JPH0713733B2 - Silver halide photographic light-sensitive material with improved sharpness - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved sharpness.

[Background of the Invention]

In general, a silver halide color photographic light-sensitive material has three kinds of photographic silver halide emulsion layers, which are selectively spectrally sensitized to have sensitivity to blue light, green light and red light, coated on a support. ing. For example, in a silver halide photographic light-sensitive material for a color negative, a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer are generally coated in this order from the exposed side, A bleachable yellow filter layer is provided between the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer to absorb blue light transmitted through the blue-sensitive silver halide emulsion layer. . Further, each emulsion layer is provided with another intermediate layer for the purpose of various kinds and a protective layer as the outermost layer. It is also known that each of these light-sensitive silver halide emulsion layers is provided in an arrangement different from that described above. Further, as each silver halide emulsion layer, light-sensitivity to each color light in substantially the same wavelength range is obtained. It is also known to use a photosensitive silver halide emulsion layer consisting of two layers having different properties and different sensitivities. In these silver halide color photographic light-sensitive materials, the exposed silver halide grains are developed by using, for example, an aromatic primary amine type color developing agent as a color developing agent to oxidize the generated color developing agent. The dye image is formed by the reaction of the dye with the dye-forming coupler. In this method, usually, in order to form a dye image of cyan, magenta and yellow, a phenol or naphthol type cyan coupler, a 5-pyrazolone type,
A pyrazolinobenzimidazole type, a pyrazolotriazole type, an indazolone type or a cyanoacetyl type magenta coupler and an acylacetamide type yellow coupler are used. The present invention is suitable as a silver halide color photographic light-sensitive material in which these dye-forming couplers are previously made non-diffusible and contained in the silver halide emulsion layer.

Conventionally, silver halide light-sensitive materials have been continuously required to have clear image contours and fine images without blurring, that is, excellent sharpness.

As a typical conventional sharpness improving technique, for example, a development inhibitor or a development inhibitor precursor (hereinafter collectively referred to as a DIR compound) which reacts with an oxidized product of a developing agent is used to suppress development during development processing. Improvement of sharpness by the adjacency effect using the concentration gradient of the agent and means for improving the interlayer effect (hereinafter referred to as IIE), or sharpness by forming an unsharp positive image at the same time as the negative image and emphasizing the edge of the image. The means etc. which improve are known. But diffusive
With the method using a DIR compound, the expected improvement in sharpness is small. Further, in the formation of an unsharp positive image, the inclination of the photographic characteristic curve (hereinafter referred to as γ) becomes small and the gradation becomes so-called soft gradation.

[Object of the Invention]

The object of the present invention is to remedy the above drawbacks. That is, an object of the present invention is to provide a silver halide photographic light-sensitive material excellent in gradation as well as sufficient sharpness in the means for forming an unsharp positive image.

[Specific Description of the Invention]

The object of the present invention is to provide a silver halide photographic light-sensitive material having two or more silver halide emulsion layers having different color sensitivities on a support in combination with at least one silver halide emulsion layer. A development inhibitor or a development inhibitor precursor is contained in at least two of the light-sensitive silver halide emulsion layers which have a means for forming a sharp positive image and which have different color sensitivities, by reacting with an oxidized product of a developing agent. At least two photosensitive halogens having different color sensitivities in a silver halide photographic light-sensitive material containing a compound (DIR compound) which is released from the DIR compound and whose development inhibitor or development inhibitor precursor is diffusible. It was achieved by a silver halide light-sensitive material characterized by satisfying the following condition A for a silver halide emulsion layer.

[Condition A]

The relationship between the magnitude of development inhibition by two DIR compounds depends on the photosensitive silver halide emulsion layer containing those DIR compounds, and the development inhibition by the photosensitive silver halide emulsion layer containing them is A DIR compound is added so that the development inhibiting power for the other photosensitive silver halide emulsion layer is greater than that for the other.

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

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.

Further, decoloring does not produce a colored compound, or the produced colored compound flows out of the photographic material during the development process, so that the unsharp positive image formation is impaired at the end of the imaging process. It means that a colored compound does not remain in the photographic material.

The decolorizable small diffusible positive compound reacts with the oxidized product of the developing agent to erase the color in the area where a color image is formed by the reaction between the color developing agent and the above diffusion resistant coupler. 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 diffusive positive compound have a reverse 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 non-diffusible dye-forming small-diffusive positive compound is unreacted or discolored in an area where no color image is formed by the anti-diffusive coupler. As a result, the color image of the antidiffusive coupler and the unreacted or discolored small diffusive positive compound have an inverse relationship with the color image,
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, an unsharp image, that is,
An unsharp positive image will be formed.

As described above, the diffusion-resistant dye-forming type small diffusible positive compound is
An unsharp positive image is formed and, at the same time, it reacts with an oxidized product of a developing agent to produce a diffusion resistant dye having a main absorption in a main absorption wavelength region of a color forming dye. The antidiffusive dye forms a color image with the antidiffusive dye formed by the reaction of the antidiffusive coupler with the oxidized product of the color developing agent.

