JPS62166338A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the quality (sharpness and graininess) of an image without deteriorating the sensitivity by using a diffusible DIR compound and a coupler assuming no color. CONSTITUTION:This sensitive material contains a diffusible DIR compound and a compound which takes part in a coupling reaction with the oxidized product of a developing agent but does not form a dye. Generally, the sensitive material has three silver halide emulsion layers and plural nonphotosensitive hydrophilic collodial layers including intermediate layers on the support. The emulsion layers have been spectrally sensitized so that they have sensitivity to blue light, green light and red light, respectively. The emulsion layers may be coated in any order from the support side,a concrete example of the diffusion DIR compound is represented by formula 1. A typical concrete example of the coupler assuming no color is represented by formula 2.

Description

Detailed Description of the Invention ■9 Background of the Invention [Technical Field] The present invention relates to a silver halide photographic light-sensitive material that provides high-quality images. This invention relates to improved silver halide photographic materials.

[Problems with conventional technology] In recent years, with the miniaturization of cameras, there has been a desire for smaller screen formats for negative films, etc. Therefore, it is necessary to increase the sensitivity and high image quality of silver halide photographic materials. There has been a marked increase in demand for

In fact, many technological improvements have been made to date to meet this demand, and the performance of silver halide photographic materials (hereinafter abbreviated as "photosensitive materials") is rapidly progressing.

Although there have been significant improvements in image quality, no technology has yet been found that is sufficient to satisfy all performance requirements such as sharpness, graininess, and color reproducibility.

For example, as a means of improving sharpness, light (
There is a method to reduce the filtration of irradiation light. Some of these methods involve adding a colored substance such as a dye to the hydrophilic colloid layer to absorb irradiation light, but this method has the problem of being accompanied by a desensitizing effect. Another method is to reduce the thickness of the entire hydrophilic colloid layer to minimize the light scattering path, especially for the silver halide emulsion layer near the support. It can be an effective method because it is shorter. However, in this method, it is essential not to reduce the amount of binder, etc. used, and for this reason, in multilayer light-sensitive materials with built-in couplers, which are the mainstream of color negative films, the number of addition ports for couplers, etc. is naturally limited, as this causes deterioration of film thickness. This makes it difficult to obtain good dye image quality. Moreover, above all, it is necessary to reduce the silver teeth contained in the silver halide emulsion layer, which is disadvantageous for achieving high image quality by improving graininess.

In order to improve the graininess, the grain size of the silver halide grains contained in the silver halide emulsion layer must be reduced, which is an unfavorable direction. Another method is to increase the number of coloring dye points by increasing the number of silver halide grains contained in the silver halide emulsion layer, but this is disadvantageous for improving sharpness for the reasons mentioned above, and it is difficult to improve sharpness during development. Latent image bleaching occurs due to the excess oxidized product of the phenomenon agent produced, and increasing the number of silver halide grains does not necessarily result in an increase in the number of coloring dye spots in the same proportion.

In addition, one of the characteristics required for color photographic materials is
When one color-sensitive layer forms a dye image, in order to prevent the phenomenon caused by the oxidized product of the developing agent generated therein,
Conventionally, an intermediate layer is installed between different color sensitivities, and to this layer a scavenger for the oxidized form of the oxidation agent, a colorless coupler, or a diffusion inhibitor such as fine silver halide particles or polymer latex is added. However, when used as a stand-alone technique, its effectiveness has not necessarily reached a satisfactory level.

Also, a compound (DIR compound) that reacts with the oxidized form of the main agent to release a development inhibitor or development inhibitor precursor.
using the interimage effect (interlayer effect below, II
A technique for improving color reproducibility by emphasizing (abbreviated as E) is known, and various DIR compounds are used as these DIR compounds. For example, a so-called DIR coupler reacts with an oxidized form of a color developing agent to form a coloring dye and releases a development inhibitor during development; So-called DIR substances that do not form coloring dyes, substances that directly release a development inhibitor by reacting with an oxidized form of a color developing agent, and substances that release a development inhibitor indirectly, such as JP-A-54-
No. 145135, No. 57-154234, No. 58-
No. 162949, No. 58-205150, No. 59-
No. 195643, No. 59-206834, No. 59-2
No. 06836, No. 59-210440, No. 60-74
29 etc. (hereinafter referred to as timing DIR)
compounds), etc. In this specification, those exhibiting the above-mentioned DIR effect are collectively referred to as DIR compounds.

