JPH0664317B2 - Silver halide photographic light-sensitive material with improved image quality - Google Patents

Description

TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having high sensitivity, high image quality and improved color reproducibility. .

[Prior Art] Conventional silver halide photographic light-sensitive materials for color, particularly silver halide color photographic light-sensitive materials for photographing, have various required performances, such as high sensitivity and good image quality, and color reproduction. There has been a demand for excellent properties and exposure latitude. For this reason, up to now, many improved techniques relating to the production of color photosensitive materials have been developed, and the performance of photographic photosensitive materials is also improving. However, generally, in designing a silver halide photographic light-sensitive material, there is a reciprocity law between the sensitivity and the image quality, and for example, the image quality is often deteriorated as the sensitivity is increased. ,
In recent years, there is an urgent need to establish a technique for obtaining a light-sensitive material having a particularly high sensitivity and an excellent image quality as the demand for a small format increases. The following technical means for improving the image quality while maintaining high sensitivity or with minimal desensitization are known.

(1) A method of reducing the grain size of a silver halide emulsion while maintaining the sensitivity.

(2) A method of improving graininess by appropriately mixing silver halide grains having different grain sizes.

(3) A method of obtaining a fine particle image by using a coupler having a poor coloring efficiency.

(4) A method of improving the graininess of a dye image by utilizing a coloring dye that reacts with an oxide of a developing agent and slightly bleeds.

(5) A method of improving the graininess of a dye image by reducing the amount of the coupler used with respect to the silver halide.

Etc.

All of the above techniques are aimed at improving the graininess of an image, but each of them has the following problems and is not necessarily satisfactory.

That is, for example, the above (1) is based on a sensitizing technique for silver halide grains that does not depend on an increase in grain size, which easily causes an increase in fog and deterioration of storage stability, and there is a limit to achieving high sensitivity. However, the above (2) is advantageous in that the exposure latitude is widened, but the effect of improving the graininess is small.

Further, in the above (3), the color density of the obtained dye image becomes low, and in order to improve this, it is necessary to increase the amount of silver halide used, which is incompatible with the demand for silver saving. It is not preferable in terms. Further, the techniques described in (4) and (5) above belong to a technique for expanding a so-called dye cloud in which a coloring dye is formed at a distance from an exposed silver halide grain, and for that reason, blurring is caused. Image is obtained and the sharpness of the image deteriorates.

Various means for improving the sharpness are also known. For example, (1) a method of dyeing a film with a water-soluble dye to prevent irradiation (US Pat. No. 3,409,433) (2) US Pat. No. 3,227,554 , No. 3,615,506, No.
Methods using the compounds described in JP 3,617,291 and JP 3,701,783, or the DIR compound and DIR coupler described in JP-B-55-34933 (3) DIR coupler having a so-called timing group described in JP-A-54-145135 , Japanese Patent Application No. 58-7150, a method for increasing edge effect and inter-image effect by using a DIR coupler having a development inhibitor having a large diffusivity (4) Method for reducing coated silver amount (5) Light scattering A method that uses fewer emulsion grains.

(6) A method of forming an unsharp positive image to enhance the sharpness by performing edge enhancement. (7) A method of reducing the emulsion film thickness. However, regarding (2) and (3),
The degree of improvement is not sufficient, and the degree of improvement in sharpness is particularly insufficient in the high frequency region of 20 cycles / mm or more, and the graininess is deteriorated.

Further, with respect to (1), (4), (5) and (7), serious side effects such as deterioration of graininess, deterioration of sensitivity, loss of film strength and the like occur. Regarding (6), although the effect on the sharpness was recognized, there was no improvement effect on the graininess.

As described above, although it is difficult to develop a technical means for achieving high image quality while having high sensitivity, the demand for the small format as described above has been increasing in recent years.
At present, it is becoming stronger.

[Object of the Invention] A first object of the present invention is to provide a silver halide light-sensitive material excellent in graininess and sharpness.

A second object of the present invention is to provide a silver halide light-sensitive material excellent in color reproducibility.

Structure of the Invention It is an object of the present invention to include means for forming an unsharp positive image in combination with at least one light sensitive silver halide emulsion layer on a support, and at least one of the constituent layers. Is a diffusible development inhibitor or a compound that releases a diffusible development inhibitor precursor (hereinafter referred to as a diffusible DIR compound) during development.

Hereinafter, the present invention will be described in detail.

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.
Is mentioned.

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 changes color into the colored compound during development processing, a so-called precursor, which has a main absorption in the main absorption wavelength region of a decolorizing or coloring dye as a result of reaction with an oxidant of a developing agent. It is a compound that produces a diffusion resistant dye (hereinafter referred to as a small diffusion positive compound).

Another preferable example of the positive compound is diffusion resistance, which is a colored compound having a main absorption in the main absorption wavelength region of the coloring dye or a compound which changes color during development processing to the colored compound. It is a compound that is decolorized as a result of a reaction with an 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 means that a colored compound is not generated, or the generated colored compound flows out of the photographic material during the development process, so that unsharp positive image formation is impaired at the end of the image forming process. It means that a colored compound does not remain in the photographic material.

