JPH0664318B2 - Silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material, more specifically, a color image and an unsharp mask are automatically formed to enhance the edge effect. The present invention relates to a silver halide color photographic light-sensitive material having improved sharpness.

[Background of the Invention]

With respect to color photographic light-sensitive materials in recent years, the screen size of photographic light-sensitive materials has become smaller due to advances in camera manufacturing technology and the like, so that the magnification of printing light-sensitive materials tends to increase. Therefore, in particular, as the image quality of the photographic light-sensitive material, the high-quality characteristics such as the improvement of graininess by making the coloring dye cloud finer or the improvement of sharpness by the prevention of optical scattering and the enhancement of the edge effect by the development effect are imparted. There is a strong demand for that, and various proposals have been made to achieve these issues.

A method of forming an unsharp mask together with a color image has been proposed as one of the technical means of sharpness.

As a photographic material capable of forming a color image and an unsharp mask for obtaining a color image having excellent sharpness, a physical development nucleus-containing layer containing a diffusion-resistant coupler, a layer containing an oxidant scavenger of a color developing agent, and A photographic material in which light-sensitive silver halide emulsion layers containing diffusible couplers are sequentially laminated is disclosed in French Patent No. 2,260,124. Then, as a preferred method for obtaining a color negative image and an unsharp positive image using the photographic material, after exposure, color development is carried out with a first color developing solution containing no silver halide solvent to obtain a color negative image, and then a silver halide. A method for obtaining an unsharp positive image by physical color development using a second color developer containing a solvent is disclosed.

However, this photographic material undergoes a color development reaction in the exposed area to obtain a color negative image, and a physical color development reaction using dissolved silver halide in the unexposed area to obtain an unsharp positive image. It is necessary to wake up. Therefore, there is a scavenger of the oxidized color developing agent between the two layers containing the diffusion resistant coupler in order to prevent the diffusion of the oxidized color developing agent into the physical development nucleus-containing layer which occurs when forming a color negative image. It is essential to let

That is, if the scavenger is not present, the oxidized product of the color developing agent generated in the exposed area is partially diffused into the physical development nucleus-containing layer, where an unsharp negative image is produced by the color developing reaction, and the desired color negative image and unsharp positive image are produced. I can't get a statue. Further, since three layers including the scavenger-containing layer are essential, it is difficult to reduce the film thickness, and it is difficult to improve the sharpness also from this point.

Further, this method requires performing color development twice using two color developers as described above. If it is assumed that color development is performed only once using only a color developing solution containing a silver halide solvent, color development for obtaining a color negative image and a silver halide complex for supplying silver ions to the physical development nucleus-containing layer Is difficult to control. When this control is lost and the amount of the complex is excessively generated, the color negative image is less likely to be produced, and as a result, excessive diffusion of the complex into the physical development nucleus layer is caused, resulting in the area where the color negative image should be originally produced. Since an unsharp positive image is generated, the desired color negative image and unsharp mask image cannot be obtained, and the object cannot be achieved.

On the other hand, in order to solve these problems, new methods have been proposed in Japanese Patent Application Nos. 59-195152, 60-10490, 60-43374 and the like. The compound disclosed in the above specification is i) a dye having substantially the same color as a dye formed by the reaction of the diffusion resistant coupler with an oxidized product of a color developing agent, or a precursor thereof, ii)
A compound that diffuses moderately during the development process, and ii
i) A compound that produces a diffusion resistant dye of substantially the same color as the dye produced by the reaction between the diffusion resistant coupler and the oxidation product of the color developing agent by reaction with the oxidation product of the color developing agent (hereinafter referred to as USM compound It is called).

More specifically, the USM compound has a property of reacting with an oxidized product of a color developing agent. Therefore, in the area where a color image is produced by the reaction between the oxidation product of the color developing agent and the diffusion resistant coupler, the USM compound also reacts with the oxidation product of the developing agent to form a diffusion resistant dye similar to the diffusion resistant coupler.
This dye forms a color image together with the diffusion resistant dye formed by the reaction of the above diffusion resistant coupler with the oxidized product of the color developing agent.

On the other hand, the USM compound remains unreacted in the area where no color image is formed by the diffusion resistant coupler. As a result, the color image formed by the diffusion-resistant coupler and the unreacted USM compound have an inverse relationship, that is, when the former is a negative image, the latter forms a positive image. Moreover, unreacted USM
Since the compound has a suitable diffusibility, it forms an unsharp image, that is, an unsharp mask image.

Moreover, as described above, the USM compound forms an unsharp mask image in the unreacted state and contributes to the formation of a color image when it reacts with the oxidant of the color developing agent.

These USM compounds have the excellent properties as described above, but on the other hand, due to their basic principle, the minimum density (fog density) increases on the characteristic curve and the gamma decreases to form a positive image. Have a point. Further, as the sharpness, if the diffusivity is imparted to emphasize the edge effect particularly in the low frequency region, it diffuses into a layer other than the desired layer or in the developing treatment solution, so that the above-mentioned effect cannot be obtained. . As a means of obtaining a more edge effect, USM is added in the non-photosensitive emulsion layer adjacent to the silver halide emulsion layer.
It has been proposed to add a compound and react with the oxidized product of the color-developing agent that diffuses from the silver halide emulsion layer, but the edge effect is much larger than when it is present in the same silver halide emulsion layer. Will fall to.

As described above, the USM compound has not yet been put to practical use as a color light-sensitive material for photography.

[Object of the Invention]

An object of the present invention is to solve the above-mentioned drawbacks of the prior art. That is, a first object of the present invention is to provide a photographic light-sensitive material capable of obtaining an image with improved sharpness by producing a color negative image and an unsharp positive image.

A second object of the present invention is to provide a photographic light-sensitive material in which the increase in minimum density is suppressed.

A third object of the present invention is to provide a photographic light-sensitive material having a high gamma.

[Structure of Invention]

As a result of intensive research aimed at achieving the above object, we have found that the object of the present invention can be achieved by a photographic light-sensitive material having the following constitution.

That is, means for forming an unsharp positive image in combination with at least one light-sensitive silver halide emulsion layer on a support, and a compound which captures an oxidant of a color developing agent but does not contribute to image formation. And a silver halide color photographic light-sensitive material characterized by containing

The present invention will be described in more detail.

A preferable means for forming an unsharp positive image is an unsharp positive image-forming compound (hereinafter referred to as a positive compound) in combination with a color negative image-forming silver halide emulsion layer containing a diffusion-resistant coupler. To be

One preferable example of the positive compound is a small diffusibility, and the main absorption in the main absorption wavelength region of a dye (hereinafter, referred to as a color forming dye) produced by the reaction of the above diffusion resistant coupler with an oxidized product of a color developing agent. A colored compound having, or a compound that is a compound that changes color during development processing, a so-called precursor, and as a result of reaction with an oxidant of a developing agent, has a main absorption in the main absorption wavelength range of a decolorizing or coloring dye. Compounds that form diffusible dyes (hereinafter referred to as small diffusible positive compounds)
Is.

Another preferable example of the positive compound is a colorant compound which is diffusion resistant and has a main absorption in the main absorption wavelength region of the coloring dye, or a compound which changes into the colorant compound during the development processing, and is a developing agent. Is a compound that is decolorized as a result of the reaction with the oxidant (hereinafter referred to as a diffusion resistant positive compound).

The small diffusible positive compound will be described in detail.

Small diffusivity means that in an image forming process using a photographic material, especially in the developing process, it diffuses more than a diffusion resistant coupler used in combination, but after the processing process is completed, It means that at least 30 wt% or more remains in the photographic material.

As for the degree of discoloration, the change in maximum absorption wavelength is preferably 10 nm or more. As such a color change mechanism, a mechanism in which the color tone is changed by the hydrolysis of the positive compound is preferably mentioned.

Decoloring does not produce a colored compound. Alternatively, it means that the colored compound does not remain in the photographic material to the extent that the unsharp positive image formation is impaired at the end of the imaging process due to the generated colored compound flowing out of the photographic material during the development processing.

Such a decolorizable small diffusible positive compound reacts with an oxidized product of the developing agent in the area where a color image is formed by the reaction between the color developing agent and the above diffusion-resistant coupler, thereby decoloring. Further, in a region where a color image due to the diffusion resistant coupler is not produced, it remains unreacted or discolored. As a result, the color image formed by the antidiffusive coupler and the decolorizable small diffusible positive compound are in the inverse relationship, that is, the former forms a negative image, while the latter forms a positive image. . Moreover, since the small diffusible positive compound has a small diffusibility, it forms an unsharp image, that is, an unsharp positive image.

Next, as a result of the reaction with the oxidant of the developing agent, a small diffusible positive compound of a type that produces a diffusion resistant dye having a main absorption in the main absorption wavelength range of the color forming dye, that is, a diffusion resistant dye forming type small diffusion. Positive compounds will be described.

The diffusion-resistant dye-forming small diffusion positive compound is unreacted or discolored in an area where a color image is not formed by the diffusion-resistant coupler. As a result, the color image formed by the antidiffusive coupler and the unreacted or discolored small diffusive positive compound have an inverse relationship, that is, when the former is a negative image, the latter forms a positive image. Moreover, since the small diffusible positive compound has a small diffusivity, it forms an unsharp image, that is, an unsharp positive image.

As mentioned above, the diffusion-resistant dye-forming type small diffusion-possible positive compound forms an unsharp positive image and has a main absorption in the main absorption wavelength range of the coloring dye due to the reaction with the oxidant of the developing agent. Produces sex pigments. The antidiffusive dye forms a color image together with the antidiffusive dye formed by the reaction between the antidiffusive coupler and the oxidized color developing agent.