This diffusion resistant dye forming type small diffusion positive compound produces both an unsharp positive image and a negative image composed of the diffusion resistant dye as described above. Therefore, it may appear that the two images overlap and 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 diffusion-resistant dye formed are diffused. Due to the difference in sex, a microscopic density change (edge effect) occurs,
It 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 a developing agent to release the Link-B portion according to the amount of the oxidized product of a developing agent, and Link is A and B. 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 unproductive product by a coupling reaction with an oxidant of a color developing agent or a component which cross-oxidizes with an oxidant 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.

The Link, for example, -N = N -, - O - , - S -, - NH-SO 2 -, - SO 2 -NH
-, And so on.

here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl, triazoyl, benztriazoyl, urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl, There is tetrazo reel. R is an alkyl which may have 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. Moreover, because of the low diffusivity of this compound, it migrates 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 [II] Coup-Link ₂ -Ar Coup- of the 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 carded couplers, for example, U.S. Patents 2,449,969, 2,688,538, and 2,706,68.
No. 4, No. 2,808,329, No. 3,005,712, Belgium Patent 57
It is known as No. 0,271 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]. 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 TypeA, and the concept of the present invention is included. Not not. That is, a part of the present invention is obviously different from the embodiment of the present invention in the case where it is used for the same color correction as the color coupler like Type A and the case where the Dye portion which is diffused and transferred and flows out is used for an 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 the general formula [I] where A is CLAS.
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.

(TypeC): Weiss coupler type general formula [IV] Wcoup-Link _4- Dye Wcoup, for example, R ₂ COCH _2- (R ₂ is alkyl, aryl, heterocyclic group having an alkyl having 16 or less carbon atoms), (Z is an atom 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 an 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 a coupling reaction such as 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.

(TypeD): 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-5 residue, Link ₅ is -NHSO _2- (nitrogen atom bonded to FUN part),
_{-O -, - SO 2 -,} - S- and the like, Dye is a dye residue or a precursor moiety thereof preferably has an alkali-soluble group.

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

As described above, the diffusion-resistant dye-forming type small diffusion compound is a dye or a precursor thereof and forms a diffusion-resistant dye by a reaction with an oxidant of a color developing agent. By the above, a dye portion may be newly formed, or a new dye portion is not formed, and the dye portion before the reaction or its precursor portion is subjected to the development treatment step,
It may remain as the dye portion of the diffusion resistant dye.

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 (pigment-forming type).

This type can be further classified into the following types.

Type I-1 A dye portion or a precursor thereof which is previously held is decolored by coupling with an oxidized product of a color developing agent, and the dye portion or a precursor portion thereof should be newly provided after the development processing step. A compound that forms a dye part having substantially the same color as the dye part 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).

There is no decolorization of the dye portion or its precursor which is already held by the coupling with the oxidant of the type II color developing agent,
It is also a compound that is resistant to diffusion without forming a new dye portion.

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 the developing agent oxidant to release Link ₁ -B ₁ portion according to the amount of the developing agent oxidant, and Li is an organic residue that can form a coupling dye.
nk ₁ is a group for connecting A ₁ and B ₁ , and B ₁ is an organic residue.

Specific examples of A ₁ include phenols, naphthols, 5-pyrazolones, pyrazolotriazoles, pyrazolotetrazoles, pyrazolobenzimidazoles, indazolones and acylacetanilides.

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,
Examples include urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl, and tetrazolyl.

The B _1, if Link ₁ is of such chromophores -N = N-in, for example, an aryl group or a heterocyclic group are preferable, 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 resulting from these flows out of the system. And an alkali-soluble group such as a carboxyl group, a sulfo group, a hydroxyl group, and a sulfamoyl group in order to make the dye formed by the coupling resistant to diffusion, and
For example, a diffusivity-reducing group such as an alkyl group may be appropriately introduced to balance the diffusivity before and after the reaction.

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

In the 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. , But D ₁ never leaves A ₂ upon coupling.

Specific examples of A ₂ include those described 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 or a group containing an alkali-soluble group which can be released upon coupling can 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), those equivalent are exemplified.

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 a compound residue of a hisalkylcarbamoyl-aryloxymethane system or a bisalkylcarbamoyl-arylthiomethane system.

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 to transfer 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 is D ₁ synonymous in the general formula (I-2), those equivalent are exemplified.

Fun reacts with the oxidant of the color developing agent and has 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 produced 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 elutes 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. A sharp positive image will be formed.

As the diffusion resistant positive compound, for example, the following general formula [A-
I] can be mentioned.

General formula [A-I] 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 soluble 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 , and B ₃ is an organic residue.

Further, the compound represented by the general formula [A-I] 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. When the product is a compound exhibiting an unsuitable hue for image formation, the product is balanced in hydrophilicity or lipophilicity so that after the reaction, the product is eluted out of the system constituting the hue of the photographic material. Substituents are attached.

A ₃ in the general formula [A-I] is, for example, a cross-oxidation reaction with a residue of a coupler which produces a colored or colorless product upon coupling reaction with an oxidant of a color developing agent or an oxidant 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 Releasing
The non-residue, after being oxidized, undergoes an intramolecular ring closure reaction,
B-SO as Link-B₂ Phenols that release
Or U.S. Patent Nos. 3,443,939, 3,443,940 and 3,44
It is described in No. 3,941. ) Residue.