The decolorizable small diffusible positive compound reacts with the oxidized form of the developing agent in the area where a color image is produced by the reaction between the color developing agent and the above diffusion resistant coupler, and decolors. Also, unreacted in the area where the color image by the diffusion resistant coupler does not occur,
Or it remains in a discolored state. As a result, the color image formed by the antidiffusive coupler and the decolorizable small diffusible positive compound are in the inverse relationship, that is, the former forms a negative image, while the latter forms a positive image. . Moreover, since the small diffusible positive compound has a small diffusivity,
An unsharp image, that is, an unsharp positive image will be formed.

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

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

The diffusion-resistant dye-forming small-diffusive positive compound forms an unsharp positive image as described above, and has a main absorption in the main absorption wavelength range of the coloring dye due to the reaction with the oxidant of the developing agent. It produces a pigment. 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 no density change occurs macroscopically.
At the edge portion (boundary portion where the intensity of irradiation light changes), due to the difference in the diffusivity of the positive compound and the diffusion resistant dye that is generated, 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 discoloration in the photographic material during the development processing, and the product generated due to A and Link-B after the reaction is a colored compound. In the above, the product is provided with a substituent having a balanced hydrophilicity or lipophilicity so that the product flows out of the system from the photographic material after the reaction.

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

Specific examples of the former include, for example, phenols, naphthols, 5-pyrazolones, pyrazolotriazoles,
Pyrazolobenzimidazoles, indazolones, acylacetanilides, RCOCH ₃ (R is, for example, alkyl, aryl, or 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.
As a Link-B by cleavage B-SO_TwoNH Naphthol, which releases
, Indanones, indoles, hydroquinones
After the residue is oxidized, it undergoes an intramolecular ring closure reaction,
B-SO as B_Two Releasing phenols (details
Are U.S. Patent Nos. 3,443,939, 3,443,940 and 3,44.
It is described in No. 3,941. ) Residue.

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

here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl, triazolyl, benztriazolyl, urazolyl, 2,4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl , Tetrazo reel and so on. R is 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, preferably an organic residue having an auxochrome group 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. With such a constitution, the compound represented by the general formula [I] may be a compound which is colored or discolored as the B 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 an alkyl group having, for example, 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 by 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, of these types, the following two ties are preferable.

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

Ar is preferably an aryl group which may have a substituent, such as a benzene type or naphthalene type, and a heterocyclic group which may have a substituent, such as isoxazole, and the compound of the general formula [II] is a photograph. Since it moves slightly in the material, it preferably has a semi-diffusion preventing group, and particularly preferably has an Ar moiety. Link ₂ is -N = N- or -CH =. Some of these compounds have already been used as colored couplers, for example, in U.S. Patents 2,449,969, 2,688,538, and
2,706,684, 2,808,329, 3,005,712,
It is known as Belgium Patent No. 570,271 and Japanese Patent Publication No. 44-32461.

However, the present invention and these prior arts have completely different usages of the compounds and different purposes, and the effects obtained are completely different. That is, the prior art is
Since the hue generated by the Coup portion, ie, the coupler portion, represented by the general formula [II] is the main absorption for image formation, the dye formed from this portion does not move in principle and is represented by the general formula [II]. The hue of the compound 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 [II] or the compound after discoloration is the same as the main absorption of the image forming layer. That is, the light-sensitive wavelength region of the silver halide layer combined with the compound of the present invention 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, while the present invention uses a magenta or magenta discoloring compound. .

(Type B): Active site substitution type general formula [III] Coup-Link ₃ -Dye Coup is the same as general formula [II]. Further, Link ₃ has the same meaning as Link of the general formula [I], and similar ones are exemplified, and preferably a group which produces alkali solubility after the coupling reaction, for example, —O—, —SO ₂ —NH—, —NHSO.
_2- and the like are 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 . General formula [III]
Since the compound represented by the formula (3) controls so as to slightly diffuse in the photographic material, it preferably has a semi-diffusion preventing group.

The group is preferably attached to the diffusible one of the coloring dye and Link ₃ -Dye. Compounds belonging to this class are U.S. Pat. Nos. 3,227,550 and 3,47.
No. 6,563, etc., but these prior arts also have Ty
Like peA, it is completely different in usage and does not include the inventive concept. That is, a part is obviously different from the embodiment of the present invention in the case where it is used for the same color correction as the colored 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 are CL in general formula [I].
It reacts similarly to the compound of ASSI, but since the reaction product is colorless, it may remain in the layer after the coupling reaction.

(Type C): Weiss coupler type general formula [IV] Wcoup-Link _4- Dye Wcoup is, for example, R ₂ COCH _2- (R ₂ is alkyl, aryl, or a heterocyclic group having an alkyl group 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 represents -O-, -S- or -SO _2- .

Dye is Link ₄ -Dye a dye residue or a precursor moiety thereof having preferably an alkali-soluble group is flowing on Sogai.

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-Cup portion. Preferably there is.

CLASS III: Redox reaction type Compounds belonging to this class do not undergo a coupling reaction such as CLASSI 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 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 moiety), —O—, —SO ₂ —, —S—, etc. , Dye is a dye residue or its precursor moiety,
It is preferable to have an alkali-soluble group.

When a semi-diffusion preventing group that cooperates with an alkali-soluble group, which may be contained in the Dye part in order to slightly diffuse the compound of the general formula [V], is added to the FUN part. preferable.

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

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

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

This tie can be further classified into the following types.