The diffusion-resistant dye-forming, small diffusion-positive compound produces both an unsharp positive image and a negative image composed of the diffusion-resistant dye, as described above. Therefore, although the two images may overlap, it may appear that the density does not change macroscopically, but at the edge part (the boundary part where the intensity of the irradiation light changes), the positive compound and the produced diffusion-resistant dye are formed. Due to the difference in the diffusivity of (1), a microscopic density change (edge effect) occurs, which is effective as an unsharp positive image forming means.

Examples of the decolorizable small diffusible positive compound include compounds represented by the following general formula [I].

General formula [I] A-Link-B In the formula, A is an organic residue capable of reacting with an oxidized product of the developing agent to release the Link-B portion in accordance with the amount of the oxidized product of the developing agent. Is a group that binds to, and B represents an organic residue.

Further, the compound represented by the general formula [I] is a compound that causes a slight color diffusion or color change in the photographic material during the development process, and the product resulting from A and Link-B after the reaction is a colored compound. In the above, the product is provided with a substituent having a balanced hydrophilicity or lipophilicity so that the product flows out of the system from the photographic material after the reaction.

Examples of A in the general formula [I] include a residue of a coupler which produces a colored or colorless product by a coupling reaction with an oxidized product of a color developing agent or a component which undergoes a cross oxidation reaction with an oxidized product of a developing agent. To be

Specific examples of the former include, for example, phenols, naphthols, 5-pyrazolones, pyrazocotriazoles,
Pyrazolobenzimidazoles, indazolones, acylacetanilides, RCOCH ₃ (R is alkyl,
Aryl, heterocyclic group) (Z is a group of atoms that completes, for example, a 5- to 8-membered saturated or unsaturated alicyclic ring or heterocyclic ring, and R'represents an aryl residue.).

Specific examples of the latter include, for example, an alkali after being oxidized.
B-SO as Link-B by cleavage₂NH Emitting fe
Knols, naphthols, indanones, indole
, Hydroquinone residues, after being oxidized, closed intramolecularly
Received ring reaction and B-SO as Link-B₂ Emit
Enols (see U.S. Pat. Nos. 3,443,939 and 3,44
Nos. 3,940 and 3,443,941. ) Is
Can be mentioned.

As the Link, for example, -N = N-, -O-, -S-,-
_{NH-SO 2 -, - SO} 2 -NH-, -CH = etc. are mentioned.

here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl, triazolyl, benztriazolyl, urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl , Tetrazo reel and so on. R is an alkyl optionally having a substituent,
Aryl and the like.

As B, when Link is a chromophore such as -N = N-, -CH =, it is, for example, an aryl group or a heterocyclic group, and preferably an organic residue having an auxochrome or a dye residue. It may be. When Link is not a chromophore, it is preferably a dye (eg, azo, anthraquinone, azomethine, indophenol, indoaniline, etc.) residue.
The compound represented by the general formula [I] having such a structure is represented by B
It may be a compound that is colored or discolored as a part or the entire A-Link-B.

To give the compound represented by the general formula [I] a property of slightly diffusing during the development processing and a diffusing property for allowing an undesirable product after the reaction to flow out of the system, for example, a carboxyl group is used. , An alkali-soluble group such as a sulfo group, a hydroxyl group, and a sulfamoyl group, and a group such as an alkyl group that reduces diffusibility may be appropriately introduced to balance the diffusivity before and after the reaction.

When the compounds of the present invention are classified according to their properties, for example, the following classifications can be mentioned.

CLASSI: Coloring dye forming type In the compounds belonging to this class, the A portion of the general formula [I] is a coupler residue and the Link portion is bonded to the active site of the coupler. However, when Link is —NHSO ₂ — (a nitrogen atom is bonded to the Coup part), it may be adjacent to the active site.

The photographic material preferably has an alkali-soluble group and, for example, an alkyl group having 16 or less carbon atoms so as to diffuse a small amount. When the portion A is coupled with the oxidized product of the color developing agent to form a colored compound, an alkali-soluble group should be present in the portion A so that the compound may flow out of the system during processing. It is preferable to use one having a group.

When the B portion forms a dye, the B portion preferably has an alkali-soluble group so that the B portion after the reaction flows out of the system.

In the exposed part, the compound A belonging to this class produces a negative colored dye image in the exposed part, but flows out of the system, and when the part B is a dye, the part B also flows out of the system after leaving the part A. Therefore, a positive image is formed with the compound represented by the general formula [I] or the compound after discoloration which remains in the unexposed area. In addition, the compound has a small diffusivity so that it moves slightly through the layer during the development process to form an unsharp positive image. Further, among these types, the following two types are preferable.

(Type A): Colored coupler type Coup-Link _2- Ar of the general formula [II] Coup- of the general formula [II] is preferably a coupler residue having an alkali-soluble group, and the dye produced by the color development reaction is a photographic material system. It leaks out.

Ar is preferably an aryl group which may have a substituent, for example, a benzene type or naphthalene type, and a heterocyclic group which may have a substituent, for example, isoxazole and the like, and a compound of the general formula [II] is photographed. Since it moves slightly in the material, it preferably has a semi-diffusion preventing group, and particularly preferably has an Ar portion. Link ₂ is -N = N- or -CH =. Some of these compounds have already been used as colored couplers, for example, U.S. Pat.Nos. 2,449,969, 2,688,538 and 2,706,68.
No. 4, No. 2,808,329, No. 3,005,712, Belgian Patent No. 5
It is known for 70,217 and Japanese Patent Publication No.44-32461.

However, the present invention and these prior arts are completely different in the use method of the compound and the purpose of use, and the effects obtained are completely different. That is, in the above-mentioned prior art, since the hue generated by the Coup portion or coupler portion represented by the general formula [II] is the main absorption for image formation, it is a principle that the dye generated from this portion does not move, The hue of the compound represented by the formula [II] is a secondary absorption portion different from the above main absorption wavelength region. According to the present invention, it is essential that the dye generated from the Coup portion is taken out of the system, and that the general formula [I
The hue of the compound represented by I] or the compound after discoloration is the same as the main absorption of the image forming layer. That is, the light-sensitive wavelength range of the silver halide layer combined with the compound of the present invention is the complementary color of the compound hue in the case of a conventional negative photographic material. Specifically, for example, with respect to a green-sensitive negative layer, prior art colored couplers use a yellow compound in this layer, while the present invention uses a magenta or magenta discoloring compound. .

(Type B): Active site substitution type General formula [III] Coup-Link _3- Dye Coup is the same as general formula [II]. Further, Link ₃ has the same meaning as Link of the general formula [I], and similar ones are exemplified, and preferably a group which produces alkali solubility after the coupling reaction, for example, —O—, —SO ₂ —NH—, —NHSO. _2- is preferable. Dye represents a dye portion or a dye precursor portion and preferably has an alkali-soluble group, but it is not essential depending on the type of Link ₃ .

Since the compound represented by the general formula [III] is adjusted to slightly diffuse in the photographic material, it preferably has a semi-diffusion preventing group.

The group is preferably attached to one of the coloring dyes and Link _3- Dye, which has a better diffusibility. Compounds belonging to this class are disclosed in U.S. Pat. Nos. 3,227,550 and 3,476,563, but these prior arts have completely different usages similar to Type A, and the concept of the present invention is included. It is not. That is, part of it is used for color correction similar to Type A color coupler, and Dye that is diffused and transferred and flows out.
This is clearly different from the aspect of the present invention when the parts are used for the image.

Next, a compound group that does not produce a color image after the color reaction is described.

CLASSII: colorless coupling body-forming type Compounds belonging to this class have CLAS as the A part of general formula [I].
It reacts similarly to the compound of SI, but since the reaction product is colorless, it may remain in the layer after the coupling reaction.

(Type C): Weiss coupler type General formula [IV] Wcoup-Link _4- Dye Wcoup is, for example, R ₂ COCH _2- (R ₂ is alkyl, aryl, heterocyclic group having alkyl having 16 or less carbon atoms), (Z is an atomic group that completes a 5- to 8-membered alicyclic ring, condensed ring or heterocyclic ring, and R ₃ represents an aryl residue).

Link ₄ is -O -, - S- or -SO ₂ - shows a.

Dye is a dye residue preferably having an alkali-soluble group or its precursor portion, and Link _4- Dye flows out of the layer.

Further, this compound preferably has a semi-diffusion preventing group so that the compound itself slightly diffuses in the layer in cooperation with the alkali-soluble group which may be present in the Dye portion, and particularly in the W-Coup portion. Preferably there is.

CLASS III: Redox reaction type Compounds belonging to this class do not undergo the coupling reaction as in CLASS I or II. Instead, it reacts with an oxidized product of a developing agent to form a quinone, a quinimide, etc., but this product releases a dye only when it reacts with an alkali in a developing solution or an intramolecular ring closure reaction.

(Type D): DRR compound type General formula [V] FUN-Link ₅ -Dye FUN shows a redox mother nucleus, and is 2-, 3- or 4-phenol, 4-α-naphthol, 1-β-naphthol, 2
-Hydroquinone, 3-indole, 4-pyrazolone-
Link ₅ is -NHSO _2- (nitrogen atom is bonded to FUN part), -O-, -SO _2- , -S-, etc. Dye is dye residue or its precursor part. It is preferable to have an alkali-soluble group.

When a semi-diffusion preventing group that cooperates with an alkali-soluble group which may be present in the Dye portion is used to allow the compound of the general formula [V] to slightly diffuse in the layer, it is preferably attached to the FUN portion. .