The Link, for example, -N = N -, - O - , - S -, - SO 2 -, - NH-SO 2 -,
-SO ₂ -NH-, And so on.

here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl, imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl, triazoyl, benztriazoyl,
Examples include urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl, and tetrazolyl. 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 [AI] may be a compound which is colored or discolored as the B ₃ portion or A ₃ -Link-B _{3 as a} whole.

In order to impart the property of not diffusing during the development processing to the compound represented by the general formula [A-I] and the diffusivity for elution to the outside of the undesired product after the reaction, 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 [AI] 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 A ₃ partial coloring oxidant coupled to produce a colored dye developing agent is inappropriate on the image formation, an alkali-soluble group in A ₃ portion so that emitting color dye is washed away out of the system during processing It is preferable to use a color developing agent having an alkali-soluble group as the color developing agent.

When the B ₃ portion forms a dye or its precursor, the B ₃ portion preferably has an alkali-soluble group so that the B ₃ portion after the reaction flows out of the system.

Compounds belonging to this category, in the exposure part ₃ A make a 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 [AI] which remains in the unexposed area or the compound whose color has changed. Moreover, the periphery of the positive image by this compound forms an unsharp positive image in the layer during the development process by reaction with the diffused oxidized developing agent. Further, among these types, the following two types are preferable.

(Type A): Colored coupler type [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 the 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. Li
nk ² is a chromophore, preferably -N = N- or -CH =. Some of these compounds have already been used as carded couplers, for example, U.S. Patents 2,449,969, 2,688,538, and 2,
No. 706,684, No. 2,808,329, No. 3,005,712, Japanese Patent Publication No.44-
It is known as 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 [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 portion or a dye precursor portion and preferably has an alkali-soluble group, but Link ³
Not required depending on the type of. Compounds belonging to this type of classification 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. Not not. That is, a part of the present invention is obviously different from the embodiment of the present invention in the case where it is used for the same color correction as the color coupler like Type A and the case where the Dye portion which is diffused and transferred and flows out is used for an image.

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

Class II: A ₃ parts of colorless coupling body forming type compound belonging to this class have the general formula [A-1] is
Although it reacts in the same manner as the CLASSI compound, the reaction product is colorless and may remain in the layer after the coupling reaction.

(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 atom group that completes a 5- to 8-membered alicyclic ring, condensed ring or heterocyclic ring, and R ₃ represents an aryl residue). And
The Wcoup portion preferably has a diffusion preventing group, for example, a group having 17 or more carbon atoms, in order to make the compound represented by the general formula [A-4] resistant to diffusion.

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

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

CLASS III: Redox reaction type Compounds belonging to this class do not undergo a coupling reaction such as 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.

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

Typical specific examples of the unsharp positive image forming compound used in the present invention will be given below.

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 converted to sulfochloride or acid chloride by a suitable acid chloride agent such as phosphorus oxychloride or thionyl chloride, and the dye moiety is bonded to another moiety having an amino group. 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, it is preferable that the diffusion resistant positive compound is 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. Therefore, 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.

Further, usually, when a DIR compound is used in a certain color-sensitive layer, a development inhibitor or its precursor (hereinafter,
Even if the development inhibitor including this precursor is diffusible, the addition layer itself, which is the release layer, is most suppressed,
It is difficult to use a large amount of DIR compound due to a decrease in concentration and a decrease in sensitivity.

Also, when a DIR compound is used in a layer, that layer experiences a certain amount of development inhibiting power as described above by the development inhibitor of the DIR compound of its own layer. Therefore, there occurs a phenomenon in which the development inhibitory effect cannot be sufficiently exhibited by the development inhibitor supplied from another layer. That is, in both directions between the two color-sensitive layers
When trying to cause IIE, both IIEs will either be of a lower level, or strong in one direction and significantly weaker in the other.

However, it is clear from the results of the study by the present inventors that the released development inhibitors show different development inhibiting powers in different color-sensitive layers, and that the development inhibiting powers differ depending on the type of the development inhibitor. became.

For example, when the development inhibitor A and the development inhibitor B are used in the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer in approximately equimolar amounts, development for the green-sensitive silver halide emulsion layer is performed. When the inhibitory power is A> B, but the development inhibitory power in the red-sensitive silver halide emulsion layer is A <B, the DIR compound having the development inhibitor B in the green-sensitive silver halide emulsion layer is red-sensitive halogenated. By adding the DIR compound having the development inhibitor A to the silver emulsion layer, the self-layer-inhibiting property in each added layer is weakened and the other color-sensitive layers are greatly affected [large IIE]. It became possible to give IIE in both directions, and it became possible to greatly increase IIE in both directions.

The usage of such a DIR compound, that is, the method for determining the color-sensitive layer to which the DIR compound should be added, is based on the above example, that is, between the green-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer. It is not only effective, but also effective in other types of different color-sensitive layers. That is, for example, when the development inhibitor C and the development inhibitor D are used in equimolar amounts in the blue-sensitive silver halide emulsion layer and the green-sensitive silver halide emulsion layer, the development for the blue-sensitive silver halide emulsion layer is performed. Inhibitory power is C> D, but development inhibitory power in green-sensitive silver halide emulsion layers is C <D
, The development inhibitor D is added to the blue-sensitive silver halide emulsion layer.
By adding a DIR compound having a development inhibitor C to the green-sensitive silver halide emulsion layer,
It becomes possible to keep the suppression of self-layer in each additive layer weak and to have a great influence (large IIE) on other color-sensitive layers, and to greatly increase IIE in both directions. Became possible.