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

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

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

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

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

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

Formula [I-1] A ₁ -Link ₁ -B _{1 In the} formula, A ₁ is coupled with an oxidized product of a developing agent to form Link ₁
-An organic residue capable of releasing a portion of B ₁ in accordance with the amount of the oxidized product of the developing agent and forming a coupling dye, Link ₁ is a group that bonds A ₁ and B ₁ , and B ₁ is an organic residue. Represents a group.

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

As Link ₁ , for example, -N = N-, -O-, -S
−, −SO ₂ , And so on. Here, -N- is a nitrogen-containing heterocyclic residue, for example, imidoyl succinate, imidoyl phthalate, pyridoyl, imidazolyl, imidazoloneyl, benzimidazolyl, hydantoyl, thiohydantoyl,
Triazolyl, benztriazolyl, urazolyl, 2,
Examples include 4-dioxyoxazolyl, 2,4-dioxothiazolyl, thiadiazolyl, and tetrazolyl.

As B ₁ , when Link ₁ is a chromophore such as —N═N—, for example, an aryl group or a heterocyclic group is preferable,
If Link ₁ is not a chromophore, a dye (eg, azo,
Anthraquinone, azomethine, indophenol, indoaniline, etc.) residue or its precursor is preferred.

The compound represented by the general formula [I-1] having the above constitution may be a dye or a precursor thereof as the 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. In order to make the dye formed by coupling resistant to diffusion, an alkali-soluble group such as a carboxyl group, a sulfo group, a hydroxyl group and a sulfamoyl group, and a group such as an alkyl group that reduces diffusibility are appropriately introduced. The diffusivity before and after the reaction may be balanced.

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

In the general formula [I-2] D ₁ -A ₂ formula, D ₁ represents a dye moiety or a precursor moiety thereof, and A ₂
Represents an organic residue capable of forming a dye by coupling with an oxidized product of a developing agent, and D ₁ represents A upon coupling.
_It never leaves ₂ .

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

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 a 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] can be mentioned.

In the general formula _{[II-1] W-D} 2 formula, _{D 2} has the same meaning as _{D 1} in the formula [I-2], similar to 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 (for example, an alkyl group such as a methyl group and a butyl group) that does not cause a leaving reaction) are substituted, and bisalkylcarbamoyl-aryloxymethane-based or bisalkylcarbamoyl-arylthiomethane-based compound residues.

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

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

In the general formula _{[III-1] Fun-D} 3 formula, _{D 3} has the same meaning as _{D 1} in the formula [I-2], similar to are exemplified.

Fun reacts with an oxidant of a color developing agent to react with the general formula [III
-1] is an organic group having a function of making the compound represented by the formula [1] resistant to diffusion, and examples thereof include a group having a hydroquinone nucleus and a group having a catechol nucleus.

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

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

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

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

General formula [A-1] A ₃ -Link-B _{3 In the} formula, A ₃ reacts with the oxidized form of the developing agent to render the Link-B ₃ portion colorless or soluble depending on the amount of the oxidized form of the developing agent. an organic residue, Link is a group, _{B 3} which binds the _{a 3} and _{B 3} represents an organic residue.

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

A ₃ in the general formula [A-1] is, for example, a cross-oxidation reaction with a residue of a coupler which produces a colored or colorless product 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, for example, alkyl, aryl, or 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.
As a Link-B by cleavage B-SO_TwoNH Naphthol, which releases
, Indanones, indole residues, after being oxidized
Alkali-cleavage yields Link-B as BO , B-
S , B-SO_Two Residues of hydroquinones that release
After being oxidized, the group undergoes an intramolecular ring closure reaction to give Link-B.
As B-SO_Two Releasing phenols (see details
U.S. Pat.Nos. 3,443,939, 3,443,940, 3,443,
941. ) Residue.

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

here, Is a nitrogen-containing heterocyclic residue, such as imidoyl succinate,
Imidoyl phthalate, pyridoyl, imidazolyl, imidazolone nile, benzimidazolyl, hydantoyl,
Thiohydantoyl, triazolyl, benztriazolyl, urazolyl, 2,4-dioxyoxazolyl, 2,
Examples include 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, preferably an organic residue having an auxochrome group 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 configuration, the general formula [A-
The compound represented by [1] may be a compound that is colored or discolored as the B ₃ moiety or A ₃ -Link-B _{3 as a} whole.

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

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

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

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

Compounds belonging to this class produce a negative color dye image at the A ₃ part in the exposed area, but flow out of the system, and when the B ₃ part is a dye, the B ₃ part also leaves the A ₃ part and then leaves the system. A positive image is formed by the compound represented by the general formula [A-1] remaining in the non-exposed area or the color-changed compound thereof because it flows out. 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, the following two are preferable as the preferable ones in this class.

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

Ar is preferably an aryl group, which may have a substituent, for example, a benzene type or naphthalene type, and a heterocyclic group which may have a substituent, for example, isoxazole, and 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.
Link ² is a chromophore, preferably -N = N- or -CH =
Is. Some of these compounds have already been used as colored couplers, for example, U.S. Patents 2,449,969 and 2,688,538.
No. 2, No. 2,706,684, No. 2,808,329, No. 3,005,71
It is known as No. 2 and Japanese Patent Publication No. 44-32461.