The diffusion-resistant dye-forming small-diffusible compound is a dye or a precursor thereof as described above, and produces a diffusion-resistant dye by a reaction with an oxidant of a color developing agent. A dye portion may be newly formed by the reaction, or a dye portion is not newly formed, and the dye portion before the reaction or its precursor portion is a diffusion resistant dye after the development treatment step. It may remain as a dye portion.

Examples of the diffusion-resistant dye-forming type small diffusible compound include the following types due to their functions.

Type I A dye portion which is previously held by coupling with an oxidized product of a color developing agent or a precursor thereof newly forms a dye portion having substantially the same color as the dye portion generated during the development processing step, and is resistant to diffusion. A compound that turns into a dye (dye-forming type).

This type can be further classified into the following types.

Type I-1 A dye portion or a precursor portion thereof which has been preliminarily erased by coupling with an oxidized product of a color developing agent, and the dye portion or a precursor portion thereof is newly provided after the development treatment step. A compound that forms a dye portion having substantially the same color as the dye portion to be formed and is diffusion resistant.

Type I-2 The dye portion or the precursor portion thereof which is previously held is not decolored by the coupling with the oxidation product of the color developing agent, and the dye portion or the precursor portion is newly developed. A compound that forms a dye portion having substantially the same color as that of a dye portion to be formed later and is diffusion resistant. Therefore, this type of compound is the result of coupling with the oxidant of the developing agent,
In addition to the dye portion that is already present or the dye portion derived from the precursor thereof, a diffusion resistant dye that also has a newly formed dye portion is produced (addition type).

Type II A compound that does not decolor the dye portion or its precursor portion that it has in advance by coupling with the oxidation product of the color developing agent, and does not form a new dye portion, and is diffusion resistant.

A compound that resists diffusion by cross-oxidation with the oxidant of type III color developing agent.

Each of the above types will be described in more detail.

Examples of the compound of type I-1 include compounds represented by the following general formula [I
-1].

General formula [I-1] A ₁ -Link ₁ -B _{1 In the} formula, A ₁ is coupled with an oxidized product of a developing agent to form Link-B ₁
It is an organic residue capable of forming a coupling dye while releasing a portion depending on the amount of the oxidized form of the developing agent.
nk ₁ group bonded to A ₁ and B _1, B ₁ represents an organic residue.

Specific examples of A ₁ include phenols, naphthols, 5-pyrazolones, pyrazolotriazoles,
Pyrazolotetrazoles, pyrazolobenzimidazoles, indazolones, acylacetanilides and the like can be mentioned.

As Link ₁ , for example, -N = N-, -O-, -S-,
-SO ₂ , And so on. here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl, imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl, triazolyl, benztriazolyl,
There are urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl, tetrazolyl and the like.

When Link ₁ is a chromophore such as -N = N-, B ₁ is preferably, for example, an aryl group or a heterocyclic group, and Li
When nk ₁ is not a chromophore, it is preferably a dye (eg, azo, anthraquinone, azomethine, indophenol, indoaniline, etc.) residue or a precursor thereof.

The compound represented by the general formula [I-1] having the above constitution may be a dye or its precursor as a whole B ₁ or A ₁ -Link ₁ -B ₁ .

The compound represented by the general formula [I-1] is imparted with a property of slightly diffusing during the development processing step, and when B ₁ is a dye or a precursor thereof, the dye generated due to these flows out of the system. In order to make the dye formed by coupling resistant to diffusion, an alkali-soluble group such as a carboxyl group, a sulfo group, a hydroxyl group and a sulfamoyl group, and a group such as an alkyl group that reduces diffusibility are appropriately introduced. The diffusivity before and after the reaction may be balanced.

Examples of the compound of type I-2 include compounds represented by the following general formula [I
-2].

In the general formula [I-2] D ₁ -A ₂ , D ₁ represents a dye moiety or a precursor moiety thereof, and A ₂ is an organic residue capable of forming a dye by coupling with an oxidized product of a developing agent. However, D ₁ does not separate from A ₂ upon coupling.

Specific examples of A ₂ include those shown above as specific examples of A ₁ .

Examples of D ₁ include the dye residues and the precursors thereof mentioned above as examples of B ₁ . A ₂ may have a group at the coupling position which can be released upon coupling. The releasable group may be a dye or its precursor, but it is not essential that it be a dye or its precursor.

Further, the compound represented by the general formula [I-2] is imparted with the property of slightly diffusing during the development processing, and
In order to prevent diffusion of the dye formed as a result of coupling of the compound of the above-mentioned with the oxidation product of the developing agent, for example, an alkali-soluble group such as a carboxyl group, a sulfo group, a hydroxyl group, a sulfamoyl group and a diffusibility such as an alkyl group. It is sufficient to appropriately introduce a group that reduces the diffusivity to balance the diffusivity before and after the reaction.

For example, an alkali-soluble group capable of leaving upon coupling or a group containing an alkali-soluble group may be bound to the coupling position of A ₂ in advance.

As the compound of type II, for example, the following general formula [II-
1] are mentioned.

In the general formula [II-1] W-D ₂ formula, D ₂ is D ₁ synonymous in the general formula (I-2),
The same thing is illustrated.

W represents a compound residue that couples with an oxidized product of a developing agent, but does not form a dye due to the coupling.

Examples of W include a reaction for transferring to a dye after coupling to a coupling position of a coupler residue such as 5-pyrazolone nucleus and β-diketomethylene group (for example, oxidation reaction,
Examples thereof include those in which a group that does not cause an elimination reaction (for example, an alkyl group such as a methyl group and a butyl group) are substituted, and bisalkylcarbamoyl-aryloxymethane-based or bisalkylcarbamoyl-arylthiomethane-based compound residues.

In the general formula [II-1], D ₂ may be present at the coupling position of W as a part of the group that does not cause the reaction of transferring to the dye, or may be bound to a position other than the coupling position. Good.

As the compound of type III, for example, the following general formula [III-
1] are included.

In the general formula [III-1] FUN-D ₃ formula, D ₃ has the same meaning as D ₁ in the general formula (I-2), those similar are exemplified.

FUN reacts with the oxidant of the color developing agent and reacts with the general formula [III-
Examples of the organic group having a function of making the compound represented by 1] resistant to diffusion include a group having a hydroquinone nucleus and a group having a catechol nucleus.

Next, the diffusion resistant positive compound will be described in detail.

Here, decoloring and discoloring are synonymous with those in the small diffusible positive compound.

In the area where a color image is generated by the reaction between the oxidized product of the color developing agent and the diffusion resistant coupler, the diffusion resistant positive compound also reacts with the oxidized product of the developing agent to produce a compound that is colorless or dissolves out of the system. This characteristic is expressed. Further, in the area where a color image is not produced by the diffusion resistant coupler, the diffusion resistant positive compound remains unreacted or discolored. As a result, the antidiffusive coupler and the antidiffusive positive compound form a color image in an inverse relationship, that is, when the former is a negative image, the latter forms a positive image. Moreover, the diffusion-resistant positive compound reaches the layer containing the diffusion-resistant positive compound while the oxidized developing agent diffuses from the layer containing the diffusion-resistant coupler, resulting in an unsharp image, that is, an unsharp image. A sharp positive image will be formed.

As the diffusion resistant positive compound, for example, the following general formula [A
-1].

General formula [A-1] A ₃ -Link-B _{3 In the} formula, A ₃ reacts with the oxidized form of the developing agent to make the Link-B ₃ part colorless or capable of being eluted depending on the amount of the oxidized form of the developing agent. An organic residue, Link is a group that connects A ₃ and B ₃ ,
B ₃ represents an organic residue.

Further, the compound represented by the general formula [A-1] is a compound having color resistance or discoloration which is resistant to diffusion in the photographic material during the development process, and is generated due to A ₃ and Link-B ₃ after the reaction. In the case where the object is a compound exhibiting an unsuitable hue for image formation,
After the reaction, the product is provided with a substituent having a balanced hydrophilicity or lipophilicity so that the product is eluted out of the system constituting the hue of the photographic material.

A ₃ in the general formula [A-1] is, for example, a cross-oxidation reaction with a residue of a coupler which produces a colored or colorless product by a coupling reaction with an oxidized product of a color developing agent or an oxidized product of a developing agent. Ingredients are included.

Specific examples of the former include, for example, phenols, naphthols, 5-pyrazolones, pyrazolotriazoles,
Pyrazolobenzimidazoles, indazolones, acylacetanilides, RCOCH ₃ (R is alkyl,
Aryl, heterocyclic group) (Z is a group of atoms that completes, for example, a 5- to 8-membered saturated or unsaturated alicyclic ring or heterocyclic ring, and R'represents an aryl residue.).

Specific examples of the latter include, for example, an alkali after being oxidized.
B-SO as Link-B by cleavage₂NH Emitting fe
Knols, naphthols, indanones, indoles
After being oxidized, the residue of is converted to Link-B by alkali cleavage.
B-O , B-S , B-SO₂ Hyde that emits
Residues of roquinone, which undergo intramolecular ring closure after being oxidized
Received, B-SO as Link-B₂ Releasing phenol
Class (For details, U.S. Patents 3,443,939 and 3,443,940,
No. 3,443,941. ) Residue
It

As the Link, for example, -N = N-, -O-, -S-,-
_{SO 2 -, - NH-SO} 2 -, - SO 2 -NH-, -CH = and the like.

here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl, imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl, triazolyl, benztriazolyl,
There are urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl, tetrazolyl and the like. R is alkyl, aryl or the like which may have a substituent.

As B, when Link is a chromophore such as -N = N-, -CH =, it is, for example, an aryl group or a heterocyclic group, and preferably an organic residue having an auxochrome or a dye residue. It may be. When Link is not a chromophore, it is preferably a dye (eg, azo, anthraquinone, azomethine, indophenol, indoaniline, etc.) residue or a precursor thereof. With such a constitution, the compound represented by the general formula [A-1] may be a compound which is colored or discolored as the B ₃ portion or A ₃ -Link-B _{3 as a} whole.