Further, for example, when the development inhibitor E and the development inhibitor F are used in equimolar amounts in the blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer, the development for the blue-sensitive silver halide emulsion layer is performed. When the inhibitory power is E <F, but the developmental inhibitory power in the red-sensitive silver halide emulsion layer is E> F, the DIR compound having the development inhibitor E in the blue-sensitive silver halide emulsion layer is red-sensitive halogenated. By adding a DIR compound having a development inhibitor F to the silver emulsion layer, the self-layer-inhibiting property in each added layer is weakened, and a large influence [large IIE] is exerted on other color-sensitive layers. It has become possible to give both IIEs a breakthrough.

Note that the present invention is not limited to the case where the development inhibitor is used in an equimolar manner as described above, but by increasing or decreasing the amount of use of each development inhibitor, if the above relationship can be shown, IIE in both directions is similarly set. It can be increased. For example, the development inhibitor G and the development inhibitor H are used, and when they are equimolar, the inhibition on the green-sensitive silver halide emulsion layer is G >> H and the inhibition on the red-sensitive silver halide emulsion layer is G> H. In this case, by reducing the addition amount of the development inhibitor G (denoted as development inhibitor G '), G'> in the green-sensitive silver halide emulsion layer.
When the relationship of H and G '<H is established in the H- and red-sensitive silver halide emulsion layers, the DIR compound having H is added to the green-sensitive silver halide emulsion layer and the DIR compound having G is added in a lower (mol) amount than the former. By adding it to the red-sensitive silver halide emulsion layer, a large IIE could be obtained in both directions.
The same was true for other types of different color-sensitive layers.

Then, when the combination of the DIR compound having each suppressing group and its additive layer is reversed (for example, in the above specific example,
DIR containing development inhibitor A in green-sensitive silver halide emulsion layer
As a compound, a DIR compound having a development inhibitor B was added to the red-sensitive silver halide emulsion layer), and the self-layer suppressing effect was very strong, and IIE in both directions was extremely small. These cases are also clarified in Examples described later.

In the present invention, the usage of the DIR compound, that is, the selection of the suppressing group of the DIR compound can be carried out by the following method.

On a (transparent) support, three types of photosensitive materials having layers having the following compositions are prepared.

Sample (I): Sample having red-sensitive silver halide emulsion layer Silver iodobromide spectrally sensitized to red sensitivity (silver iodide 6 mol%, average particle size 0.48 μm) and exemplified coupler (C-7) were silver. A gelatin coating solution containing 0.08 mol per mol of silver is applied.
It was applied at 4 g / m ² .

Sample (II): Sample having green-sensitive silver halide emulsion layer Silver iodobromide spectrally sensitized to green sensitivity (silver iodide 6 mol%, average particle size 0.48 μm) and exemplified coupler (M-2) were silver. A gelatin coating solution containing 0.07 mol per mol of silver was applied.
It was applied so as to be 1 g / m ² .

Sample (III): Sample having blue-sensitive silver halide emulsion layer. Blue-sensitive spectrally sensitized silver iodobromide (silver iodide 6 mol%, average particle size 0.48 μm) and exemplified coupler (Y-4) were silver. A gelatin coating solution containing 0.34 mol per mol of the silver coating was used.
It was applied at 5 g / m ² .

In addition to the above, each layer contains a gelatin hardening agent and a surfactant.

The obtained samples (I) to (III) were exposed to white with a wedge, and the developing time was changed to 1 minute 45 seconds for (I), 2 minutes 40 seconds for (II) and 3 minutes 15 seconds for (III). Except for the above, the treatment is performed according to the treatment method of Example 1 described later. Sample (II) for developer
The amount of various development inhibitors added was changed and the amount of each development inhibitor was not added so that the development inhibitory powers were almost the same. Sensitivity of each sample (I) to (III) treated with a developer without a development inhibitor ^* 1 (S _O ), and sensitivity of each sample obtained by development of a developer with a development inhibitor added ^* The difference (ΔS) from 2 (S) is used as a measure of the development inhibiting power of each color-sensitive layer by each development inhibitor. ^* 1) The logarithm of the reciprocal of the exposure amount (E _O ) at the density point of fog density +0.3, that is, _−log E _O is taken as the sensitivity S _O. ^* 2) As in ^* 1) above, the sensitivity S is defined as the logarithm of the reciprocal of the exposure amount (E) at the density point of fog density +0.3, that is, _-log E.

Table 1 below shows the difference in the development inhibiting power for each color-sensitive layer for several types of development inhibitors, which were conducted based on the above standard experiment.

When the DIR couplers having the development inhibitors A-1 to A-6 are used, they may be used in a combination in which the development inhibition of the added layer itself is small and the development inhibition of the other layers is large, as described above.

In order to form a preferable combination between the red-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer from the difference in the development-inhibiting power of each development inhibitor exemplified in Table 1, for example, red-sensitive silver halide is used. The value of the emulsion layer (sample (I)) is normalized to the value of one compound, and the value obtained by dividing the value of the blue-sensitive silver halide emulsion layer (sample (III)) by the ratio at that time is obtained ( (See Table 2).

That is, the following combination examples and the like are listed in Table 1.