However, the present invention and these prior arts have completely different usages of the compounds and different purposes, and the effects obtained are completely different. That is, the prior art is
Since the hue generated by the Coup portion, ie, the coupler portion, represented by the general formula [A-2] is the main absorption for forming an image, it is a principle that the dye generated from this portion does not move, and in addition, the general formula [A-2 ] The hue of the compound represented by the above is a secondary absorption portion different from the above main absorption wavelength region. The present invention is C
It is essential that the dye generated from the oup 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 general formula [A-
The photosensitive wavelength range of the silver halide layer combined with the compound of 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]. Further, 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—, -N
HSO ₂ − and the like are desirable. 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 . Incidentally, the compounds belonging to this type of classification, U.S. Patent No. 3,227,550,
As disclosed in JP-A-3,476,563, these prior arts have completely different usages similar to Type A and do not include the concept of the present invention. That is, a part is obviously different from the embodiment of the present invention in the case where it is used for the same color correction as the colored 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 react in the same manner as the compound of CLASSI in the A ₃ part of the general formula [A-1], but since the reaction product is colorless, the layer after the coupling reaction is formed. It may remain inside.

(Type C): Weiss coupler type general formula [A-4] Wcoup-Link ^4- Dye Wcoup is, for example, R ₂ COCH _2- (R ₂ represents an alkyl, aryl or heterocyclic group.) (Z is an atom group that completes a 5- to 8-membered alicyclic ring, condensed ring, or heterocyclic ring, and R ₃ represents an aryl residue). And since the Wcoup part makes the compound represented by the general formula [A-4] resistant to diffusion, it is preferably a diffusion preventing group such as a carbon number of 1
It has 7 or more groups.

Link ⁴ represents -O-, -S- or -SO _2- .

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

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

(Type D): DRR compound type General formula [A-5] FUN-Link ⁵ -Dye FUN shows a redox mother nucleus, and preferably 2-, 3-.
Or 4-phenol, 4-α-naphthol, 1-β-naphthol, 2-hydroquinone, 3-indole, 4-
A pyrazolone -5 residues, Link ⁵ is -NHSO ₂ -
(Nitrogen atom bonded to FUN part), -O-, -SO
_2- , -S- and the like, Dye is a dye or a precursor residue thereof, and preferably has 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.

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. As a result, an unsharp positive image is formed.

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

In the present invention, the diffusible DIR compound is a development inhibitor which is released by a reaction with an oxidant of a color developing agent, or
The diffusivity of the compound capable of releasing the development inhibitor is 0.34 or more in the diffusivity according to the evaluation method described below, and the diffusivity is 0.4.
The above is preferable.

In the present invention, the diffusivity can be evaluated by the following method.

Photosensitive material samples (I) and (II) each having a layer of the following composition were prepared on a (transparent) support.

Sample (I): 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) as silver The amount of silver coated with a gelatin coating liquid containing 0.07 mol per mol is
1.1 g / m ² of gelatin was applied so that the amount of gelatin would be 3.0 g / m ² , and a protective layer was formed on it; silver iodobromide not chemically and spectrally sensitized (2 mol of silver iodide) %, And an average particle size of 0.08 μm) was applied so that the coating silver amount was 0.1 g / m ² and the gelatin coating amount was 0.8 g / m ² .

Sample (II): Silver iodobromide removed from the protective layer of Sample (I).

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

Samples (I) and (II) were subjected to white exposure using a wedge and then processed according to the processing method of Example 1 described below except that the development time was 2 minutes and 40 seconds. The sensitivity of Sample (II) is 6 for the developer.
There were used 0% (logarithmic expression, -ΔlogE = 0.22) to which each development inhibitor was added in an inhibitory amount, and one to which no development inhibitor was added.

The sensitivity of the sample (I) when the development inhibitor is not added is So,
The sensitivity of the sample (II) is So ', the sensitivity of the sample (I) when the development inhibitor is added is S _I, and the sensitivity of the sample (II) is S _II.
Then, the desensitization of the sample (IV) ΔSo = So′−S _{II The} desensitization of the sample (V) ΔS = So−S _I Diffusivity = ΔS / ΔSo

However, all the sensitivities were set to the logarithm (-logE) 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 1 illustrates the diffusivity of several development inhibitors.

The diffusible DIR compound used in the present invention can be selected from compounds represented by the following general formulas, for example.

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 is sufficient 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 thiazolideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl group, an N-alkylcarbamoyl group,
N, N-dialkylcarbamoyl group, nitro group, amino group, N-arylcarbamoyloxy group, sulfamoyl group, N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group,
Arylthio group, aryl group, heterocyclic group, cyano group,
It represents an alkylsulfonyl group or an aryloxycarbonylamino group. n represents 1 or 2, 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) is _{R 1} in (2A) ~ (2D)
And X represents an oxygen atom or a sulfur atom.

In the general formula (4), R ₂ represents an alkyl 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, R ₄ represents a hydrogen atom,
It represents an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino 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 group. Substituents are 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 Alternatively, it is an arylthio group or the like.

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

When R ₁ , R ₂ , R ₃ or R ₄ represents a heterocyclic group, a 5-membered or 6-membered monocyclic or condensed ring containing at least one selected from a nitrogen atom, an oxygen atom and a sulfur atom as a hetero atom. Represents a ring, pyridyl group, quinolyl group, furyl group, benzothiazolyl group, oxazolyl group,
It is selected from an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imide group, an oxazine group and the like, which may be further substituted with the substituents listed for the aryl group.

