preservative is required, but another preservative may be added. Other preservatives for color developers include sulfinic acids,
Α-hydroxyketones and α-aminoketones described in -44656, various sugars described in 63-36244,
JP-A Nos. 63-4235, 63-24254, and 6
3-21647, 63-146040, 63-
Monoamines described in each of JP-A Nos. 27841 and 63-25654;
Diamines described in JP-A-3-146040 and JP-A-63-43439, polyamines described in JP-A-63-21647 and JP-A-63-26655, and diamines described in JP-A-63-44655. Polyamines, JP-A-6
The alcohols described in JP-A-3-43140 and JP-A-63-53549, the oximes described in JP-A-63-56654, and the tertiary amines described in JP-A-63-239947 are used. No.

Other preservatives are described in JP-A-57-44.
Nos. 148 and 57-53749, various metals, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, and JP-A-56-94349. The poly (ethylene imines) described above and the aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544 may be contained as necessary.

The reversal color developer used in the present invention can contain compounds of other known developer components.

The color developer used in the present invention contains an appropriate alkaline agent and p
Use H buffer. Examples of the alkaline agent and the pH buffering agent include carbonates such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate, alkali hydroxides such as sodium hydroxide and potassium hydroxide, trisodium phosphate, dipotassium phosphate and the like. , Borate such as potassium borate and sodium tetraborate, and organic acid salts such as dipotassium 5-sulfosalicylate and disodium 4-sulfosalicylate can be used.

The amount of the alkali agent or buffer added to the color developer is 0.01 mol / l to 0.5 mol / l, and 0.01 mol / l to 0.2 mol / l. Preferably, there is.

In addition, various chelating agents can be used in the reversal color developing solution as an agent for preventing precipitation of calcium and magnesium, or for improving the stability of the color developing solution. As the chelating agent, an organic acid compound is preferable, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenesulfonic acid, ethylenediamine-N, N, N ′, N ′.
-Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 1-phosphonobutane-1,2,4-tricarboxylic acid Acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2-dihydroxyoxybenzene-3,5-disulfonic acid And the like. These chelating agents may be used in combination of two or more as necessary.

The preferable addition amount of the chelating agent is 0.01 to 20 g per liter of the reversal color developer.
Particularly preferably, it is 0.1 g / 10 g. An optional development accelerator can be added to the reversal color developer if necessary. In particular, a thioether-based fogging accelerator may be added to maximize development activity. As thioether-based fogging agents, JP-B-37-16088,
No. 37-5987, No. 38-7826, No. 44-1
Nos. 2380 and 45-9019 and U.S. Pat.
No. 813,247, etc. are used. In addition, an amine compound such as ethylenediamine can be used. Among these compounds, 3,6-dithiaoctane-1,8-diol is preferred. When a fogging agent is added to the reversal color developer, the amount of addition is about 1 to 20 mmol / liter.

The replenishment amount of the reversal color developer in the present invention can be processed at 40 to 4000 ml / m ² , but wastewater can be reduced by reducing the replenishment amount as much as possible, so long as the developer is stable. , Less is preferred. The preferred replenishment rate is 40-1100 ml /
m ² , more preferably 400 to 1100 ml / m ² .

In the present invention, after color development, desilvering is performed using a processing solution having bleaching ability. In the desilvering process, a bleaching solution, a bleach-fixing solution or both are used, and these processing solutions contain a bleaching agent. As the bleaching agent, for example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Typical bleaching agents include organic complexes of iron (III), for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol ether diaminetetraacetic acid, and JP-A-4-121739.
No., 1,3-from the lower right column of page 4 to the upper left column of page 5
Bleaching agents such as iron propylenediaminetetraacetate complex; carbamoyl bleaching agents described in JP-A-4-73647; bleaching agents having a heterocyclic ring described in JP-A-4-174432; N- (2-carboxy); European Patent Publication No. 5204, including ferric complex salts of phenyl) iminodiacetic acid
No. 57, the bleaching agent described in European Patent Publication No. 530828 A1, including ethylenediamine-N-2-carboxyphenyl-N, N ′, N′-ferric acetic acid acetic acid, the bleaching agent described in European Patent Publication No. No. 501479, bleaching agent described in JP-A-4-127145, coating agent described in JP-A-4-127145,
No. 3,303,186 and JP-A-3-144446, ferric aminopolycarboxylic acid salts or their salts described in page 11 are preferably used.