[Example of combination of development inhibitor of DIR compound added to red-sensitive silver halide emulsion layer / development inhibitor of DIR compound added to green-sensitive silver halide emulsion layer] A-1 / A-2, A-1 / A-3, A-1 / A-4, A
-1 / A-5, A-1 / A-6, A-2 / A-3, A-2 / A
-4, A-2 / A-5, A-2 / A-6, A-4 / A-
3, A-5 / A-3, A-5 / A-4, A-6 / A-3,
A-6 / A-4 etc.

Similarly, for the green-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer, and for the red-sensitive silver halide emulsion layer and the blue-sensitive silver halide emulsion layer, addition layer suppression is small and other layer suppression is large. You can choose.

Further, in order to emphasize IIE, it is preferable that the working distance of the suppressing group is large. That is, it is preferable that the so-called diffusivity is large.

In the present invention, the diffusibility of the suppressing group can be evaluated by the following method.

Photosensitive material samples (IV) and (V) each having a layer having the following composition were prepared on a (transparent) support.

Sample (IV): Sample having a green-sensitive silver halide emulsion layer Silver iodobromide spectrally sensitized to green sensitivity (silver iodide 6 mol%, average particle size 0.48 μm) and exemplified coupler (M-2) as silver A gelatin coating solution containing 0.07 mol per mol of silver was applied.
1 g / m ² , coated so that the amount of gelatin is 3.0 g / m ² , and a protective layer thereon; chemically sensitized and spectrally sensitized silver iodobromide (silver iodide 2 mol%, A gelatin coating solution containing an average particle size of 0.08 μm) was coated so that the coating silver amount was 0.1 g / m ² and the gelatin coating amount was 0.8 g / m ² .

Sample (V): The protective layer of the above sample (IV) from which silver iodobromide was removed.

In addition to the above, each layer contains a gelatin hardening agent and a surfactant.

Samples (IV) and (V) were exposed to white using a wedge and then processed according to the processing method of Example 1 described below except that the development time was set to 2 minutes and 40 seconds. The sensitivity of the sample (V) is 60% in the developer.
(In logarithmic representation, -Δ _log E = 0.22) was used as the addition of the inhibiting amount of various development inhibitor, and those with no added development inhibitor.

The sensitivity of the sample (IV) when the development inhibitor is not added is S _O , the sensitivity of the sample (V) is S _O ′, the sensitivity of the sample (IV) when the development inhibitor is added is S _W , and the sample If the sensitivity of (V) is S _V , the desensitization of sample (IV) ΔS _O = S _O ′ −S _V , the desensitization of sample (V) ΔS = S _O −S _W diffusivity = ΔS / ΔS _O expressed.

However, all the sensitivities were set to the logarithm ( _−log E) of the reciprocal of the exposure amount at the density point of fog density + 0.3.

The value obtained by this method was used as a measure of diffusivity. Table 3 illustrates the diffusivity of several development inhibitors.

Those with relatively low diffusivity (A-5: 0.34 or less)
Since IIE is also small, it is preferable that the diffusivity exceeds 0.34. In the present invention, the diffusivity is more preferably 0.4 or more.

The diffusible DIR compound of the present invention can be selected from the following general formulas.

Diffusible DIR compound General formula (1) AY) _{m In the} formula, A represents a coupler component, m represents 1 or 2, and Y binds to the coupling position of the coupler component A and reacts with an oxidized product of a color developing agent. Represents a development inhibitor having a large diffusivity or a compound capable of releasing a development inhibitor, which is released by

It suffices that A has the properties of a coupler, and it is not always necessary to form a dye by coupling.

In the general formula (1) of the diffusible DIR compound, Y represents the following general formulas (2A) to (5).

Diffusible DIR compound general formula (2A) Diffusible DIR compound general formula (2B) Diffusible DIR compound general formula (2C) Diffusible DIR compound general formula (2D) Diffusible DIR compound general formula (2E) Diffusible DIR compound general formula (3) Diffusible DIR compound general formula (4) Diffusible DIR compound general formula (5) In the above general formulas (2A) to (2D) and (3), R ₁ is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolilideneamino group, an aryloxycarbonyl group, an acyloxy group, carbamoyl. Group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-
It represents an alkylcarbamoyloxy group, a hydroxy group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, R ₁ may be the same or different, and the total number of carbon atoms contained in n R ₁ is 0 to 10.

R _{2 in the} general formula (2E) has the same meaning as R _{1 in} (2A) to (2D), X represents an oxygen atom, a sulfur atom or a selenium atom, and in the general formula (4), R ₂ is alkyl. Represents a group, an aryl group or a heterocyclic group.

In the general formula (5), R ₃ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and R ₄ represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonyl. It represents an amino group, an alkanesulfonamide group, a cyano group, a heterocyclic group, an alkylthio group or an amino group.

When R ₁ , R ₂ , R ₃ or R ₄ represents an alkyl group, it may be substituted or unsubstituted, linear or branched, or cyclic alkyl. The substituent is a halogen atom nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group or And an arylthio group.

When R ₁ , R ₂ , R ₃ or R ₄ represents an aryl group, the aryl group may be substituted. As a substituent, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, a halogen atom nitro group, an amino group, a sulfamoyl group, a hydroxy group, a carbamoyl group, an aryloxycarbonylamino group, an alkoxycarbonylamino group,
Examples thereof include an acylamino group, a cyano group and a ureido group.