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

In the 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 further represents the following general formula (6).

General formula (6) -TIME-INHIBIT In the formula, the TIME group is a group which is bonded to the coupling position of the coupler and can be cleaved by the reaction with the color developing agent, and after the cleavage from the coupler, the INHIBIT group is appropriately suppressed. It is a group that can be released. The INHIBIT group is a group which becomes a development inhibitor by the above release.

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 represents 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 or an alkanesulfonyl group, and represented by the general formulas (7), (8), (9), (11) and (13)
Is an integer of 1 or 2, and in the general formulas (7), (11), (12) and (13), k is an integer of 1 or 2, and 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 in the general formulas (12) and (13), B is an oxygen atom or (R ₆ has the same meaning as previously defined), and the INHIBIT group is represented by the general formula (2A), (2B),
Except for the carbon number, it has the same meaning as the general formula defined in (3), (4) and (5).

However, in the general formulas (2A), (2B) and (3),
The total number of carbon atoms contained in each R ₁ in the molecule is 1 to 3
2, the number of carbon atoms contained in R ₂ in the general formula (4) is 1 to 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 above for the R _{1 to} R ₄ 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.

Among the diffusible DIR compounds represented by the general formula (1), those having a leaving group represented by the general formulas (2A) and (2B) to (5) are particularly preferable.

Examples of the yellow image-forming coupler residue represented by A in the general formula (1) include pivaloyl acetanilide type,
Benzoyl acetanilide type, malon diester type, malon diamide type, dibenzoyl methane type, benzothiazolyl acetamide 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,
Coupler residues derived from heterocycle-substituted acetamide or heterocycle-substituted acetate contained in U.S. Pat.No. 3,841,880 or U.S. Pat.No. 3,770,446, U.K. Patent 1,459,171
No. 2, West German Patent (OLS) 2,503,099, JP-A-50-139738
Or a coupler residue derived from an acylacetamide described in Research Disclosure 15737 or a heterocyclic coupler residue described in US Pat. No. 4,046,574.

The magenta color image coupler residue represented by A is 5-
Oxo-2-pyrazoline nucleus, pyrazolo- [1,5-a]
A coupler residue having a benzimidazole nucleus or a cyanoacetophenone type coupler residue is preferred.

The cyan image forming coupler residue represented by A is preferably a coupler residue having a phenol nucleus or an α-naphthol nucleus, and an indazolone or pyrazolotriazole coupler residue.

Further, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after releasing the development inhibitor by coupling with the oxidized product of the developing agent. Examples of this type of coupler residue represented by A include U.S. Pat. No. 4,052,213
Issue, Issue 4,088,491, Issue 3,632,345, Issue 3,958,99
Examples thereof include coupler residues described in No. 3 or No. 3,961,959.

Preferred diffusive DIR compounds used in the present invention include, but are not limited to, the following compounds.

These compounds are disclosed in U.S. Patents 4,234,678 and 3,227,554.
No., No. 3,617,291, No. 3,958,993, No. 4,149,88
6, 3,933,500, JP-A-57-56837, 51-13239
No. 2,072,363, 2,070,266, Research Disclosure, No. 21228, December 1981, and the like.

The diffusible DIR compound of the present invention is 0.0001 per mol of silver.
It is suitable to use 0.1 mol, preferably 0.001 to 0.05 mol.

To describe the background of the present invention, the present inventors have earnestly conducted research on a method for improving the deterioration of graininess when a diffusive DIR is used, and as a result, surprisingly, the graininess improvement effect is not inherently present. The present inventors have found that the graininess can be improved by concomitant use with a possible positive compound, and arrived at the present invention.

The silver halide emulsion used in the present invention includes silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride. Any of those used in emulsions can be used, but 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 pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method,
Silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. A conversion method 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. The salts can be removed according to the method described in Research Disclosure (hereinafter abbreviated as RD) No. 17643, Item II.

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

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

The silver halide grain may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these 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,
The noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

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

As the sensitizing dye, a cyanine dye, a merocyanine dye,
A complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a steryl dye and a hemioxanol dye are used.

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

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

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

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners which crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in 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 (dimethylol urea, methylol dirohtylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5 -Triacryloyl-hexahydro-s-triazine, 1,3
-Vinylsulfonyl-2-propanol etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s
-Triazine, etc.), mucohalogen acids, (mucochloric acid, mucophenoxycyclolic acid, etc.) and 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 RD17643, section XII.

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

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

In the color development processing, the emulsion layer of the light-sensitive material forms a dye by a coupling reaction with an oxidant of an aromatic primary amycin 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 sip coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce 4 molecules of silver ion in order to form 1 molecule of dye. Either of two equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidized product of a developing agent to develop a development accelerator, a bleaching accelerator, a developer, a silver halide solvent,
Included are compounds that release photographically useful fragments such as toning agents, hardeners, fog agents, chemical sensitizers, spectral sensitizers.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color forming couplers that can be used include, for example, U.S. Pat.
No. 7, No. 3,265,506, No. 3,408,194, No. 3,551,1
No. 55, No. 3,582,322, No. 3,725,072, No. 3,891,
445, West German patent 1,547,868, West German published application 2,219,917
No. 2,261,361, No. 2,414,006, U.S. Pat.No. 1,42
5,020, JP-B-51-10783, JP-A-47-26133, 48-
73147, 50-6341, 50-87650, 50-123342
50, 130442, 51-21827, 51-102636, 51-102636
52-82424, 52-115219, 58-95346, etc.