The iron (III) complex salt of an organic aminocarboxylic acid is particularly useful in a bleaching solution and a bleach-fixing solution.
The pH of the bleaching solution or bleach-fixing solution using these organic aminocarboxylic acid iron (III) complex salts is usually from 4.0 to 8.0, but the processing may be carried out at a lower pH to speed up the processing. it can.

In the present invention, in addition to the bleaching agent, a rehalogenating agent, a pH buffering agent and known additives described in page 12 of JP-A-3-144446 described above may be added to the processing bath having the bleaching ability. Carboxylic acids, organic phosphonic acids and the like can be used.

In the present invention, various bleaching accelerators can be added to the bleaching solution or its prebath (adjustment solution). Such bleaching accelerators are described, for example, in U.S. Pat. No. 3,893,858;
No. 821, British Patent No. 1,138,842, JP-A-5
3-95630, Research Disclosure No. 1
Compounds having a mercapto group or a disulfide group described in No. 7129 (July 1978);
No. 0129, thiourea derivatives described in U.S. Pat. No. 3,706,561, iodides described in JP-A-58-16235, German Patent No.
748,430, polyethylene oxides,
Polyamine compounds described in JP-B-45-8836 can be used. Further, U.S. Pat.
The compounds described in No. 834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Preferably British Patent 1,138,842
And mercapto compounds described in JP-A-2-190856.

It is preferable that a processing solution having a bleaching ability (a bleaching solution or a bleach-fixing solution) contains an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (PKa) of 2 to 5, specifically acetic acid, lactic acid, malonic acid, maleic acid, glutaric acid, succinic acid, propionic acid, hydroxyacetic acid and the like.

These organic acids are preferably contained in an amount of 0.005 to 3 mol per liter of a processing solution having a bleaching ability. The bleaching process is preferably performed immediately after the color development, but in the case of the reversal process, it is generally performed via an adjusting solution (a bleach accelerating solution may be used).

Examples of the adjusting solution include aminopolycarboxylic acid chelating agents such as ethylenediaminetetraacetic acid, diethylaminetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, and cyclohexanediaminetetraacetic acid; sodium sulfite,
A sulfite such as ammonium sulfite and various bleaching accelerators described below such as thioglycerin, aminoethanethiol, and sulfoethanethiol can be contained.
For the purpose of preventing scum, US Pat. No. 4,839,262
No. 4,059,446 and Research Disclosure, vol. 191 and 19104.
It is preferable to include a polyoxyethylene compound described in (1980). These compounds can be used in a range of 0.1 g to 20 g per liter of the adjustment liquid, but preferably in a range of 1 g to 5 g.

The adjusting solution may contain an image stabilizer described below. The pH of the adjusting solution is usually used in the range of 3 to 11, preferably 4 to 9, and more preferably 4.5 to 7. The processing time with the adjustment liquid is 20 seconds-
Preferably, it is 15 minutes. More preferably 20 seconds or more
100 seconds, most preferably 20 to 60 seconds. The replenishment amount of the adjusting solution is 30 m per 1 m ^{2 of the} light-sensitive material.
1 to 3000 ml is preferred, but especially 50 to 150 ml.
It is preferably 0 ml. The processing temperature of the conditioning liquid is 20
C. to 50.degree. C. is preferred, and particularly preferably 30.degree.

In the present invention, after the desilvering treatment, a treatment with a stabilizing bath may be carried out after a washing treatment, or a treatment with a stabilizing solution may be carried out directly without a washing treatment.
The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of
the Society of Motion Picture and Television Engi
neers, vol. 64, p. 248-253 (May, 1955). According to the multi-stage countercurrent method described in the literature, the amount of washing water can be significantly reduced, but due to an increase in the residence time of water in the tank,
There is a problem that bacteria proliferate and the generated suspended matter adheres to the photosensitive material. In the treatment of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, isothiazolone compounds and thiabendazoles described in JP-A-57-8542, chlorine-based disinfectants such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Bactericidal and Fungicide Chemistry". (1986) Sankyo Publishing,
"Sterilization, Sterilization, and Mold Prevention Technology for Microorganisms" edited by the Sanitary Technology Society (19
1982) It is preferable to use a bactericide described in "Encyclopedia of Bactericidal and Fungicide" (ed. 1986) edited by the Japan Society of Industrial Technology and the Japan Society of Bacterial and Fungicide.