When R ₁ , R ₂ , R ₃ or R ₄ represents a heterocyclic group, it represents a 5-membered or 6-membered monocyclic or condensed ring containing a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, and a pyridyl group, A quinolyl group, a furyl group, a benzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a bend triazolyl group, an imide group, an oxazine group, or the like, which are further substituted by the substituents listed for the aryl group. It may be replaced.

In the general formulas (2E) and (4), the number of carbon atoms contained in R ₂ is 1 to 15.

In the above general formula (5), the total number of carbon atoms contained in R ₃ and R ₄ is 1 to 15.

In the above general formula (1), Y represents the following general formula (6).

Diffusible DIR compound General formula (6) -TIME-INHIBIT In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by the reaction with the color developing agent. After cleavage from the coupler, the INHIBIT group is appropriately cleaved. It is a group that can be controlled and released.

The INHIBIT group is a development inhibitor.

In the general formula (6), the -TIME-INHIBIT group represents the following general formulas (7) to (13).

Diffusible DIR compound general formula (7) Diffusible DIR compound general formula (8) Diffusible DIR compound general formula (9) Diffusible DIR compound general formula (10) Diffusible DIR compound general formula (11) Diffusible DIR compound general formula (12) Diffusible DIR compound general formula (13) In formulas (7) to (13), R ₅ is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkoxycarbonyl group, an anilino group, an acylamino group, a ureido group, a cyano group, a nitro group. , A sulfonamide group, a sulfamoyl group, a carbamoyl group, an aryl group, a carboxy group, a sulfo group, a hydroxy group, and an alkanesulfonyl group, represented by the general formulas (7), (8), (9), (11) and (13) In, 1 represents 1 or 2, and in the general formulas (7), (11), (12) and (13),
k represents an integer of 0 to 2, and in the general formulas (7), (10) and (11), R ₆ represents an alkyl group, an alkenyl group, an aralkyl group, a cycloalkyl group or an aryl group, ) And (13), B is an oxygen atom or (R ₆ has the same meaning as previously defined.), And the INHIBIT group is the general formula defined by the general formulas (2A), (2B), (3), (4) and (5) and the carbon number. And have the same meaning.

However, in the general formulas (2A), (2B) and (3), the number of carbon atoms contained in each R ₁ in one molecule is ₁ to 32 in total, and included in R ₂ in the general formula (4). Carbon number is 1
32, and the total number of carbon atoms contained in R ₃ and R ₄ in the general formula (5) is 0 to 32.

When R ₅ and R ₆ represent an alkyl group, they may be substituted or unsubstituted, linear or cyclic. Examples of the substituent include the substituents enumerated when R _{1 to} R ₄ are alkyl groups.

When R ₅ and R ₆ represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents enumerated when R _{1 to} R ₄ are aryl groups.

Of the above diffusible DIR compounds, those of general formula (6) are preferred, and -INHIBIT has the general formula (2E), (4)
Those having a leaving group represented by are particularly preferable.

Examples of the yellow color image forming coupler residue represented by A in the general formula (1) include pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, Malon ester monoamide type, benzothiazolyl acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type,
Malon diester type, benzimidazolyl acetamide type or benzimidazolyl acetate type coupler residues, heterocyclic-substituted acetamides contained in U.S. Pat.No. 3,841,880 or coupler residues derived from heterocyclic-substituted acetates or U.S. Pat.No. 3,770,446, British Patent 1, Four
59,171, West German Patent (OLS) 2,503,099, JP-A-50-139
Coupler residues derived from acylacetamide compounds described in No. 738 or Research Disclosure No. 15737, and heterocyclic coupler residues described in US Pat. No. 4,046,574.

Examples of the magenta color image forming coupler residue represented by A include 5-oxo-2-pyrazoline nucleus, pyrazolo- [1,5-
a] A coupler residue having a benzimidazole nucleus or a cyanoacetophenone type coupler residue is preferable.

The shea color image-forming coupler residue represented by A is a coupler residue having a phenol nucleus or an α-naphthol nucleus,
Indazolone or pyrazolotriazole coupler residues are preferred.

Furthermore, the effect as a DIR coupler is the same even when the coupler does not substantially form a dye after coupling with the oxidized product of the developing agent and releasing the development inhibitor. Examples of this type of coupler residue represented by A include U.S. Pat. No. 4,052,213
No. 4,088,491, No. 3,632,345, No. 3,958,993 or No. 3,961,959, and the like.

Specific examples of the diffusible DIR compound of the present invention will be given below, but the invention is not limited thereto.

[Exemplified compound]

These compounds are disclosed in U.S. Patents 4,234,678 and 3,227,554.
Issue 3,617,291, Issue 3,958,993, Issue 4,149,886,
3,933,550, JP-A-57-56837, JP-B-51-13239
No. 2,072,363, No. 2,070,266, Research Disclosure No. 21228, December 1981, and the like.

The silver halide emulsion used in the present invention may be a conventional silver halide emulsion such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Although any of those used can be used, silver bromide, silver iodobromide and silver chloroiodobromide are particularly preferable.