To give the compound represented by the general formula [A-1] the property of not diffusing during the development processing and the diffusibility of the undesirable product after the reaction for eluting out of the system, for example, a carboxyl group is used. , An alkali-soluble group such as a sulfo group, a hydroxyl group, and a sulfamoyl group, and a group such as an alkyl group that reduces diffusibility may be appropriately introduced to balance the diffusivity before and after the reaction.

When the compounds of the present invention are classified according to their properties, for example, the following classifications can be mentioned.

CLASSI: Coloring dye forming type In the compounds belonging to this class, the A ₃ portion of the general formula [A-1] is a coupler residue and the Link portion is bonded to the active site of the coupler. However, when the A ₃ portion is a phenol residue or a naphthol residue and Link is —NHSO ₂ — (a nitrogen atom is bonded to the Coup part), it may be adjacent to the active site. Further, it has a ballast group, for example, an alkyl group having 17 or more carbon atoms so as to have diffusion resistance in the photographic material. When the color-forming dye formed by coupling the A ₃ portion with the oxidant of the color developing agent is unsuitable for image formation, the color-forming dye may be washed out of the system during the processing, and an alkali-soluble group may be added to the A ₃ portion. It is preferable to use a compound having an alkali-soluble group as a color developing agent.

Also, B ₃ parts dye or, it is preferable that B ₃ portions to B ₃ portion after the reaction in the case of forming the precursor from flowing out of the system has an alkali-soluble group.

Compounds belonging to this class, A ₃ moieties in the exposed portion to make the negative color dye image is washed away from the system, if B ₃ moiety is a dye, the B ₃ moiety also A ₃ after withdrawal from subsystem Since it is washed away to the outside, a positive image is formed by the compound represented by the general formula [A-1] which remains in the unexposed area or the compound whose color has changed. In addition, the periphery of the positive image formed by this compound forms an unsharp positive image in the layer during the development process due to the reaction with the diffused oxidized developing agent. Further, among these types, the following two types are preferable.

(Type A): Colored coupler type general formula [A-2] Coup-Link ² -Ar Coup-of the general formula [A-2] is preferably a coupler residue having an alkali-soluble group, and a dye produced by a color development reaction. Elutes out of the photographic material system.

Ar is preferably an aryl group which may have a substituent, for example, a benzene type or naphthalene type, and a heterocyclic group which may have a substituent, for example, isoxazole, and a compound of the general formula [A-2]. Has a diffusion preventing group so as not to diffuse in the photographic material, and it is particularly preferable to have it in the Ar portion. Link
² is a chromophore, preferably -N = N- or -CH =.
Some of these compounds are already colored couplers,
For example, U.S. Pat.Nos. 2,449,969, 2,688,538 and 2,70
No. 6,684, No. 2,808,329, No. 3,005,712, Japanese Patent Publication No.44-32
It is known as No. 461.

However, the present invention and these prior arts are completely different in the use method of the compound and the purpose of use, and the effects obtained are completely different. That is, in the above-mentioned prior art, since the hue generated by the Coup portion or coupler portion represented by the general formula [A-2] is the main absorption for image formation, the dye formed from this portion does not move in principle. The hue of the compound represented by the general formula [A-2] is a secondary absorption portion different from the above main absorption wavelength region. In the present invention, it is essential that the dye generated from the Coup portion is taken out of the system, and the hue of the compound represented by the general formula [A-2] is the same as the main absorption of the image forming layer. That is, the light-sensitive wavelength range of the silver halide layer combined with the compound of the formula [A-2] is a complementary color of the compound hue in the case of a conventional negative photographic material. Specifically, for example, with respect to a green-sensitive negative layer, prior art colored couplers use a yellow compound in this layer, whereas the present invention uses a magenta compound.

(Type B): Active site substitution type general formula [A-3] Coup-Link ^3- Dye Coup is the same as general formula [A-2]. Link ³ has the same meaning as Link of the general formula [A-1], and similar ones are exemplified, and preferably, a group which produces alkali solubility after the coupling reaction, for example, —O—, —SO ₂ —NH—, -NHSO ₂ - such as is desirable. Dye represents a dye moiety or its precursor moiety and preferably has an alkali-soluble group, but Link ³
Not required depending on the type of. Compounds belonging to this class are disclosed in U.S. Pat. Nos. 3,227,550 and 3,476,563, but these prior arts have completely different usages similar to Type A, and the concept of the present invention is included. It is not. That is, part of it is used for color correction similar to Type A color coupler, and Dye that is diffused and transferred and flows out.
This is clearly different from the aspect of the present invention when the parts are used for the image.

Next, a compound group that does not produce a color image after the color reaction is described.

CLASSII: colorless coupling body forming type Compounds belonging to this class react in the same manner as the compound of CLASSI in the A ₃ portion of the general formula [A-1], but since the reaction product is colorless, the layer after the coupling reaction is formed. It may remain inside.

(Type C): Weiss coupler type general formula [A-4] Wcoup-Link ^4- Dye Wcoup is, for example, R ₂ COCH _2- (R ₂ represents an alkyl, aryl or heterocyclic group.) (Z is an atomic group that completes a 5- to 8-membered alicyclic ring, condensed ring or heterocyclic ring, and R ₃ represents an aryl residue). The Wcoup part is preferably a diffusion preventing group such as a carbon number of 17 in order to make the compound represented by the general formula [A-4] resistant to diffusion.
It has the above groups.

Link ⁴ is -O -, - S- or -SO ₂ - shows a.

Dye is preferably a dye having an alkali-soluble group, or
After reaction with the precursor residue, Link ^4- Dye flows out of the layer.

CLASS III: Redox reaction type Compounds belonging to this class do not undergo the coupling reaction as in CLASS I or II. Instead, it reacts with an oxidized product of a developing agent to form a quinone, a quinimide, etc., but this product releases a dye only when it reacts with an alkali in a developing solution or an intramolecular ring closure reaction.

(Type D): DRR compound type General formula [A-5] FUN-Link ⁵ -Dye FUN represents a redox mother nucleus, and is preferably 2-, 3- or 4-phenol, 4-α-naphthol, 1-β-. Naphthol, 2-hydroquinone, 3-indole, 4-pyrazolone-5 residue, Link ⁵ is -NHSO _2- (nitrogen atom is bonded to FUN part), -O-, -SO _2- , -S-, etc. And Dye is a dye or its precursor residue, and preferably has an alkali-soluble group. In addition, the general formula [A-5]
The FUN portion preferably has a diffusion-preventing group so that the compound of (1) does not move in the layer.

The above-mentioned positive compounds are synthesized according to a general synthetic method, but there are roughly two main routes. That is, one is a method in which a dye moiety is pre-synthesized and finally the dye moiety is combined with another moiety having an amino group as sulfochloride or acid chloride by a suitable acid chloride agent such as phosphorus oxychloride or thionyl chloride. The other synthetic method is to obtain a dye moiety by diazo coupling in the final step.

In the case of a dye precursor, it can be obtained by, for example, acylating the auxochrome after forming the dye.

The positive compound is contained in a silver halide emulsion layer containing the above-mentioned diffusion-resistant coupler and / or in a photographic constituent layer separate from the silver halide emulsion layer.

The other photographic constituent layer need not be adjacent to the silver halide emulsion layer, but is preferably adjacent to it.
Further, when the positive compound itself has a main absorption in the main light-sensitive wavelength region of the emulsion layer, it is necessary to position it on the side opposite to the light incident side at the time of exposure with respect to the silver halide emulsion layer to lower the sensitivity. It is preferable for preventing Further, the other photographic constituent layer may be a light-sensitive silver halide emulsion layer having the same color sensitivity as that of the light-sensitive silver halide emulsion layer or a non-light-sensitive layer.

Further, the diffusion resistant positive compound is preferably contained in a non-photosensitive manner.

When the positive compound is contained in the non-photosensitive layer, the positive compound reacts with the oxidized product of the developing agent generated by the development of the photosensitive silver halide emulsion layer, which has diffused into the non-photosensitive layer. As a result, an unsharp positive image is formed.

The amount of the positive compound used is preferably 0.01 to 1.00 mol, and particularly preferably 0.05 to 0.60 mol, per mol of the diffusion resistant coupler used in combination with the compound. Further, as a method of adding the same, a method similar to that of the diffusion resistant coupler described later can be used.

In order to exert the effects of the present invention most effectively, it is most preferable that the diffusion-resistant coupler and the compound of the present invention coexist in the light-sensitive silver halide emulsion layer.

The amount of the compound of the present invention used is preferably 0.01 to 1.00 mol, and more preferably 0.05 to 0.60 mol, per mol of the diffusion resistant coupler used in combination with the compound. Further, as a method of adding the same, a method similar to that of the diffusion resistant coupler described later can be used.

Next, as a compound (hereinafter, referred to as DP 'scavenger) that supplements the oxidized product of the color developing agent according to the present invention but does not contribute to image formation, there are the following compounds.

Any compound that effectively scavenges the oxidized product of the color developing agent may be used, but the compounds represented by the following general formulas [VI] to (XX) are preferable.