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,
No. 418,959, No. 2,424,467, Japanese Patent Publication No. 40-6031, JP-A No. 4
9-74027, 49-74028, 49-129538, 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
The one described in No. 0943 can be mentioned.

As the cyan dye-forming coupler, a phenol or naphthol coupler is used in the general formula. 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.

Dye-forming couplers, colored couplers, DIR couplers, DIRs that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, antifoggants, UV absorbers,
Among the fluorescent whitening agents and the like, various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method can be used for the hydrophobic compound, which is the chemical structure of the hydrophobic compound such as the coupler. It can be selected as appropriate. 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. With a water-soluble organic solvent, and using a surfactant in a hydrophilic binder such as an aqueous gelatin solution, a stirrer, homogenizer, colloid mill, flowgit mixer,
It may be added to the target hydrophilic colloid liquid after emulsifying and dispersing using a dispersing means such as an ultrasonic device. 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.

When the dye-forming coupler, the DIR coupler, the colored coupler, the DIR compound, the image stabilizer, the antifoggant, the ultraviolet absorber, the optical brightener, etc. have an acid group such as carboxylic acid or sulfonic acid, they are treated as an alkaline aqueous solution. It can also be incorporated into a hydrophilic colloid.

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 which can be preferably used are those described in Item VII, J of RD17643.

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

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

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

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, a compound such as a development accelerator or a development retarder which changes the developability and a bleaching accelerator can be added. A compound which can be preferably used as a development accelerator is RD1764.
No. 3, Item XXI, B to D, and the development retarder is the compound No. 17643, Item XXI, Item E. A black and white developing agent and / or its precursor may be used for the purpose of promoting development and other purposes.

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

A fluorescent brightening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. The compound which can be preferably used as the optical brightening agent is described in the item V of RD17643.

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

Reduction of gloss of the light-sensitive material, improvement of writing property on the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material,
A matting agent can be added for the purpose of preventing sticking of the photosensitive materials to each other. Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resins, 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 in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be a protective colloid layer other than the emulsion layer and / or the emulsion layer on the side of the support on which the emulsion layer is laminated. May be used for. Antistatic agents preferably used are the compounds described in RD17643 XIII.

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

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

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

At the time of applying the light-sensitive material, a thickener may be used to improve the coatability. For a hardener such as a hardening agent, which causes gelation before coating because it has a high reactivity, it should be mixed just before coating with a static mixer or the like. Is preferred.

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

The surfactant is not particularly limited, and examples thereof include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide-based, glycerin-based, glycidol-based, higher alkylamines, quaternary ammonium salts, pyridine and the like. Heterocycles, cation surfactants such as phosphonium or sulfonium, carboxylic acids, sulfonic acids,
Anionic surfactants containing an acidic group such as phosphoric acid, sulfuric acid ester and phosphoric acid ester, and amphoteric surfactants such as amino acids, aminosulfonic acids, sulfuric acid of amino alcohols or phosphoric acid ester 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, a bleach-fixing treatment step can be carried out using a 1-bath bleach-fixing solution, or a monobath processing using a 1-bath development bleach-fixing solution capable of performing color development, bleaching and fixing in a single bath. The steps can also be performed.

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-bleach fixing processing step-activator processing step-bleaching processing step-fixing processing step-monobath processing step The processing temperature is usually 10 ° C. ~ 65 ℃ is selected,
The temperature may exceed 65 ° C. Preferably from 25 ° C
Treated at 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 aminoenol type and p-phenylenediamine type 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 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 color developing agents are N, N '.
It is a -dialkyl-p-phenylenediamine compound, and the alkyl group and the phenyl group may be substituted or may not be substituted. Among them, particularly useful compound examples are N-N'-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-hydroxy Ethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N- (2-methoxyethyl)-
N-methyl-3-rotylaniline-p-toluene sulfonate and the like can be mentioned.

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 more, preferably about 9 to 13.

In the color developing solution used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, an aromatic secondary alcohol, hydroxamic acid, bentose or an antioxidant is used. Hexose, pyrogallol-1,
It may contain 3-dimethyl ether or the like.

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

The bleaching process may be performed at the same time as the fixing process as described above. It may be done individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt, copper are coordinated are used. . Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N- (β-oxyethyl) -N, N ′,
N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminenatetrapropionic acid , Phenylenediamine tetraacetic acid and the like.

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

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

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

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

The fixer may have a commonly used composition. As the fixing agent, a compound that reacts with silver halide as used in a usual fixing process to form a complex salt of an aqueous solution, 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, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / or more so that they can be dissolved, but generally 70 to 250 g / is used. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

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

The pH of the fixer used is 3.0 or higher, but generally 4.5 to 1
0, 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. In addition, a bleach-fixing solution having a composition in which a small amount of a halogenide such as ammonium bromide other than the above-mentioned silver halide fixing agent and an ethylenediaminetetraacetic acid iron (III) complex bleaching agent is added, or conversely, a halogenating agent such as ammonium bromide is used. A bleach-fixing solution having a composition containing a large amount of a halide, and a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetic acid iron (III) complex bleaching agent and a large amount of a halide such as ammonium bromide are used. I can do things. Examples of the halide include hydrochloric acid, hydrobromic acid, in addition to ammonium bromide,
Lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used.