As the stabilizer of the present invention, a stabilizer containing formaldehyde is generally used, but other stabilizers such as US Pat. Nos. 4,786,583 and 4,859,574,
JP-A-3-33847, 4-270344, and 4
-317553, 4-359249, 5-34
No. 889, No. 5-165178, JP-A-57-854.
No. 3, 58-14834, 60-220345, etc., known stabilizers and treatment methods can be applied.

The stabilizing solution or the adjusting solution of the present invention contains a compound for stabilizing a dye image (hereinafter referred to as an image stabilizing agent). Examples thereof include benzaldehydes such as formalin and m-hydroxybenzaldehyde, and formaldehyde polymerization. Examples include sulfurous acid adducts, hexamethylenetetramine and its dielectric, hexahydrotriazine and its derivatives, dimethylolurea, and N-methylol compounds such as N-methylolpyrazole. In the present invention, when the concentration of free formaldehyde in the liquid is 0 to 0.01%, more preferably 0 to 0.005%, the effect is large and preferable. Examples of image stabilizers for achieving such a free formaldehyde concentration include m-hydroxybenzaldehyde,
N-methylolazoles described in JP-A-4-270344, such as hexamethylenetetramine and N-methylolpyrazole, and JP-A-4-, 344, such as N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine. 313
Azolylmethylamines described in No. 753 are preferred.

The content of these image stabilizers is preferably from 0.001 to 0.1 mol, more preferably from 0.001 to 0.05 mol, per liter of the stabilizing solution. The stabilizer of the present invention preferably contains various surfactants in order to prevent unevenness of water droplets during drying of the processed photosensitive material.
Examples of such surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzene sulfonate type anionic surfactants, and higher alcohol sulfate ester type anionic surfactants. Agents, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant Can be It is preferable to use a nonionic surfactant,
In particular, nonionic surfactants of alkyl polyethylene oxides, alkyl phenoxy polyethylene oxides, and alkyl phenoxy polyhydroxypropylene oxides are preferable.

The stabilizer of the present invention may contain a chelating agent for collecting heavy metals to improve the stability of the stabilizer,
It is preferable in reducing the generation of dirt. As the chelating agent, the same compounds as those added to the developer and the bleaching solution can be used. The stabilizer of the present invention is preferably added with a bactericidal / antifungal agent for the purpose of preventing the generation of fungi, and commercially available products can be used.

The pH of the stabilizer and washing water of the present invention is from 4 to
9, preferably 5 to 8. The processing temperature and the processing time can also be variously set depending on the characteristics of the photographic material, the application, etc., but generally at 15 to 45 ° C. for 20 seconds to 10 minutes, preferably 25 to 45 ° C.
30 seconds to 2 minutes at 40 ° C. Further, when the stabilizer of the present invention is treated directly with the stabilizer after desilvering without washing with water, the effect of preventing contamination is remarkably exhibited.

The replenishing amount of the stabilizer of the present invention is preferably 200 to 2000 ml per 1 m ^{2 of the} light-sensitive material. The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

In order to reduce the amount of washing water used, ion exchange or ultrafiltration may be used, and it is particularly preferable to use ultrafiltration. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Usually 33 ° C ~ 3
Although a temperature of 8 ° C. is standard, a higher temperature can accelerate the processing to shorten the processing time, or a lower temperature can achieve an improvement in the image quality and an improvement in the stability of the processing solution.

In particular, it is preferable to use a surfactant as a stabilizing liquid as described below in order to improve the unevenness generated during drying.

[0090]

Embedded image

[0091]

Embedded image

[0092]

Embedded image

[0093]

Embedded image

[0094]

Embedded image

The description of the reversal developing process of the present invention is completed above. Next, the color reversal film to which the developing method of the present invention is applied will be described. In this film, photosensitive units are arranged in the order of red-sensitive unit, green-sensitive unit, and blue-sensitive unit in order from the one near the support, and between the red-sensitive unit and the green-sensitive unit, or between the green-sensitive unit and the blue-sensitive unit. A silver halide color photographic material having at least one non-color-forming layer on at least one of the units.