These DIR compounds are processed into silver halide color photosensitive UPI
When used in 1.1., the development inhibitor is released from the DIR compound during development, resulting in the effect of inhibiting the development of other silver halide emulsion layers, that is, 1.1. In particular, DIR compounds capable of releasing a so-called diffusible inhibitory group or a diffusible development inhibitor precursor are effective.

As a result of extensive research, the present inventors have found that by incorporating both a diffusible DIR compound and a compound that undergoes a coupling reaction with the oxidized form of a color developing agent but does not form a dye into a silver halide photographic light-sensitive material, We found a greater effect than expected.

■0 Purpose of the Invention The purpose of the present invention is to improve image quality (sharpness, sharpness, etc.) without impairing sensitivity.
Another object of the present invention is to provide a silver halide photographic material with improved graininess (graininess), and another object of the present invention is to provide a silver halide photographic material with improved color reproducibility.

The above object of the present invention and other objects that will become clear from the following description are, in a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support,
A compound that reacts with the oxidized form of the current Q active ingredient to release a diffusible phenomenon inhibitor or a phenomenon inhibitor breaker (diffusible DIR)
This is achieved by a silver halide photographic light-sensitive material characterized by containing both a compound (compound) and a compound (colorless coupler) that undergoes a coupling reaction with the oxidized form of a developing agent but does not form a dye.

■1 Specific structure of the invention As described above, the silver halide photographic light-sensitive material of the present invention (hereinafter referred to as "photosensitive material") is a light-sensitive material having at least one hydrophilic colloid layer on a support. It contains both a compound and a compound that undergoes a coupling reaction with the oxidized form of a developing agent but does not form a dye.

The silver halide emulsion layer contained in this light-sensitive material is most commonly composed of three types of emulsion layers on a support that are selectively spectrally sensitized to have sensitivity to blue light, green light, and red light. and a plurality of non-photosensitive hydrophilic colloid layers (including an intermediate layer). The three types of photosensitive emulsion layers may be applied in any order when viewed from the support side. Further, each emulsion layer having the same color sensitivity may be separated into a plurality of emulsion layers having different sensitivities, each containing a diffusion-resistant coupler that develops substantially the same hue, and preferably into two or three emulsion layers. It is something that Examples of layer configurations include the following. In a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer (stubborn structure) which are sequentially coated on a support, the high-sensitivity halogen in each light-sensitive silver halide emulsion layer is The silver halide emulsion layer and the low-sensitivity silver halide emulsion layer are separated and stacked adjacently. Including this stubborn configuration, JP-A-51-4902
No. 7, JP-A-53-97424, JP-A-58-521
The object of the present invention can be achieved with any of the reverse layer configurations described in No. 15 and the like. A non-photosensitive hydrophilic colloid layer (intermediate layer) can be arbitrarily provided between emulsion layers having different color sensitivities, or between emulsion layers having substantially the same color sensitivity but different sensitivities. In the present invention, a compound that undergoes a coupling reaction with an oxidized developing agent but does not form a dye may be added to any layer, but is preferably added to the most sensitive emulsion layer of each color-sensitive emulsion layer. or added to an intermediate layer adjacent to the most sensitive emulsion layer. This intermediate layer may be located either on the far side or near the emulsion layer when viewed from the support.

In addition, in the present invention, the diffusible DIR compound may be added to one layer of the same color-sensitive layer in the case where there are a plurality of same color-sensitive layers. The effect becomes even greater when used for.

When there are a plurality of same-color sensitive layers and it is added to only one layer, it is preferable to use it in the layer containing the most silver m. Also, diffusivity D
It is better to use IR compounds that have timing properties in the group that leaves when reacting with the oxidized form of the developing agent (after the leaving group is cleaved from the DIR compound, the development-inhibiting component can be released in an appropriately controlled manner). More preferred.

The amount of m to be added varies depending on the type of diffusible DIR compound and the layer to which it is added, and is preferably from 1.times.10@-4 to 2.times.10@-2 mol per mol of silver, although it cannot be generalized.

Next, the diffusible DIR compound preferably used in the present invention will be explained.

The diffusible DIR compound of the present invention has the following general formula.

Diffusible DIR Compound General Formula (1) % Formula %) In the formula, A represents a coupler component, m represents 1 or 2, and Y is bonded to the coupling position to the coupler component to form a bond with the oxidized product of the color developing agent. It is a group that leaves by reaction and represents a highly diffusible development inhibitor or a compound capable of releasing a development inhibitor.