General formula [VI] In the formula, n represents 2 or 3. R ₄ represents a hydrogen atom, an alkyl group, an alkenyl group or an acyl group, and l, m
Represents 0 or 1, R ₅ represents a halogen atom, an aliphatic group or an aromatic group, R ₆ represents an aliphatic group, an aromatic group, a carboxyl group or a salt thereof, a sulfo group or a salt thereof, a carboalkoxy group, −COR ₇ , −SO ₂ R ₈ −, −CONHR
It represents a ₉ or -NHCOR _10, wherein R _7, R _8, R ₉ and R ₁₀ each represents an aliphatic group or an aromatic group. More specifically, the aliphatic group represented by R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may have a substituent, and examples thereof include an alkyl group and an alkenyl group. The alkyl group preferably has 1 to 20 carbon atoms (more preferably 1 to 18).
And a linear or branched alkyl group such as methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, dodecyl group and octadecyl group. The alkenyl group is preferably an alkenyl group having 3 to 20 carbon atoms (more preferably 3 to 18), such as an allyl group, a butenyl group, an octenyl group, a dodecenyl group, an oleyl group. The aromatic group represented by R ^{5 to} R ¹⁰ may also have a substituent, and examples thereof include an aryl group such as a phenyl group and a naphthyl group.

Examples of the substituent that the aliphatic group and aromatic group represented by R ^{5 to} R ¹⁰ may have include a halogen atom, a hydroxyl group, a sulfo group, a carboxyl group, a cyano group, an amino group,
Alkyl group, alkenyl group, aryl group, alkoxy group, aryloxy group, acyl group, acyloxy group, acylamino group, alkylamino group, arylamino group, alkoxycarbonyl group, aryloxycarbonyl group,
Examples thereof include a carbamoyl group, an alkylcarbamoyl group and an aryloxycarbamoyl group.

Examples of the salt of the carboxyl group or sulfo group represented by R ⁶ include alkali metal salts (for example, sodium salt, potassium salt and the like), ammonium salt and the like.

The polyhydroxybenzene compound represented by the general formula [VI] is represented by U.S. Patent Nos. 2,360,290, 2,701,197 and 2,72.
Compounds that can be obtained according to the synthetic method described in No. 8,659, No. 2,732,300 or the Beilstein series and are commercially available as antioxidants can also be used.

General formula (VII) In the formula, A represents —CO— or —SO ₂ —, R ¹¹ and R ¹² each represent an alkyl group, an aryl group or a heterocyclic group, Z represents a hydrogen atom or an alkali decomposable precursor group, and m represents It represents 1 or 2, n is 0 or 1, at least one of -NH-a-R ¹² and -OZ- is in the ortho or para position relative to the -NHSO ₂ R ^11. R ¹³ is a halogen atom, cyano group, nitro group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylthio group, arylthio group, heterocyclic thio group, carbamoyl group, alkoxycarbonyl group,
It represents an acyl group, an alkoxycarbonylamino group, a ureido group, an amino group, a sulfinyl group, an acylamide group, a sulfonyl group or a sulfonamide group. Q represents an atomic group forming a ring, and this ring may not be present.

More specifically, the alkyl groups represented by R ¹¹ and R ¹² may be linear or branched and preferably have 1 to 30 carbon atoms, and include, for example, methyl, ethyl, isopropyl, butyl,
Examples include octyl, dodecyl and hexadecyl.

The aryl group represented by R ¹¹ and R ¹² preferably has 6 to 30 carbon atoms, and examples thereof include phenyl and naphthyl.

The heterocyclic group represented by R ¹¹ and R ¹² preferably has 5 to 30 carbon atoms and has at least one of O and N as a hetero atom, and examples thereof include pyridyl and morpholino.

These groups represented by R ¹¹ and R ¹² may have a substituent, and examples of the substituent include the aliphatic groups and aromatic groups represented by R ^{5 to} R ¹⁰ in the general formula [VI]. Group.

The ring represented by Q represents an atomic group necessary for forming a naphthalene ring together with a benzene ring.

In the alkali-decomposable precursor group represented by Z, the hydrogen atom of the hydroxyl group is replaced with a blocking group which is removed upon contact with alkali. Typical blocking groups can be removed by hydrolysis or intermolecular nucleophilic substitution. Typical groups that can be removed by hydrolysis are acyl groups such as aliphatic and aromatic carbonyl and sulfonyl groups (eg alkylsulfonyl, arylsulfonyl). Typical groups that can be removed by intermolecular nucleophilic substitution are described in US Pat. No. 4,310,612.
No. specification.

The compound represented by the general formula [VII] can be synthesized by a known method. Regarding the synthesizing method, JP-A-55-72158
No. 59-5247, 59-192246, 59-192247, 5
9-195238, 59-195239, 59-202465, 59-204
039, 59-204040, 59-206833, 59-212837
No. 59-220733, 59-222836, 60-108843,
Reference can be made to Nos. 60-118835 and 60-118836.

Next, a compound that undergoes a coupling reaction with the oxidant of a color developing agent but does not form a dye (hereinafter referred to as a non-color coupler)
Included as DP 'scavenger.

(1) Coupler that is dissolved in the processing solution due to the water-solubility of the dye formed by coupling with the oxidant of the color developing agent (2) Coupler that is coupled with the oxidant of the color developing agent, but remains in the leuco form (3) A coupler produced by coupling with an oxidized product of a color-developing agent to give a substantially colorless product having no noticeable visible absorption, in the non-color-forming coupler according to the present invention, the above-mentioned (1) The compound to which it belongs can be represented by the following general formula [VIII].

General formula [I] Wherein, COUP ₁ represents a coupler mother nucleus having a coupling site (asterisk *), BALL is bonded to the coupling site of COUP _1, COUP ₁ upon reaction with an oxidation product of the COUP ₁ with a color developing agent Is a stable group having a size and a shape that makes the compound of the general formula [I] resistant to diffusion. The SOL is a solubilizing group, attached to the non-coupling position of COUP _1, the photosensitive material in a color developing time or after the coupling product produced by coupling with an oxidation product of COUP ₁ with a color developing agent It is a group that imparts mobility that flows out of the system from the inside.

The coupler mother nucleus represented by COUP ₁ is known or used in the art to form a reaction product having a hue or a colorless color by a coupling reaction with an oxidant of a color developing agent. Any coupler mother nucleus can be mentioned. For example, yellow dye-forming coupler nuclei are acylacetanilides, such as acetoacetanilides and benzoylacetanilides, magenta dye-forming coupler nuclei are pyrazolones,
Pyrazolotriazoles, pyrazolobenzimidazoles and indazolones, and cyan dye-forming coupler nuclei include phenols and naphthols.

BALL is a stable group having a molecular size and shape that makes the compound of the general formula [VIII] resistant to diffusion.
The useful group represented by BALL is, but not limited to, 8 as long as it imparts diffusion resistance to the compound of I].
Alkyl groups, aryl groups and heterocyclic groups having ˜32 carbon atoms are mentioned. These groups represent those which are unsubstituted or substituted, but as a substituent, the compound of the general formula [VIII] increases the diffusion resistance and the general formula [VIII]
It is a group that increases the diffusivity of BALL after the compound is removed by changing the reactivity of the compound or by causing a coupling reaction. Further, BALL is preferably bound to the coupling site of COUP ₁ via a linking group. Representative linking groups, oxy (-O-), thio (-S-), carbonyloxy (-OCO-), a sulfonyloxy (-OSO ₂ -), amide (-NHCO-), sulfonamide (- NHSO ₂ −) and the like.

Preferred BALL is an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, an arylthio group, a heterocyclic thio group, an acyloxy group, an alkylsulfonyloxy group having an alkyl group and / or an aryl group having a total of 8 to 32 carbon atoms. , An arylsulfonyloxy group, an acylamino group, an alkylsulfonamide group, an arylsulfonamide group, or a nitrogen-containing heterocyclic group (pyrrole,
Pyrazole, imidazole, triazole, tetrazole, indole, indazole, benzimidazole,
Benzotriazole, phthalimide, succinimide,
2,4-imidazolidinedione, 2,4-oxazolidinedione, 2,4-thiazolidinedione, triazolidine-3,5-dione and the like).

The solubilizing group represented by SOL is a group that imparts mobility to the coupling product generated by the coupling reaction so that the coupling product can flow out of the photosensitive material system, such as an ionizable hydroxyl group, a carboxyl group, a sulfo group and an amino group. There are sulfonyl groups and their ionizable salts, as well as ester groups, ether groups and the like.

It is also preferable that one or more of these groups be bonded to the uncoupling site of COUP ₁ , or an alkyl group having an appropriate size, for example, 1 to 10 carbon atoms, 6
A solubilizing group such that an aryl group having 12 to 12 carbon atoms has one or more of the above ionizable groups is COUP.
Some are bound to the non-coupling site of ₁ advantageously used.

Further, a compound that is bonded to the non-coupling site of the COUP ₁ via a linking group is also preferable. Representative linking groups include oxy (-O-), thio (-S-), carbonyl group,
Carbonyloxy group, oxycarbonyl group, amino group,
Examples thereof include a carbamoyl group, an aminocarbonyl group, a ureido group, a sulfamoyl group and an aminosulfonyl group.

Although useful solubilizing groups are mentioned above, particularly preferred solubilizing groups are carboxyl groups directly bonded to the uncoupling site of COUP ₁ , sulfo groups, or ionizable salts thereof,
Or directly bound to the uncoupling site of COUP ₁ ,
Alternatively, an alkyl group having 1 to 10 carbon atoms or 6 to 12 carbon atoms containing one or more carboxy groups, sulfo groups or their ionizable salts bonded via an amino group or a carbonyl group. Aryl groups having

Further, the compounds according to the present invention capable of forming yellow, magenta and cyan dyes preferably used in the present invention can be represented by the following general formulas [IX] to [XIV].