A photosensitive material having a three-layered photosensitive unit is as follows:
It is preferable to coat the low-speed emulsion layer, the medium-speed emulsion layer, and the high-speed emulsion layer in this order from the side close to the support, and a non-color-forming intermediate layer or halogen is interposed between these light-sensitive emulsion layers. A layer containing a silver halide emulsion may be applied. The photosensitive unit preferably has a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer, all of which have a three-layer structure. Good. The blue-sensitive layer contains a yellow coupler, the green-sensitive layer contains a magenta coupler, and the red-sensitive layer contains a cyan coupler. Other combinations of couplers may be mixed for the purpose of adjusting color reproducibility.

Of the units having a three-layer structure, the coating amount of the silver halide emulsion is 10% to 60% for the high-sensitivity layer and 1% for the intermediate layer of the silver halide emulsion coating weight of the whole unit.
Preferably, 0% to 50% and 30% to 70% are distributed to the low-sensitivity layer, and the silver / coupler ratio in each photosensitive layer is set so that the low-sensitivity layer is maximized. Preferably, there is.

It is preferable to have a non-color-forming intermediate layer between units having different color sensitivity. The non-color-forming intermediate layer may contain a light-sensitive, non-light-sensitive or pre-fogged silver halide emulsion. In particular, it is preferable that the intermediate layer has a structure of two or more layers and five or less layers. In this case, the layer located farther from the support is provided with a colloidal silver grain or a silver halide emulsion whose surface or inside is previously fogged. Is preferably contained. When a silver halide emulsion is contained in the intermediate layer, a color mixture inhibitor is preferably added to the intermediate layer or an adjacent layer.

More preferred embodiments of the color reversal film according to the present invention include the following. A red-sensitive unit, a green-sensitive unit, and a blue-sensitive unit are applied from the side near the support, and at least the red-sensitive unit and the green-sensitive unit are composed of three photosensitive emulsion layers, and they are close to the support. To low, medium, and high sensitivity. The silver / coupler ratio in each of these light-sensitive layers is the largest in the low-speed layer, and the silver / coupler ratio in the green-sensitive emulsion layer having the highest visual sensitivity of a color image is 2 in particular.
5-150 is preferred. In this case, the silver / coupler ratio of the intermediate layer is 5 to 30, and the silver / coupler ratio of the high-sensitivity layer is 2 to 30.
20 is preferred.

Further, between the red-sensitive unit and the green-sensitive unit, and between the green-sensitive unit and the blue-sensitive unit, two or more and five or less intermediate layers are provided, and a layer adjacent to the former green-sensitive layer, The layer adjacent to the latter blue-sensitive layer contains colloidal silver grains or a previously fogged silver halide emulsion. The thickness of the intermediate layer is 0.5 to 5 μm in total for the two layers.
m, and more preferably 1.0 to 3.0 μm.
This film thickness can be theoretically easily determined by the specific gravity of the additive, and the actual coated material can be easily measured by observing the cross section with an electron microscope. The antihalation layer is provided on the side closer to the support than the red-sensitive unit, and the intermediate layer is provided with at least one protective layer on the side farther from the support than the blue-sensitive unit. Preferably contains a silver halide emulsion.

Regarding various techniques and inorganic and organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same, Research Disclosure No. 308119 (1
989) can be used. In addition to this, more specifically, for example, regarding the technology and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied,
It is described in EP 436,938 A2 at the following places and in the patents cited below.

Item Corresponding section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler, page 137 Line 35 to page 146, line 33, page 149, lines 21 to 23 4) Magenta coupler, page 149, lines 24 to 28; page 3, line 5 of EP 421,453A1 5th page, line 25, 5) Cyan coupler, page 149, lines 29 to 33; EP 432,804A2, page 3, line 28 to page 40, line 6) Polymer coupler 149 Page 34, lines 38 to 38; EP 113, 334A2, page 113, lines 39 to 123, line 37 7) Colored couplers, page 53, lines 42 to 137, lines 34, 149 Page 39th line-45th line 8 Other functionalities, page 7, line 1 to page 53, line 41, page 149, line 46 Coupler to page 150, line 3; EP 435,334A2, page 3, line 1 to line 3 Page 29, line 50 9) Antiseptic / anti-inhibitor, page 150, lines 25-28

10) Formalin, page 149, lines 15-17 Scavenger 11) Other additives, page 153, lines 38-47; EP 421, 453A1, page 75, lines 21- Page 84, line 56, page 27, line 40 to page 37, line 40 12) Dispersion method page 150, lines 4 to 24 13) Support page 150, lines 32 to 34 14) Membrane Thickness / Film physical properties, page 150, lines 35 to 49 15) Color development, black and white, page 150, line 50 to page 151, line 47; European special development, fogging process No. 442, 323A2 Page 34, lines 11 to 54, page 35, lines 14 to 22 16) Desilvering process Page 151, line 48 to page 152, line 53 17) Automatic developing machine Page 152, lines 54 to 54 Page 153, 2nd line 18) Washing and stabilization step Page 153, 3rd to 37th lines.