A only needs to have the properties of a coupler, and it is not necessarily necessary to create a dye by coupling.

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

Below are the blank spaces: General formula of diffusible DIR compound (2 people) General formula of diffusible DIR compound (2B) General formula of diffusible DIR compound (2C) General formula of diffusible DIR compound (2D) General formula of diffusible DIR compound (2E) N ( X; 0.S Se) Diffusible DTTt compound general formula (3) Diffusible DIR compound general formula (4) Diffusible DIR compound general formula (5) Above general formulas (2A) to (2D) and (3 ), in
R1 is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group, a thiazolylideneamino group, an aryloxycarbonyl group, an acyloxy group, a carbamoyl N-alkylcarbamoyl group, N,N
-Dialkylcarbamoyl group, nitro group, amino group, N
-Arylcarbamoyloxy represents a N-alkylcarbamoyloxy group, hydroxy group, alkoxycarbonylamino group, alkylthio group, arylthio group, aryl group, heterom group, siam L alkylsulfonyl group or aryloxycarbonylamino group. n represents 1 or 2, and when n is 2, R
1 may be the same or different, and the total number of carbon atoms contained in n R1 is 0 to 10.

R2 in the above general formula (2E) is R1 in (2A) to (2D)
X represents an oxygen atom, a sulfur atom or a selenium atom, and in the general formula (4), R2 represents an alkyl group, an aryl group or a heterocyclic group.

In general formula (5), R3 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and R4 represents a hydrogen atom, an alkyl group, an aryl group, a halogen atom, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylaminoalkane. Represents a sulfonamide group, cyano group, heterocyclic group, alkylthio group or amino group.

R1, R2, Ra or R4 represents an alkyl group, which may be substituted or unsubstituted, linear or branched, or cyclic alkyl. Substituents include halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group,
Examples include carbamoyl group, hydroxy group, alkanesulfonyl group, arylsulfonyl group, alkylthio group, and arylthio group.

When R+, R2, R3 or R4 represents an aryl group, the aryl group may be substituted.

As substituents, alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups, sulfamoyl groups, hydroxy groups, carbamoyl groups, aryloxycarbonylamino groups, acylamino groups, cyano groups Alternatively, it may be a ureido group.

When R+, R2, R3 or R4 represents a heterocyclic group, it represents a 5- or 6-membered monocyclic or condensed ring containing a nitrogen atom, oxygen atom, or sulfur atom as a heteroatom, such as a pyridyl group, a quinolyl group, selected from a furyl group, a benzothiazolyl group, an oxacylyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imido group, an oxazine group, etc., which are further substituted with the substituents listed for the above aryl group. Good too.

In general formulas (2E) and (4), the number of carbon atoms contained in R2 is 1 to 15.

In the above general formula (5), the total number of carbon atoms contained in R3 and R4 is 1 to 15.

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

Diffusible DIR compound general formula (6) %Formula% In the formula, the TIME group is a group that is bonded to the coupling position of the coupler and can be cleaved by reaction with a color developing agent,
It is a group that can release an INHIBIT group in a moderately controlled manner after being cleaved from a coupler.

The INHIBIT group is a development inhibitor.

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

The following are blank spaces ^ Diffusible DIR compound general formula (11) Diffusible DIR compound general formula (12) Diffusible DIR compound general formula (13) In general formulas (7) to (13), R5 is a hydrogen atom, a halogen atom, Represents an alkyl group, alkenyl group, aralkyl group, alkoxy group, alkoxycarbonyl group, cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group, hydroxy group, alkanesulfonyl group, General formulas (7), (8), (9), (1o) and (13
), l represents 1 or 2, and general formula (7),
In (11), (12) and (13), K represents an integer from O to 2, and in general formulas (7), (10) and (
In 11), R6 represents an alkyl group, alkenyl group, aralkyl group, cycloalkyl group or aryl group, and in general formulas (12) and (13), B represents the same meaning as. ), and the INHIBIT group has the general formula (2A), (2B), (3)
, (4) and (5) have the same meanings except for the number of carbon atoms.

However, in general formulas (2A), (2B), and (3), the total number of carbon atoms contained in each R1 in the -molecule is 1 to
32, and in the general formula (4), the number of carbon atoms contained in R2 is 1 to 32, and in the general formula (5), the total number of carbon atoms contained in R3 and R4 is 0 to 32.