[Yellow pigment forming compound]

General formula [IX] In the formula, R ¹⁴ is an aryl group (eg phenyl group) or an alkyl group (particularly a tertiary alkyl group, eg t-butyl group)
R ¹⁵ is the above-mentioned stabilizing group (BALL), R ¹⁶ is the above-mentioned solubilizing group (SOL), R ¹⁷ is a hydrogen atom or a halogen atom, an alkyl group or an alkoxy group, and n
+ M = 5 (where n≈0, m≈0, and n, m
When two or more, each may be the same or different).

[Magenta dye-forming compound]

In formulas [X], [XI] and [XII], R ¹⁵ has the same meaning as R ¹⁵ in formula [IX], R ¹⁷ represents a solubilizing group (SOL), and R ¹⁸ represents a hydrogen atom. , A halogen atom, an alkyl group, an alkoxy group or an amino group, and p ≦
5 (however, when p≈0 and p is 2 or more, they may be the same or different). R ¹⁹ and R
^{One of 20} represents the solubilizing group (SOL) described above, and the other represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an amino group.

R ²¹ and R ²² are R ¹⁹ and R ²⁰ in the general formula [XI].
Is synonymous with.

[Cyan dye-forming compound]

In the formulas [XIII] and [XIV], R ¹⁵ is represented by the formula [I
X] has the same meaning as R ¹⁵ and at least one of R ²³ and R ²⁴ represents the above-mentioned solubilizing group (SOL), and the rest represent a hydrogen atom or a halogen atom, an alkyl group, an alkoxy group or an alkylamido group. , Q ≦ 3 (where q≈0), and R ²⁵ represents the solubilizing group (SOL) described above.

Unless otherwise specified above, alkyl, alkoxy, and alkylamido groups each contain 1-8 carbon atoms, aryl groups contain 6-10 carbon atoms, and amino groups are primary, Includes secondary and tertiary amino groups. These substituents and stable groups (BALL) are halogen atom, hydroxy, carboxy, amino, amido, carbamoyl, sulfamoyl, sulfonamide,
Also included are those further substituted with groups such as alkyl, alkoxy and aryl.

In the color-free coupler of the present invention, the compound belonging to the above (2) can be represented by the following general formula [XV].

General formula (XV) In the formula, COUP ₂ has the same meaning as COUP _{1 in} formula [VIII], and R
²⁶ binds to the coupling site of COUP ₂ and has the general formula [XV]
Represents a group which cannot be eliminated by the reaction between the coupler of (4) and the oxidation product of the color developing agent.

The coupler mother nucleus represented by COUP ₂ has the general formula [VII
Examples of the group represented by R ²⁶ include the mother nucleus of the coupler described in I] include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group and a cyano group.

The compound represented by the general formula [XV] is a compound represented by COUP ₂ at the non-coupling site of the mother nucleus of the coupler through a connecting group.
Those which are resistant to diffusion with alkyl groups, aryl groups and heterocyclic groups having .about.32 carbon atoms are preferred. Representative linking groups include oxy (-O-), thio (-S)
-), Carbonyl group, carbonyloxy group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group, sulfamoyl group, and aminosulfonyl group.

In the colorless coupler of the present invention, the compound belonging to the above (3) can be represented by the following general formula [XVI].

General formula [XVI] In the formula, COUP ₃ represents a coupler mother nucleus that gives a substantially colorless product by a coupling reaction with an oxidized product of the color developing agent, and R ²⁷ is bonded to the coupling site of COUP ₃ to form a color developing agent. Represents a group capable of leaving from COUP ₃ by a coupling reaction with the oxidant of.

Preferable releasable groups include halogen atom, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, heterocyclic thio group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, nitrogen-containing heterocyclic group, etc. Is mentioned.

In the colorless coupler represented by the general formula [XVI],
More preferable ones can be represented by the general formulas [XVII] to [XX].

General formula (XVII) In the formula, R ²⁷ has the same meaning as R ²⁷ in formula [XVI],
R ²⁸ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an alkoxy group, an acyloxy group or a heterocyclic group, and X represents an oxygen atom or = N—R ²⁹ . R ²⁹ represents an alkyl group, an aryl group, a hydroxy group, an alkoxy group or a sulfonyl group. Z represents a 5- to 7-membered carbon number (for example, indanone, cyclopentanone, cyclohexanone, etc.) or a nonmetallic atomic group necessary for forming a heterocycle (for example, piperidone, pyrrolidone, hydrocarbostyril, etc.).

General formula (XVIII) Wherein, R ^27, R ²⁸ and X have the same meanings as R ^27, R ²⁸ and X in the general formula [XVII], R ³⁰ is an alkyl group, an aryl group, a heterocyclic group, a cyano group, hydroxy group, an alkoxy group , An aryloxy group, a heterocyclic oxy group, an alkylamino group, a dialkylamino group, or an anilino group.

General formula [XIX] In the formula, R ²⁷ has the same meaning as R ²⁷ in formula [XVI]
³¹ and R ³² may be the same or different, and are an alkoxycarbonyl group, a carbamoyl group, an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, an ammoniumyl group or Represents A represents a group of non-metal atoms necessary for forming a 5- to 7-membered heterocycle (eg, phthalimide, triazole, tetrazole, etc.) with a nitrogen atom.

General formula [XX] Wherein R ²⁷ has the same meaning as R ²⁷ in the general formula [XVI], R ³³ is an alkyl group, an aryl group, an anilino group, an alkylamino group or an alkoxy group,, B is an oxygen atom, a sulfur atom or a nitrogen atom Represent.

Colorless couplers according to the present invention are disclosed in JP-A-59-113440 and JP-A-5-113440.
9-171955, 52-82423, British Patents 914,145, 1,284,649, U.S. Patents 2,742,832, 3,227,55.
No. 0, No. 3,928,041, No. 3,958,993, No. 3,961,9
No. 59, No. 4,046,574, No. 4,052,213, No. 4,149,
It can be synthesized by the method described in No. 886 or the like.

The general formula [VI] used in the present invention from the general formula [X
Specific compound examples up to X] will be shown, but the present invention is not limited thereto.

Among the compounds represented by the general formulas [VI] to [XX] used in the present invention, hydroquinone derivatives, gallic acid esters / gallic acid amides and general formula [XIV] are preferable.

For the purpose of the present invention, it is most preferable that the compounds represented by the above general formulas [VI] to [XX] according to the present invention are directly added to the silver halide emulsion layer to be contained. At the same time, it may be added to a non-photosensitive layer such as an intermediate layer, a protective layer, a yellow filter layer and an antihalation layer. Also, the content of the above compound is 0 per mol of silver halide.
The range of 01 g to 100 g is preferable, and the range of 0.05 g to 50 g is particularly preferable, but the addition amount is appropriately selected depending on the type of silver halide, the type of compound and the like. When applied to a layer containing no silver halide such as an intermediate layer, a protective layer, a yellow filter layer and an antihalation layer, 1 g of gelatin is used.
Within the range of 0.01g to 50g, more preferably 0.05g
Good results can be obtained by applying an aqueous gelatin solution containing the compound according to the present invention in the range of 1 to 10 g.

The DP 'scavenger of the present invention can be incorporated into a silver halide emulsion layer by known methods, such as U.S. Pat.
The method described in No. 7 is used. For example, phthalic acid alkyl ester (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid ester (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate),
A high-boiling organic solvent such as a citric acid ester (eg, tributyl acetylcitrate), a benzoic acid ester (eg, octyl benzoate), an alkylamide (eg, diethyllaurylamide), or a boiling point of about 30 ° C. to 150 ° C.
Low boiling point organic solvent at ℃, for example, lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl kent,
After being dissolved in β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid.
The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

When the DP 'scavenger has an acid group such as carboxylic acid or sulfonic acid, it is added to the alkaline aqueous solution and then introduced into the hydrophilic colloid.

The silver halide emulsion used in the present invention includes a common silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride as silver halide. Any of those used in can be used, especially silver bromide,
Silver iodobromide and silver chloroiodobromide are preferred.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The conversion may be used at any step in the formation of AgX to change the halogen composition of the grains.

A known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of silver halide grains.

The silver halide grains are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming and / or growing the grain). Metal ions are added using at least one selected from the group consisting of complex salts)
Alternatively, these metal elements can be contained on the grain surface, and reduction sensitizing nuclei can be imparted to the inside of the grain and / or the grain surface by placing in a suitable reducing atmosphere.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research Disclosure (RD)
It can be carried out based on the method described in Item 17643, Item II.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grain may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these particles, any ratio of {100} faces to {111} faces can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The size of silver halide grains may be 0.05 to 30 μm, preferably 0.1 to 20 μm.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. When divided by the average grain size, the value is 0.20 or less, where the grain size is the diameter in the case of spherical silver halide and the projected image in the case of grains other than spherical. The diameter when converted to a circular image of the same area is shown).
Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
The noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a steryl dye and a hemioxanol dye are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye.

Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and / or after the completion of chemical ripening, before coating a silver halide emulsion, Compounds known in the art as antifoggants or stabilizers can be added.