[0104]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Example 1 Preparation of photosensitive material sample A An undercoated 127 μm thick cellulose triacetate fill
A multilayer color image composed of the following layers on a support
An optical material was prepared and used as a light-sensitive material sample A. The number is m ^TwoPer hit
Indicates the amount added. First layer: Antihalation layer Black colloidal silver 0.10 g Gelatin 2.20 g UV absorber U-1 0.20 g UV absorber U-3 0.040 g UV absorber U-4 0.15 g High boiling organic solvent Oil- 1 0.10 g Dye E-1 microcrystalline solid dispersion 0.10 g Dye D-8 2.5 mg Dye D-4 1.0 mg

Second layer: Intermediate layer Gelatin 0.40 g UV absorber U-6 8.0 mg Compound Cpd-C 0.5 mg Compound Cpd-J 1.5 mg Compound Cpd-K 4.0 mg High boiling organic solvent Oil-3 10 mg High-boiling organic solvent Oil-4 20 mg High-boiling organic solvent Oil-5 2.0 mg High-boiling organic solvent Oil-7 2.0 mg High-boiling organic solvent Oil-8 5.0 mg Dye D-7 2.5 mg

Third layer: Intermediate layer A fine-grain silver iodobromide emulsion whose surface and inside are fogged (average particle size: 0.06 μm, variation coefficient: 18%, AgI content: 1 mol%) Silver amount: 0.020 g Yellow colloidal silver 0 0.030 g Gelatin 0.40 g Compound Cpd-M 15 mg High boiling organic solvent Oil-3 20 mg Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.20 g Emulsion B silver amount 0.20 g Emulsion C 0.15 g gelatin 0 0.70 g Coupler C-1 0.10 g Coupler C-2 0.050 g Coupler C-3 0.050 g Coupler C-9 10 mg Coupler C-11 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-I 20 mg Compound Cpd- J 5.0 mg High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Fifth layer: Medium-sensitivity red-sensitive emulsion layer Emulsion C silver content 0.25 g Emulsion D silver content 0.25 g gelatin 0.70 g coupler C-1 0.15 g coupler C-2 0.050 g coupler C-30 .20 g Coupler C-11 0.070 g High-boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion E Silver amount 0.20 g Emulsion F 0.25 g Gelatin 1.20 g Coupler C-1 0.10 g Coupler C-2 0.10 g Coupler C-3 0.50 g Coupler C-11 0.15 g Compound Cpd-K 2.0 mg Additive P-1 0.10 g

Seventh layer: Intermediate layer Gelatin 0.60 g Additive P-2 0.30 g Color mixing inhibitor Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-M 040 g Compound Cpd-O 3.0 mg Compound Cpd-P 2.5 mg High-boiling organic solvent Oil-1 0.020 g High-boiling organic solvent Oil-6 0.050 g Eighth layer: Intermediate layer Iodine odor on the surface and inside Silver halide emulsion (average particle size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) Silver amount 0.020 g Yellow colloidal silver Silver amount 0.030 g Gelatin 0.60 g Additive P-1 0.20 g Color mixing inhibitor Cpd-A 0.10 g Compound Cpd-M 0.10 g High boiling organic solvent Oil-6 0.10 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion G silver content 0.25 g Emulsion H silver content 0.30 g Emulsion I silver content 0.25 g gelatin 0.80 g Coupler C-4 0.050 g Coupler C-70 .10 g Coupler C-8 0.12 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-G 2.5 mg Compound Cpd-K 5 mg Compound Cpd-L 0.020 g High boiling organic solvent Oil-1 0.10 g High boiling organic solvent Oil-2 0.10 g