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 pll ₃ 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 the salts are removed, RISA DISC (Research Disclosure RD
It can be carried out based on the method described in Item 17643, Item II.

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

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 grains, any ratio of {100} plane to {111} plane 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,
A 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,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.

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 the photographic performance stable, during chemical ripening, at the end of chemical ripening, and / or after the completion of chemical ripening, before the silver halide emulsion is coated, the photographic industry Compounds known as antifoggants or stabilizers in 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 such an amount that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid.
It is also possible to add a hardening agent 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, Mukifenokicyclo acid, etc.) or the like 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 XII of RD17643.

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 so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. 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.

These dye-forming couplers nondiffuse couplers called baerato groups in the molecule. It is desirable to have a group having 8 or more carbon atoms. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye, but they need only reduce 2 molecules of silver ion even if they are 4 equivalence. Either of two equivalence may be used. Dye-forming couplers have a color-correcting effect, and by coupling with colored couplers and oxidants of developing agents, development accelerators, bleaching accelerators, developers, silver halide solvents, toning agents, hardeners. Included are compounds that release photographically useful fragments such as agents, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers.

The DIR compound that releases a non-diffusible development inhibitor can be used alone or in combination depending on the application.
Coupling reaction with the oxidation product of the primary amine developer,
A colorless coupler that does not form a dye (also called a competing coupler) can be used in combination with the dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and bivaloylacetanilide 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 2,983,608.
No. 3, No. 3,062,653, No. 3,127,269, No. 3,311,47
No. 6, No. 3,419,391, No. 3,519,429, No. 3,558,3
No. 19, No. 3,582,322, No. 3,615,506, No. 3,834,
908, 3,891,445, West German patent 1,810,464, West German patent application (OLS) 2,408,665, 2,417,945, 2,41
8,959, 2,424,467, JP-B-40-6031, JP-A-49-
74027, 49-74028, 49-1295381, 50-60233
No. 50, No. 50-159336, No. 51-20826, No. 51-26541, No. 5
2-42121, 52-58922, 53-55122, Japanese Patent Application No. 55-11
Examples include those described in 0943.

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.

Among the dye-forming couplers, colored couplers, DIR couplers, DIR compounds, image stabilizers, antifoggants, UV absorbers, and fluorescent brighteners that do not need to be adsorbed on the surface of silver halide crystals, hydrophobic compounds are Various methods such as a solid dispersion method, a latex dispersion method and an oil-in-water emulsion dispersion method can be used, which can be appropriately selected depending on 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, homogenizer, colloid mill, flowgit mixer, ultrasonic device, etc., using a surfactant in a hydrophilic binder such as an aqueous gelatin 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.

A low boiling or water soluble organic solvent can be used with or in place of the high boiling solvent. 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, image stabilizer, antifoggant, ultraviolet absorber, and fluorescent whitening agent 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.

Between the emulsion layers of the light-sensitive material (same color-sensitive layer and / or different color-sensitive layer), the oxidant of the developing agent or the electron transfer agent moves to cause color turbidity, deterioration of sharpness, and graininess. An antifoggant can be used to prevent the property from being conspicuous.

The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds that can be preferably used are those described in VII J of RD 17643.

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. The compound which can be preferably used as the development accelerator is the compound described in the paragraphs XXI to B of RD 17643, and the development retarder is 1
The compound is described in Item XXI, Item E of 7643. 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 whitening 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 which can be preferably used as the fluorescent whitening agent are described in RD 17643, item V.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an anti-irradiation 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, polycarbonate and styrene. And the 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 as an antistatic agent on the side of the support on which the emulsion is not laminated, and a protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated on the emulsion layer and / or the support. May be used for. Antistatic agents preferably used are the compounds described in RD 17643 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 capable of simultaneously coating 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 .about.30 g, more preferably in a concentration of about 1 to 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-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine-based color developing agents are N, N-dialkyl-p-phenylenediamine-based compounds, in which the alkyl and phenyl groups may or may not be 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, diethylhydroxylamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or an antioxidant is used. 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
-Hydroxyethylidene-1,1'-diphosphonic acid or other organic phosphonic acid, aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid or other aminopolyphosphonic acid, citric acid or gluconic acid or other oxycarboxylic acid, 2-phosphonobutane, 1 Examples thereof include phosphonocarboxylic acid such as 2,2,4-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, siminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediamine Tetraacetic acid etc. can be mentioned.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. These bleaching agents are used at 5-450 g / l, more preferably 20-250 g / l.

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, JP-A-46-280, JP-B-45-8506, 46-566, Belgium Patent 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 ordinary fixing processing, for example, thiosulfates such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, liourea and thioether. These fixatives
5g / l or more, used in an amount that can be dissolved, but generally
Use at 70-250g / l. 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. Further, various fluorescent whitening agents, 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 in which 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 are added in a small amount, 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 comprising a combination 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 and the like can be used in addition to ammonium bromide.

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.

A multilayer 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.

Sample-1 first layer; antihalation layer (HC-1) A gelatin layer containing black colloidal silver.