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, the pH buffer which can be contained in the bleach-fixing solution, and other additives 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.

The preferred use of the diffusible DIR compound and the positive compound of the present invention will be described. It is preferable that the diffusible DIR compound of the present invention is contained in a light-sensitive silver halide emulsion layer. In a layer structure in which a plurality of layers are made different and separated and laminated (hereinafter referred to as a multilayer structure), it is preferable to mainly add to a photosensitive layer other than the highest sensitivity layer.

The positive compound of the present invention is preferably added to the highest sensitivity layer when the color-sensitive layer (hereinafter referred to as DIR layer) to which the diffusible DIR compound of the present invention is added has a multi-layer structure (case-A). ), And when a non-photosensitive layer is provided between the same color-sensitive layers, it is more preferable to add to the non-photosensitive layer (case-B), most preferably the present invention. The diffusible DIR compound is added to the non-photosensitive layer provided between the photosensitive layer and the photosensitive layer having different color sensitivity (case-C). .

In case-A, the effect as an anti-irradiation dye is exerted on the low-sensitivity layer, and a larger sharpness improving effect is exhibited, and in case-B, in addition to the effect in case-A, a developing agent is added. As an scavenger of the oxidant, the color from the most sensitive layer is turbid, so that the so-called diffuse projection effect is reduced and the graininess improving effect is increased.

In case-C, when it is positioned on the side opposite to the incident side of light during exposure from the DIR layer, the light that has once passed through the DIR layer is reflected and sharpened with a minimum decrease in sensitivity. When the so-called antihalation effect that prevents the deterioration of the property is caused, and further, the scavenger of the oxidized developing agent is used to prevent the color from the different color sensitive layer from becoming turbid, and when the different color sensitive layer develops a color, Since the concentration of the positive compound is low and the concentration is high when no color is developed, a larger interimage effect can be obtained.

In addition, when it is located on the same side as the incident side of fog light from the DIR layer, the effect of preventing color fogging and the effect of increasing the inter-image effect are the same as when it is located on the opposite side. In addition, the action as an anti-irradiation dye has an advantage that it is more greatly expressed than the effect in case-A. However, the term "anti-irradiation" as used herein also includes the meaning of preventing the sharpness deterioration action due to the spread of light in the non-photosensitive layer provided between the emulsion layer (scattering layer) and the scattering layer.

[Examples] Specific examples of the present invention will be described below, but embodiments of the present invention are not limited thereto.

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

Second layer; monodispersity composed of AgBrI containing 0.35 μm average particle size (AgI) and 6 mol% AgI (Emulsion I)
…… Total silver coating 1.6g / m ² Sensitizing dye III …… 2.3 × 10 ^-5 mol sensitizing dye IV per 1 mol silver …… 1.3 × 10 ^-5 mol magenta coupler (M -1) ... 0.050 mol per 1 mol of silver Colored magenta coupler (CM-1) ... 0.009 mol per 1 mol of silver Third layer: polymethylmethacrylate particles (diameter 1.5 μm)
And a gelatin layer containing formalin scavenger (HS-1). In addition to the above composition, each layer contains a gelatin hardening agent (H-
1) and a surfactant were added.

Second layer of Sample 1, as shown in Table-1, except that the compound of the present invention or the comparative compound is added is
o. 2-14 were created.

Each sample No. created in this way Wedge exposure of 1 to 14 was performed using white light, and then the following development processing was performed.

Processing step (38 ° C) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Used in each processing step The composition of the treatment liquid is as follows.

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

[Bleach] Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 m Add water to adjust the pH to 1 and adjust the pH to 6.0 with ammonia water.

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 using acetic acid.

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

The sharpness (MTF) and RNS of each of the obtained samples were measured using white light (W). The results are shown in Table-1.

The effect of improving the sharpness is the MTF (Modulation T
ransfer function) was obtained and indicated as a relative value of MTF at 20 lines / mm (sample No. 1 is 100).

The RMS value is the minimum density + 0.3, and the aperture scanning area is 250 μm.
^The value is expressed as 1,000 times the standard deviation of the fluctuation of the density value caused by scanning with a microdecitometer of No. ² .

It can be seen that by using the diffusible DIR of the present invention and the positive compound in combination, the graininess is remarkably improved, and the sharpness is improved more than expected.