Tenth Layer: Medium-Sensitive Green-Sensitive Emulsion Layer Emulsion I Silver content 0.20 g Emulsion J Silver content 0.20 g Gelatin 0.60 g Coupler C-4 0.10 g Coupler C-7 0.050 g Coupler C-80 0.050 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound CPd-F 0.050 g Compound CPd-G 2.0 mg Compound Cpd-L 0.010 g High boiling organic solvent Oil-2 0.010 g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver amount 0.55 g Gelatin 0.70 g Coupler C-4 0.25 g Coupler C-7 0.10 g Coupler C-8 0.050 g Compound Cpd-B 0 0.080 g Compound Cpd-D 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-2 0.020 g 12th layer: Intermediate layer Gelatin 0.30 g Compound CPd-M 0.050 g High boiling organic solvent Oil-3 0.025 g High boiling organic solvent Oil-6 0.025 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 5.0 mg Gelatin 1.0 g Color mixing inhibitor Cpd-C 0.010 g Compound Cpd-L 0.010 g Compound Cpd-M 0.030 g High boiling point solvent Oil-1 0.010 g Solid crystalline dispersion of dye E-2 0.030 g Fine crystalline solid dispersion of dye E-3 0.020 g 14th layer: Intermediate layer Gelatin 0.40 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.20 g Emulsion M silver amount 0.20 g gelatin 0.80 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-100 .10 g Compound Cpd-I 0.010 g Compound Cpd-M 0.010 g Sixteenth layer: medium-sensitivity blue-sensitive emulsion layer Emulsion N Silver content 0.20 g Emulsion O Silver content 0.20 g Silver iodobromide emulsion with an internal fogging (Average particle size 0.08, Coefficient of variation 15%, AgI content 0.5 mol%) 0.050 g Gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.10 g Compound 2.0mg Cpd-K 2.0mg Compound Cpd-N

17th layer: High-sensitivity blue-sensitive emulsion layer Emulsion O Silver content 0.20 g Emulsion P silver content 0.25 g Gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-100 .80 g Compound Cpd-N 5.0 mg Formalin scavenger Cpd-Q 0.20 g High boiling organic solvent Oil-2 0.10 g 18th layer: 1st protective layer Gelatin 0. 70 g UV absorber U-10. 20 g UV absorber U-20. 050 g UV absorber U-50 30 g Compound Cpd-O5. 0 mg formalin scavenger Cpd-H 0. 20 g Dye D-10. 15 g Dye D-20. 050 g Dye D-3 0.10 g

Nineteenth layer: Second protective layer Yellow colloidal silver Silver content 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.10 g Gelatin 0.60 g Twenty Layer: Third protective layer Gelatin 0.80 g Polymethyl methacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methyl methacrylate and methacrylic acid (average particle size 1.5 μ) 0.10 g Silicone oil SO-1 0.030 g Surfactant WW-1 3.0 mg Surfactant WW-2 0.030 g

In addition, additives F-1 to F-10 were added to all the emulsion layers in addition to the above composition. Furthermore, in addition to the above composition, gelatin hardener H-1 and surfactants for coating and emulsification WW-3, WW-4, WW-5, WW-
6 was added. Phenol as an antiseptic and fungicide,
1,2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, butyl p-hydroxybenzoate were added.

Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, 1430 g of a wet cake of a dye containing 30% of methanol was added to water and Pluronic F88 (ethylene oxide-manufactured by BASF).
200 g of propylene oxide block copolymer) was added and stirred to obtain a slurry having a dye concentration of 6%. Next, Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd.
Zirconia beads with an average particle size of 0.5 mm
and pulverized for 8 hours at a peripheral speed of about 10 m / sec and a discharge rate of 0.5 l / min. The beads were removed by filtration, diluted with water by adding water to a dye concentration of 3%, and heated at 90 ° C. for 10 hours for stabilization. The average particle size of the obtained fine dye particles was 0.60 μm, and the width of the particle size distribution (particle size standard deviation × 100 / average particle size) was 18%. Similarly, solid dispersions of dyes E-2 and E-3 were obtained. The average particle sizes were 0.54 μm and 0.56 μm.

Table 1 shows the silver iodobromide emulsions used for the light-sensitive material sample A. Table 2 shows the spectral sensitizers used for spectral sensitization of each emulsion and the amounts used. In addition, the chemical formulas of the respective compounds indicated by the abbreviations in the composition formula of the light-sensitive material sample A are also shown below.