As the binder (or protective colloid) of the silver halide emulsion, it is advantageous to use gelatin, but gelatin derivatives, graft polymers of gelatin and other macromolecules, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, a hydrophilic colloid such as a synthetic hydrophilic polymer substance such as a copolymer can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners which crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in an amount such that the light-sensitive material can be hardened to the extent that it is not necessary to add the hardener during processing, but it is also possible to add the hardener to the processing liquid.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5 -Triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol and the like), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine and the like), mucohalogen acids (mucochloric acid, Mucophenoxycyclo acid, etc.) can be used alone or in combination.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of enhancing flexibility. Preferred plasticizers are the compounds described in A of RD17643, section XII.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color development processing, the emulsion layer of the light-sensitive material forms a dye by a coupling reaction with an oxidant of an aromatic primary amine developer (eg, p-phenylenediamine derivative, aminophenol derivative). A coupler is used. The dye-forming couplers are usually selected for each emulsion layer so that a dye that absorbs the light in the light-sensitive spectrum of the emulsion layer is formed, and in the blue-sensitive emulsion layer, the yellow dye-forming coupler is green. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye. Either of two equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidation product of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Among these, a coupler which releases a development inhibitor with development and improves the sharpness of images and the graininess of images is called a DIR coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and the DIR compound used are those in which the inhibitor is directly bonded to the coupling position, and those in which the inhibitor is bonded to the coupling position via a divalent group and which are separated by the coupling reaction. Those which are bound so as to release the inhibitor by the intermolecular nucleophilic reaction, the intramolecular electron transfer reaction or the like (referred to as a timing DIR coupler and a timing DIR compound). Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color forming couplers that can be used include, for example, U.S. Pat.
No. 7, No. 3,265,506, No. 3,408,194, No. 3,551,1
No. 55, No. 3,582,322, No. 3,725,072, No. 3,891,
445, West German patent 1,547,868, West German published application 2,219,917
No. 2,261,361, No. 2,414,006, British Patent No. 1,425,
No. 020, Japanese Patent Publication No. 51-10783, JP-A Nos. 47-26133 and 48-73.
No. 147, No. 50-6341, No. 50-87650, No. 50-123342,
50-130442, 51-21827, 51-102636, 52-8
2424, 52-115219, and 58-95346.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, indazolone couplers and the like can be used. Specific examples of magenta color couplers that can be used include, for example, U.S. Pat.Nos. 2,600,788 and 2,983,6.
No. 08, No. 3,062,653, No. 3,127,269, No. 3,311,
No. 476, No. 3,419,391, No. 3,519,429, No. 3,55
No. 8,319, No. 3,582,322, No. 3,615,506, No. 3,8
34,908, 3,891,445, West German Patent 1,810,4
64, West German patent application (OLS) 2,408,665, 2,417,945
No. 2,418,959, 2,424,467, Japanese Patent Publication No. 40-6031
No. 4, JP-A-49-74027, 49-74028, 49-129538
50, 50-60233, 50-159336, 51-20826, 5
1-26541, 52-42121, 52-58922, 53-55122
And Japanese Patent Application No. 55-110943.

As the cyan dye forming coupler, a phenol or naphthol type coupler is generally used. Specific examples of cyan color forming couplers that can be used include, for example, U.S. Pat.
No. 0, No. 2,474,293, No. 2,801,171, No. 2,895,8
No. 26, No. 3,476,563, No. 3,737,326, No. 3,758,
No. 308, No. 3,893,044, JP-A-47-37425,
50-10135, 50-25228, 50-112038, 50-1174
No. 22, No. 50-130441, etc.,
The couplers described in JP-A-58-98731 are preferred.

Of the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, optical brighteners, etc. that do not need to be adsorbed on the silver halide crystal surface, hydrophobic compounds are solid. Various methods such as a dispersion method, a latex dispersion method and an oil-in-water type emulsion dispersion method can be used, which can be appropriately selected according to the chemical structure of the hydrophobic compound such as a coupler. The oil-in-water emulsification dispersion method can be a conventionally known method of dispersing a hydrophobic additive such as a coupler, and usually has a low boiling point of about 150 ° C. or higher and a high boiling point organic solvent, and / or an aqueous solution. Using a dispersing means such as a stirrer, a homogenizer, a colloid mill, a Frosit mixer, an ultrasonic device, etc. using a surfactant in a hydrophilic binder such as a gelatin aqueous solution. After emulsifying and dispersing, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion or dispersion.

As a high boiling point solvent, organic compounds with a boiling point of 150 ° C or higher, such as phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acid esters, trimesic acid esters that do not react with the oxidized product of the developing agent. A solvent is used.

Low boiling or aqueous organic solvents can be used with or instead of high boiling solvents. Examples of the organic solvent having a low boiling point and substantially insoluble in water include ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane and benzene.

Dye forming coupler, DIR coupler, Colored coupler, D
When the IR compound, the image stabilizer, the color antifoggant, the ultraviolet absorber, the fluorescent whitening agent and the like have an acid group such as carboxylic acid and sulfonic acid, they can be introduced into the hydrophilic colloid as an alkaline aqueous solution. .

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds which can be preferably used are those described in Item VII J of RD17643.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction and the like and to prevent deterioration of the image by ultraviolet rays. Good.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye, an ultraviolet absorber or the like, they may be mordanted with a mordant such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. A compound that can be preferably used as a development accelerator is RD17643 No. X
The compound described in the paragraphs XI to D, wherein the development retarder is 1764
It is the compound described in Item XXI, Item E of Item 3. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

The emulsion layer of the photographic light-sensitive material comprises a polyalkylene oxide or a derivative thereof such as an ether, ester or amine, a thioether compound, a thiomorpholine compound, a quaternary ammonium compound or a urethane derivative for the purpose of increasing sensitivity, increasing contrast or promoting development. It may include a urea derivative, an imidazole derivative and the like.

A fluorescent brightening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. Compounds that can be preferably used as optical brighteners are described in RD17643, item V.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which are bleached or bleached from the light-sensitive material during the development processing may be contained. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

Reduction of gloss of the light-sensitive material, improvement of writing property on the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other. Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, polycarbonates and Examples thereof include styrene polymers and copolymers thereof. The matting agent preferably has a particle size of 0.05 μ to 10 μ. The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant may be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. May be used for. Antistatic agents preferably used are the compounds described in RD17643 XIII.

For the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property improvement, antistatic property, slipperiness improvement, emulsion dispersion,
Various surfactants can be used for the purpose of preventing adhesion, improving photographic properties (acceleration of development, hardening, sensitization, etc.).

The support used in the light-sensitive material of the present invention includes an α-olefin polymer (for example, polyethylene, polypropylene,
Flexible reflective support such as paper laminated with ethylene / butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate and polyamide. And a flexible support in which a reflective layer is provided on these films, glass, metal, pottery, and the like.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support, if necessary, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness,
It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

At the time of applying the light-sensitive material, a thickener may be used to improve the coatability. For a hardener such as a hardener that causes gelation before coating when it is added to the coating solution in advance because it has a high reactivity, it is recommended to mix it with a static mixer or the like immediately before coating. preferable.

As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful, but packet coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, and examples thereof include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide-based, glycerin-based, glycidol-based, higher alkylamines, quaternary ammonium salts, pyridine and the like. Heterocycles, cation surfactants such as phosphonium or sulfonium, carboxylic acids, sulfonic acids,
Anionic surfactants containing an acidic group such as phosphoric acid, sulfuric acid ester and phosphoric acid ester, and amphoteric surface active agents such as amino acids, aminosulfonic acids and sulfuric acid or phosphoric acid esters of amino alcohol may be added. Further, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilization processing step if necessary, but instead of a processing step using a bleaching solution and a processing step using a fixing solution. In addition, the bleach-fixing treatment step can be carried out using the 1-bath bleach-fixing solution, and the mono-bath processing step using the 1-bath development bleach-fixing solution capable of performing color development, bleaching and fixing in a single bath. You can also do

In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. In these processes, instead of the color development processing step, a color developing agent, or a precursor thereof may be contained in the material, and an activator processing step in which the development processing is carried out with an activator solution may be performed, or an activator for the monobath processing. Treatments can be applied. Typical processing is shown below among these processings. (These steps include any one of a washing step, a washing step and a stabilizing step as the final step.) ・ Color development processing step-bleaching step-fixing step-Color development processing step-bleach-fixing step Process-Pre-hardening process-Color development process-Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplement Color development processing step-Stop processing step-Bleaching processing step-Fixing processing step-Activator processing step-Bleaching fixing processing step-Activator processing step-Bleaching processing step-Fixing processing step-Mono bath processing step The processing temperature is usually 10 ° C. ~ 65 ℃, but 65 ℃
The temperature may be higher than that. It is preferably treated at 25 ° C to 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can.

These compounds generally account for about 0.1 for Color Developer 1.
It is used in a concentration of -30 g, more preferably in a concentration of about 1-15 g for color developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethylbenzene and the like are included.

A particularly useful primary aromatic amine-based color developing agent is an N, N ¹ -dialkyl-p-phenylenediamine-based compound, in which the alkyl group and the phenyl group may be substituted or not substituted. . Among them, particularly useful compound examples are NN-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride,
2-amino-5- (N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N
-Ethyl-N-β-hydroxyethylaminoaniline,
4-amino-3-methyl-N, N-diethylaniline, 4
-Amino-N- (2-methoxyethyl) -N-ethyl-
Examples thereof include 3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of the color developing solution,
Immediately after the alkaline solution treatment, a bleach-fixing treatment is carried out.

The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or a development modifier such as citrazinic acid, and a preservative such as hydroxylamine or sulfite. You may. Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. may be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or higher, preferably about 9-13.

In the color developer used in the present invention, if necessary, an antioxidant such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, a secondary aromatic alcohol, hydroxamic acid, bentose or Hexose, pyrogallol-1,3
-Dimethyl ether and the like may be contained.

In the color developing solution used in the present invention, various chelating agents can be used together as a sequestering agent. For example, as the chelating agent, an amine polycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminopentaacetic acid, 1
-Organophosphonic acid such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane 1, Examples thereof include phosphonocarboxylic acid such as 2,4-tricarboxylic acid, polyphosphoric acid such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compound.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper are coordinated are used. . Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, Examples include phenylenediamine tetraacetic acid. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are used at 5-450 g /, more preferably 20-250 g /.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative is applied if necessary.
Further, it may be a bleaching solution having a composition containing an ethylenediaminetetraacetic acid iron (III) complex salt bleaching agent and adding a large amount of a halide such as ammonium bromide. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

The bleaching solution used in the present invention includes JP-A-46-280, JP-B-45-8506, 46-556, and Belgian Patent No. 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0.