Example 2 A multilayer color photographic element sample 15 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-15 (Comparison) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL) 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) ... Silver coating amount 1.8 g / m ² Sensitizing dye I ... 6 × 10 1 mol of silver ^-5 mol Sensitizing dye II: 1.0 × 10 ^-5 mol for 1 mol of silver Cyan coupler (C-1): 0.06 mol for 1 mol of silver Colored cyan coupler (CC-1): 1 silver 0.003 mol per mol DIR compound (DR-1) ... 0.002 mol per 1 mol silver Fourth layer; high-sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size () 0.60 μm, AgI monodisperse emulsion comprising AgBrI containing 7.0 mol% (emulsion II) ...... silver coating amount 1.3 g / m ² sensitizing dye I ...... 1 mol of silver relative to 3 × 10 ^-5 mol sensitizing dye II ...... silver 1.0 × 10 ^-5 mol cyan coupler per 1 mol of (C-1) ...... silver mole relative to 0.02 mole colored cyan coupler (CC- ) 0.0015 mol DIR compound against ...... silver mole (DR-1) 0.001 mol fifth layer against ...... silver mole; intermediate layer (I.L.) The same as the second layer, the gelatin 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 increase per 1 mol of silver Sensitizing 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): / 1 mol of silver 0.009 mol DIR compound (DR-1) ... 0.0010 mol per 1 mol of silver 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II ... Coating silver amount 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol per 1 mol of silver Sensitizing dye IV: 1.0 × 10 ^-5 mol per 1 mol of silver Magenta coupler (M-1): 1 mol of silver 0.020 mol Colored magenta coupler (CM-1) ... 0.002 mol per 1 mol of silver DIR compound (DR-1). 0.0010 mol Eighth layer; Yellow filter layer (YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Ninth layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (Emulsion III) consisting of AgBrI with an average grain size of 0.48 μm and 6 mol% of AgI ... Silver coating amount increased by 0.9 g / m ^2. Sensitizing dye V: 1.3 × 10 ⁻⁵ moles per 1 mole of silver Yellow coupler (Y-1): 0.34 moles per 1 mole of silver 10th layer; high-sensitivity blue-sensitive emulsion layer (BH-1) average AgBrI containing 0.8 μm particle size and 115 mol% Ag
Monodispersed emulsion (Emulsion IV): Silver coating amount 0.5 g / m ² Sensitizing dye V: 1.0 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (Y-1): 1 mol of silver On the other hand, 0.13 mol DIR compound (DR-1) ... 0.0005 mol per mol of silver Eleventh layer; First protective layer (Pro-1) Silver iodobromide (AfI 1 mol% average particle size 0.07 μm) Silver Coating amount 0.5g / 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) Each layer contains a gelatin hardener (H −
1) and a surfactant were added.

With the contents shown in Table 2 in Sample 15, only the addition of the compound of the present invention or the comparative compound was changed to Sample No. 16
~ 31 was created. Sample No. thus obtained
15 to 31 were treated in the same manner as the method shown in Example 1.

The sharpness (MTF) and RMS of each of the obtained samples were measured using green light (G). The results are also shown in Table 2.

The sharpness improving effect evaluation method is to obtain the MTF of the dye image,
Relative value of MTF at 20 lines / mm (Sample No. 15 is 100
And)).

The RMS value is the minimum density + 0.7, and the aperture scanning area is 250 μm.
^The value is represented by 1,000 times the standard deviation value of the fluctuation of the density value caused by scanning with the microdensitometer of No. ² .

As shown in Table 2, in the present invention, similar to Example 1, a great improvement in graininess and sharpness is recognized. Further, it can be seen that the effect of the present invention is remarkable when the positive compound is added to the non-photosensitive layer provided between the different color photosensitive layers. Further, in the present invention, the color purity of green is higher than that of the comparative example.

Example 3 Sample 31 was prepared except that the same gelatin layer as the second layer was applied between the third layer and the fourth layer of the sample 15 in the same manner. At this time, in Sample 31, regarding the layer including the fourth layer of Sample 15 and separated from the support from the fourth layer, the layer No. Shall be incremented by 1 and represented.

Samples 32 to 4 were different from the sample 31 except that the compound of the present invention or the comparative compound was added, as shown in Table 3.
2 was prepared, and the samples 31 to 42 thus obtained were treated in the same manner as in the method described in Example 1.

The sharpness (MTF) and RMS of each of the treated samples were measured using red light (R). The results are also shown in Table-3.

For the improvement in sharpness, the MTF of the dye image is calculated,
Relative value of MTF at 20 lines / mm (Sample No. 31 is 100
And)).

The RMS value is the minimum density + 0.7, and the aperture scanning area is 250 μm.
^The value is expressed as 1,000 times the standard deviation of the fluctuation of the density value caused by scanning with the microdensitometer of No. ² .

From Table 3, it can be seen that the effects of the present invention are exhibited in the same manner as in Examples 1 and 2. Further, a great effect is recognized when the positive compound is added to the non-photosensitive layer provided between the photosensitive layers having the same color sensitivity. Further, in the present invention, the color purity of the belled is higher than that of the comparative example.

Example 4 Sample No. in Example 2 19, 20, 23, 24, the positive compound U-18 of the present invention was converted into U-33, U-1.
When changed to 3, the same results as in Example 2 were obtained.

In addition, the sample No. 16, 23 and 24, the diffusible DIR compound D-57 of the present invention was added to D-2, D
When changed to −40, the same result as in Example 2 was obtained.

Example 5 Sample No. in Example 3 When the positive compound U-26 of the present invention was changed to U-6, U-10, U-16 in 40, the same results as in Example 3 were obtained.

The compounds contained in each layer of the samples in Examples 1 to 5 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'- The-
(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'-dibenzooxacarboxyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5 ′ -Methoxythiacyanine

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References The theory of the Photographic Procedures P. 495

Claims (1)

[Claims] 1. A means for forming an unsharp positive image in combination with at least one light-sensitive silver halide emulsion layer on a support, wherein at least one of the constituent layers is diffusive during development. A silver halide photographic light-sensitive material comprising a compound that releases a development inhibitor or a diffusion-type development inhibitor precursor.