[0120]

[Table 1]

[0121]

[Table 2]

[0122]

[Table 3]

[0123]

[Table 4]

[0124]

[Table 5]

[0125]

Embedded image

[0126]

Embedded image

[0127]

Embedded image

[0128]

Embedded image

[0129]

Embedded image

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image

[0137]

Embedded image

[0138]

Embedded image

[0139]

Embedded image

[0140]

Embedded image

[0141]

Embedded image

[0142]

Embedded image

Exposure and Development After the obtained photosensitive material sample A was cut into a 35 mm width, the photosensitive material sample A was exposed to light of 20 CMS using a standard light source of 4800K through a light wedge for sensitometry of neutral color. The exposed sample was subjected to a color reversal process by the following processing steps.

(Process 1) Processing Step Time Temperature Tank Capacity Replenishment First Black and White Development 6 min 38 ° C 12 L 2200 mL / m ² First Rinse 2 min 38 ° C. 4 L 7500 mL / m ² Reversal 2 min 38 ° C. 4 L 1100 mL / m ² color developing 6 min 38 ° C. 12L 2200 mL / m ² before bleaching 2 min 38 ° C. 4L 1100 mL / m ² bleaching 6 min 38 ° C. 2L 220 mL / m ² Fixing 4 min 38 ° C. 2L 1100 mL / m ² second water washing 4 minutes 38 ° C 8L 7500mL / m ² Final rinse 1 minute 25 ° C 2L 1100mL / m ²

The composition of each processing solution was as follows. [First black and white developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphone 1.5g 1.5g Acid ・ pentasodium salt Diethylenetriaminepentaacetic acid ・ pentasodium salt 2.0g 2.0g Sodium sulfite 30g 30g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Sodium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to 1000 mL 1000 mL pH 9.60 9.60 The pH was adjusted with sulfuric acid or potassium hydroxide.

[Reversing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3.0 g Same as tank solution Stannous chloride dihydrate 1.0 g p-amino acid Phenol 0.1 g Sodium hydroxide 8 g Propionic acid 15 mL Potassium sorbate 0.5 g Myristyltrimethylammonium boromide (MTAB) 0.1 g Water was added, and the pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 hydrate 36 g 36 g Sodium bromide 0.7 g-Potassium iodide 40 mg-Sodium hydroxide 3.0 g 3.0 g Citrazinic acid 0.5 g 0.5 g Hydroxylamine sulfate 2.0 g 2.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3 -Methyl-4-aminoaniline 3/2 sulfuric acid monohydrate 11g 11g 3,6-dithiaoctane-1,8-diol 1.0g 1.0g Add water 1000mL 1000mL pH 11.70 12.00 pH is adjusted with sulfuric acid or potassium hydroxide It was adjusted.

[Pre-bleaching] [Tank liquid] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g Sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g Formaldehyde sodium bisulfite adduct 20 g 25 g Methanol 2 g 2 g Water was added to 1000 mL 1000 mL pH 6.30 6.10 The pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g 240 g potassium bromide 100 g 200 g Ammonium nitrate 10 g 20 g Water was added 1000 mL 1000 mL pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g To the tank solution was added the same sodium sulfite 5.0 g sodium bisulfite 5.0 g water, and 1000 mL pH 6.60 pH was adjusted with acetic acid or aqueous ammonia.

[Stabilizing solution] [Tank solution] [Replenishment solution] 1,2-benzizothiazolin-3-one 0.02g Same as tank solution Dipropylene glycol 0.3g Organic silicon surfactant 0.2g Polyoxyethylene-dodecane ether (Average degree of polymerization: 10) Add 0.2 g water and add 1000 mL pH 7.0

Development Test Both the tank solution and the replenisher of the above color developing solution formulation contained the compound of the present invention in an amount of 1 per liter as shown in Table 3.
0 mg was added, and the pH was adjusted with sulfuric acid and potassium hydroxide so that trisodium phosphate / 12-hydrate was replaced with equimolar potassium carbonate, and the pH value was 10.10 for the tank solution and 10.30 for the replenisher. The color developing solution thus prepared was also prepared and, as shown in Table 3, was developed by entanglement with the addition of the compound of the present invention. At the time when the development processing was performed until the cumulative replenishment amount of the color development replenisher in the above-mentioned processing step became three times the tank capacity, the color density of the processed sample was measured according to the measurement method of International Standard (ISO5). The maximum color density of the cyan color portion corresponding to the separated red exposure portion of the light wedge was obtained and used for evaluating the color density.