The fixer may have a commonly used composition. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in which they can be dissolved at 5 g / or more, but generally 70 to 250 g /. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution are various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrates, hardening agents such as water-soluble aluminum salts, methanol,
An organic solvent such as dimethyl sulfamide or dimethyl sulfoxide can be appropriately contained.

The fixer is used at a pH of 3.0 or above, but generally 4.5-10
Is used, preferably 5 to 9.5, and most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the bleaching treatment step, and preferable compounds and concentrations in the processing solution are the same as in the bleaching treatment step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition containing a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent, or conversely, a halide such as ammonium bromide. A bleach-fix solution composed of a large amount of iron, and further ethylenediaminetetraacetate iron (II
I) A special bleach-fixing solution having a composition composed of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the fixing agents described in the fixing processing step. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as those in the fixing processing step.

The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5, most preferably 6.5-8.5.

〔Example〕

Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Example-1 A color photographic element (Sample-1) was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

First layer: green-sensitive silver halide emulsion layer Monodisperse emulsion consisting of AgBrI containing 0.30 μm average grain size () and 6 mol% of AgJ-I ... coating amount of silver 2.0 g / m ² sensitizing dye I ... to 1 mol of silver On the other hand, 2.5 × 10 ^-5 moles Sensitizing dye II: 1.2 × 10 ^-5 moles per 1 mole of silver Magenta coupler (M-1): 0.075 moles per 1 mole of silver Colored magenta coupler (CM-1): Silver For 1 mole
0.01 mol DIR compound (D-1) ... 0.0012 mol per 1 mol of silver DIR compound (D-2) ... 0.0030 mol per 1 mol of silver Second layer protective layer Gelatin layer In addition to the above composition for each layer A gelatin hardener (H-
1) and a surfactant were added.

The compounds contained in each layer in Sample 1 are as follows.

Sensitizing dye I: anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine hydroxide Sensitizing dye II: anhydro 9-ethyl-3,3'- The- (3
-Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Then, in the same manner as in Sample-1, except that the compounds shown in Table 1 were added to the first layer and the second layer in Sample-1, Sample-
2 to Sample-15 were prepared.

Samples 1 to 15 obtained as described above were exposed to green light through a sensitometric wedge and a rectangular wave chart, and then color-developed according to the following processing steps.

[Processing step] (38 ℃) Color development 2 minutes 40 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Processing liquid composition used in each processing step Is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxyamine ・ 1/2 sulfate 2.0g anhydrous potassium carbonate 37.5g sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

[Bleaching solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid iron diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0m Add water to make 1 and adjust the pH to 6.0 with ammonia water.

[Fixer]

Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to make 1 and adjust to pH = 6.0 with acetic acid.

[Stabilizer]

 Formalin (37% aqueous solution) 1.5 m Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 m Add water to make 1.

Then, the color image formed on each of the above samples was measured for sensitometric characteristics and sharpness (MTF) using green light. The results are shown in Table 2.

The gamma is shown as the slope (tan0) in the range of logE1.5 as the exposure amount from the sensitivity point (fog density + 0.1).

In addition, the effect of improving the sharpness is the MTF (Modulation Trans
fer function), the relative value of MTF at 10 lines / mm (sample
No. 1 is 100).

As is clear from Table 2, sample 2 using only USM compound
Also, Sample 3 has an unsuitable performance as a color light-sensitive material because it shows an increase in fog density and a decrease in gamma, and if it is added non-photosensitively even if DP 'scavenger is used in Samples 4 and 6, it is a USM compound. Has not produced enough effect to make up for the shortcomings of.

On the other hand, in Samples (7) to (15), by using the DP 'scavenger for the silver halide emulsion layer,
It can be seen that the increase in fog density and the decrease in gamma, which are the drawbacks of the M compound, were significantly improved, and the sharpness was also unexpectedly improved. Also, especially in the silver halide emulsion layer, USM compound and D
By using P'scavenger simultaneously, the effect is remarkable.

Also, as DP 'scavenger, especially hydroquinone Fpe
It can be seen that (SC-2) gallic acid ester (SC-22) and the colorless coupler (general formula VIIISC-129) are more effective.

[Example-2] A multilayer color photographic element sample 16 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-1 (Comparison) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer; intermediate layer (I.L.) Gelatin layer.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Average grain size () 0.30 μm, AgBrI containing 6 mol% AgI Monodisperse emulsion (Emulsion I) ... Silver coating amount 1.8 g / m ² Sensitizing dye III: 6 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): 0.06 mol per mol of silver Colored cyan coupler (CC-1) ... 1 mol silver
0.003 mol DIR compound (D-1) ... 0.0015 mol per 1 mol of silver DIR compound (D-3) ... 0.002 mol per 1 mol of silver Fourth layer; high-sensitivity red-sensitive silver halide emulsion layer (RH- 1) Monodisperse emulsion consisting of AgBrI containing 0.5 μm average particle size () and 7.0 mol% AgI (Emulsion II) ... Silver coating amount 1.3 g / m ² Sensitizing dye III ... 3 × 10 3 to 1 mol silver. ^-5 mol Sensitizing dye IV: 1.0 × 10 ^-5 mol per 1 mol of silver Cyan coupler (C-1): 0.02 mol per mol of silver Colored cyan coupler (CC-1): 1 mol of silver 0.
Mol DIR compound (D-3): 0.001 mol per mol of silver Fifth layer; intermediate layer (IL) The same gelatin layer as the second layer.

Sixth layer: low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Coating amount of silver 1.5 g / m ² Sensitizing dye I ... 2.5 × 10 ^-5 mol sensitizing dye per mol of silver II ... 1.2 × 10 ^-5 moles per mole of silver Magenta coupler (M-1) ... 0.050 per mole of silver
Molar colored magenta coupler (CM-1) ... 0.009 mol per mol of silver DIR compound (D-1) ... 0.0010 mol per mol of silver DIR compound (D-2) ... 0.0030 mol per mol of silver 7th layer: High-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II ... Coating amount of silver 1.4 g / m ² Sensitizing dye I ... 1.5 × 10 ^-5 mol sensitizing dye per 1 mol of silver II ... 1.0 × 10 ^-5 moles per mole of silver Magenta coupler (M-1) ... 0.020 per mole of silver
Molar colored magenta coupler (CM-1) ... 0.002 mol per mol of silver DIR compound (D-2) ... 0.0010 mol per mol of silver Eighth layer; gelatin layer ninth layer; Yellow filter layer (YC-) 1) A gelatin layer containing yellow colloidal silver.

Layer 10: Low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (Emulsion III) consisting of AgBrI containing 0.48 μm average grain size and 6 mol% AgI ... Silver coating amount 0.9 g / m ² sensitization Dye V: 1.3 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (Y-1): 0.34 mol per 1 mol of silver 11th layer: High-sensitivity blue-sensitive emulsion layer (BH-1) Average particle size 0.8 Monodisperse emulsion consisting of AgBrI containing 15 μm of AgI and 15 mol% AgI (Emulsion IV) ... Silver coating amount 0.5 g / m ² Sensitizing dye V ... 1.0 × 10 ^-5 mol yellow silver coupler (Y-1) per 1 mol silver ... 0.13 mol per mol of silver DIR compound (D-3) ... 0.0015 mol per mol of silver Twelfth layer; first protective layer (Pro-1) Silver iodobromide (AgI 1 mol% average particle size 0.07) μm) Silver coating amount 0.5 g / m ² Gelatin layer containing UV absorbers UV-1 and UV-2.

Thirteenth layer; Second protective layer (Pro-2) Gelatin layer containing polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1) Each layer contains a gelatin hardener (H −
1) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye III; Anhydro 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3,3'- The-
(3-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5 ′ -Methoxythiacyanine Then, in the same manner as in Sample 16, except that the compounds shown in Table 3 were added to the 6th, 7th and 8th layers of Sample 16,
Sample 27 was prepared.

Sample 16 to Sample 27 obtained as described above were exposed with white light, and the color development processing time was changed to 3 minutes and 15 seconds. The metric properties and sharpness (MTF) were measured. The results are shown in Table 4.

As is apparent from Table 4, Samples (19) to (27) according to the present invention are problems of USM compounds as compared with Comparative samples (16), (17) and (18) as in Example-1. The improvement of the minimum density and the softening of the image are improved, and the sharpness is greatly improved.
0), (22), (25) and (27) were good.

Also, when samples (16) to (27) were photographed and printed in a color print photosensitive material, and image quality was evaluated, especially sample (17) could not obtain a satisfactory print due to softening, The sample according to the present invention was able to obtain a print with high sharpness and image quality with excellent details.

[Example-3] Samples 28 to 36 were prepared in the same manner as in Sample 16 except that the compounds shown in Table 5 were added to the third layer, the fourth layer and the fifth layer of Sample 16 in Example-2. It was made.

From the sample (28) obtained in the above to the sample (36) and Examples-
The sample (16) prepared in 2 was color-developed in the same manner as in Example-2, and the sensitometric characteristics and sharpness (MTF) were measured using red light. The results are shown in Table 6.

As can be seen from Table 6, the sample according to the present invention, even in the red-sensitive unit, has improved the defects caused by the USM compound and has dramatically improved sharpness.

Claims (1)

[Claims] 1. A means for forming an unsharp positive image in combination with at least one light-sensitive silver halide emulsion layer on a support and an oxidant of a color developing agent for capturing an image. A silver halide color photographic light-sensitive material containing a compound that does not contribute