Second layer: intermediate layer (I.L.-1) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Monodisperse emulsion (Emulsion I) consisting of AgBrI containing 0.35 μm average grain size () and 8 mol% AgI ... Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): relative to 1 mol of silver 0.06 moles Colored cyan coupler (CC-1) ... 0.003 moles per mole of silver DIR compound (DA) ... 0.0015 moles per mole of silver DIR compound (D-61) ... 1 mole of silver 0.002 mol 4th layer; high-sensitivity red-sensitive silver halide emulsion layer (RH-1) average grain size () 0.58 μm, AgI containing 7.0 mol% AgBrI monodisperse emulsion (emulsion II) ... silver Coating amount 1.3 g / m ² Sensitizing dye I …… 3 × 10 ^-5 mol per 1 mol silver Sensitizing dye II …… 1.0 × 10 ^-5 mol per 1 mol silver Cyan coupler (C-1) ...... 1 mol silver On the other hand, 0.02 mol Colored cyan coupler (CC-1) ... 0.0015 mol per mol of silver DIR compound (D-61) ... 0.001 mol per mol of silver Fifth layer; Intermediate layer (IL-2) 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 III: 2.5 × 10 ^-5 mol sensitized per 1 mol of silver Dye IV: 1.2 × 10 ^-5 mol / mol of silver Magenta coupler (M-1): 0.050 mol / mol of silver Colored magenta coupler (CM-1): 0.009 / mol of silver Mol DIR compound (DA): 0.0010 mol per 1 mol of silver DIR compound (D-57): 0.0030 mol per 1 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 III: 1.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 per mol of silver Mol Magenta coupler (M-1): 0.020 mol per mol of silver Colored magenta coupler (CM-1): 0.002 mol per mol of silver DIR compound (D-57): 1 mol of silver Yellow filter layer (YC-1) Gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di -t- octyl Le hydroquinone; 0.0010 mol eighth layer against.

Ninth layer: 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 10th layer; high-sensitivity blue-sensitive emulsion layer (BH-1) Average grain Monodispersed emulsion consisting of AgBrI containing 0.8 μm in diameter 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 per 1 mol silver ( Y-1) ... 0.13 mol per mol of silver DIR compound (D-61) ... 0.0015 mol per mol of silver 11th layer; 1st protective layer (Pro-1) Silver iodobromide (AgI1) Mol% average particle diameter 0.07 μm) Silver coating amount 0.5 g / m ² Gelatin layer containing UV absorbers UV-1 and UV-2.

Twelfth layer; Second protective layer (Pro-2) Gelatin layer containing polymethylmethacrylate particles (diameter: 1.5 μm) and formalin scavenger (HS-1). H-1) and (H-2) and a surfactant were added.

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

Sensitizing dye I; anhydro 5,5'-dichloro-9-ethyl-
3,3'-Di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) -Oxacarbocyanine hydroxide sensitizing dye IV; anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanin H-2 _{[(CH 2 = CHSO 2 CH 2} ) 3 CCH 2 SO 2 CH 2 CH 2 ] _{H-CH 2 CH 2 SO 3} K A colored compound was dispersed in the second, third, fifth and sixth layers of Sample 1 at the same time as other dispersions to prepare Samples 2 to 4 as shown in Table-A.

・ The amount of the third layer added is 3.2 × 10 ^-3 mol per mol of silver ・ The amount of the second layer added is the same as that of the third layer per unit area ・ The amount of the sixth layer added is 3.0 × 10 3 per mol of silver ^-3 mol ・ The addition amount of the 5th layer is the same amount per unit area in the 6th layer Sample-5 replaces D-61 and D-57 of sample-2 with DA, and adjusts the amount of DA. The tone of sample-6 is the same as sample-1 except that D-61 and D-57 of sample-1 are replaced with D-A and the amount of D-A is adjusted to adjust the gradation. Light and Gr
After performing wedge exposure using een, Blue, and Red filters, the following development processing was performed.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. Is the street.

[Color developer]

4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine ・ 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 diammonium salt 10.g Ammonium bromide salt 150.0g Glacial acetic acid 10.0 ml 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 ml Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5 ml Add water to make 1.

The densities and sharpness (MTF) of the developed samples 1 to 3 were measured and summarized in Table-B. The sharpness improvement result is
Calculate MTF (Modulation Transfer Function), 40 lines / mm
It was shown by the relative value of MTF at (Sample No. 1 is 100).

As shown in Table-B, the present invention was excellent in sharpness and had a high γ at the time of decomposition.

Further, as a result of actually photographing and printing Samples 1 to 6, Sample-2 of the present invention was very excellent in sharpness and had a sufficiently satisfactory gradation.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer having two or more different color sensitivities on a support, and being unsharp in combination with at least one silver halide emulsion layer. A development inhibitor or a development inhibitor precursor is released into at least two of the light-sensitive silver halide emulsion layers containing a means for forming a positive image and reacting with an oxidized product of a developing agent. Compound (DI
R compound), and the development inhibitor or development inhibitor precursor released from the DIR compound is a diffusible silver halide photographic light-sensitive material, and at least two light-sensitive silver halide emulsions having different color sensitivities. A silver halide photographic light-sensitive material characterized in that the layer satisfies the following condition A. [Condition A] The relationship between the magnitude of development inhibiting power of two DIR compounds varies depending on the photosensitive silver halide emulsion layer containing these DIR compounds, and the photosensitive silver halide emulsion layers contained therein. The DIR compound is added so that the development inhibiting power for the other photosensitive silver halide emulsion layer is greater than the development inhibiting power for the other.