Results As shown in Table 3, Sample 104 in which the compound of the present invention is present
Has a sufficient color density, whereas in a developer having a high pH exceeding the range of the present invention, the effect of adding the compound of the present invention is poor (sample 102).
It was also shown that, just by lowering the value to the range of the present invention, if the compound of the present invention was not contained, a sufficient color density could not be obtained (sample 103).

[0154]

[Table 6]

Embodiment 2 In this embodiment, the effect of the present invention is shown by the processing in which the reversal bath is removed from the above processing steps. Removing the reversal bath and p
Development was carried out in the same manner as in Example 1, except that the H value was changed as shown in Table 4, and that the compound of the present invention was added as shown in Table 4. As in the case of Example 1, the pH of the color developing solution was 11.7 as the alkaline agent and pH buffer.
In the case of 0, trisodium phosphate / 12-hydrate was used, and equimolar potassium carbonate was used in the color developing solution having a pH other than that.

Results Comparative Examples 201 to 207 to which the compound of the present invention was not added were as follows:
Regardless of the pH value, the color density was insufficient regardless of the pH value, whereas the samples 210 to 216 of the present invention each had a sufficient color density, and in particular, the remarks column showed "○".
As shown by "", the pH value is in the range of 9.5 to 10.5, and the samples 212 to 214 having the pH value in the range of 10.0 to 10.3 are particularly excellent in color density. . On the other hand, when the pH value was higher or lower than the range of the present invention, it was also shown that satisfactory coloring was not obtained even when the compound of the present invention was added (Samples 217 and 20).
8, 209).

[0157]

[Table 7]

Example 3 In this example, the effect of the present invention is shown by changing the compound of the general formula (I). The development was performed in the same manner as in Sample 213 of Example 2 except that Compound I-4 of Sample 213 of Example 2 was changed to another compound of the general formula (I) having an equal weight as shown in Table 5. .

Results As can be seen from Table 5, each of the compounds of the present invention exhibited a sufficient color density, although there were some differences.

[0160]

[Table 8]

Example 4 This example demonstrates the effect of the substituted hydroxylamine, which is a preferred embodiment of the present invention. A development test was conducted in the same manner as in Sample 213, except that the hydroxylamine sulfate in the color developing solution in Sample 213 of Example 2 was replaced with the substituted hydroxylamine represented by the general formula (II) in an equimolar amount.
Further, after the development was continued until the cumulative replenishment amount of the color developing replenisher became three times the tank volume, the color density of the developed sample (described immediately after running in Table 6) and the developing machine were stopped for one week. A comparison of the developed samples, which were run again afterwards (described as 1 week after stopping running in Table 6), shows that after a lapse of time, the decrease in the color development density does not include the substituted hydroxylamine but includes the hydroxylamine sulfate. It is shown to be significantly less than the comparative sample.

[0162]

[Table 9]

[0163]

In the reversal color developing treatment, a compound of the general formula (I), preferably a compound of the general formula (II) is added, and a color developing solution having a pH of 9.0 to 11.0 is used. According to the method of the present invention, the fogging bath can be omitted, and even if it is omitted, excellent photographic characteristics having a high color density can be maintained, and a reversal development process in which the process is stable can be performed.

Claims (3)

[Claims] 1. A method for processing a silver halide color reversal photographic light-sensitive material, in which a second development is carried out with a color developer after the first black-and-white development and washing with water, the color developer having a pH of 9.0
-11.0, and at least one compound represented by the following general formula (I). General formula (I) (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent. A represents a group adsorbed on a silver halide surface. L represents a linking group. Where m is 0
Represents an integer of from 4 to 4. n represents 0 or 1. ) 2. The method for processing a color reversal photographic material according to claim 1, wherein the color developer contains at least one kind of substituted hydroxylamine represented by the following general formula (II). General formula (II) (In the formula (I), L ¹ represents an alkylene group which may be substituted, A ¹ represents a carboxyl group, a sulfo group, a phosphono group,
Phosphinic acid residue, hydroxyl group, amino group optionally substituted with alkyl, ammonium group optionally substituted with alkyl, carbamoyl group optionally substituted with alkyl, sulfamoyl group optionally substituted with alkyl or alkyl optionally substituted R represents a hydrogen atom or an alkyl group which may be substituted; Further, L ¹ and R may be linked to form a ring. ) 3. A color developer for color reversal photographic light-sensitive materials, comprising at least one compound represented by the general formula (I) according to claim 1 and having a pH of 9 to 11. .