When R5 and R6 represent an alkyl group, it may be substituted or unsubstituted, chain-like or cyclic. Examples of the substituent include the substituents listed when R1-R2 are alkyl groups.

When R5 and R6 represent an aryl group, the aryl group may be substituted. Examples of the substituent include the substituents listed when R1 to R4 are aryl groups.

Among the above diffusible DIR compounds, general formulas C2A), (
2B), (2F) to 5) having a 2i leaving group are particularly preferred.

The yellow image-forming coupler residue represented by A in general formula (1) includes pivaloylacetanilide type, benzoylacetanilide type, malondiester type,
malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malon ester monoamide type,
Benzothiazolylacetate type, benzoxacylylacetamide type, benzoxacylylacetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type coupler residue, heterocycle included in U.S. Pat. No. 3,841,880 Coupler residues derived from substituted acetamides or heterocyclic substituted acetates or U.S. Pat. No. 3,770,44
No. 6, British Patent No. 1, 459, 171, West German Patent (
OLS) No. 2,503,099, Japanese Patent Application Publication No. 1973
Coupler residues derived from acylacetamides described in No. 0-139738 or Research Disclosure No. 15737, or U.S. Pat. No. 4,046,57
Examples include the heterocyclic coupler residue described in No. 4.

The magenta color image forming coupler residue represented by A is 5-oxo-2-pyrazoline nucleus, pyrazolo-N, 5-a
] Coupler residues having a benzimidazole core or a cyanoacetophenone type coupler residue are preferred.

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

In general, the effect as a DIR coupler is the same even if the coupler does not substantially form a dye after coupling with the oxidized form of the developing agent and releasing the development inhibitor. This type of coupler residue represented by A is described in U.S. Pat.
, No. 213, No. 4.088.491, No. 3,632,
No. 345, No. 3.958.993 or No. 3,961.
Examples include the coupler residues described in No. 959.

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

0 margins below IQ lo
Lo dumb
0
v0
ROCI CI2 Hzs OOCCHCOOCt 2 H25■ -ROρ ρ0
ρN"LN D-23 D-24 0 mouth D-29 D-30 = size U u''
j 8's 0 mouth ρ mouth D-39 0ρ, 1 ■ Q-C,) C) N01 D-49 r/o3H D-54CH・D-56 D-59 C2H.

H These compounds are described in U.S. Pat. Nos. 4,234,678 and 3
．． No. 2218554, No. 3.617.291, No. 2218554, No. 3.617.291, No.
No. 3.958.993, No. 4.149.886, No. 3
．． No. 933.500, Japanese Patent Publication No. 57-56837, Japanese Patent Publication No. 51-13239°, British Patent No. 2.072.363
No. 2,070,266, Research Disclosure, December 1981, No. 21228, etc.

Compounds that undergo a coupling reaction with the oxidized form of a color developing agent but do not form a dye (hereinafter referred to as colorless couplers) include:
The following compounds are included.

(1) A coupler that couples with an oxidized form of a color developing agent and dissolves into the processing solution because the dye formed is water-soluble. (2) A coupler that couples with an oxidized form of a color developing agent but remains as a leuco form. (3) Coupler that produces a substantially colorless product with no significant visible absorption in which the dye formed by coupling with the oxidized form of a color developing agent 3g! Although any of the above-mentioned colorless couplers are effective, type (1) is particularly preferred for the present invention. In addition, when the non-coloring coupler of the present invention is added to an emulsion layer, it is added in an amount of lX10-4 to 2.0 mol per 1 mol of the coloring coupler contained in the emulsion layer, and hydrophilic couplers other than the emulsion layer When added to the colloid layer, 1. Although not limited to 1.0X10-” depending on the added layer
1.0X10-2 mol/? It is preferable that

In the colorless coupler according to the present invention, the compound belonging to the above (1) can be represented by the following general formula (14).

General formula (14) % formula % In the formula, C0UP1 represents a coupler core having a coupling site (asterisk *), BALL is bonded to the coupling site of C0UP1, and the oxidized product of C0UP1 and a color developing agent is combined. It is a group that can be separated from C0UP1 by the reaction, and is a stable group having a size and shape that makes the compound of general formula (14) diffusion resistant. SQL is a solubilizing group that binds to the non-coupling position of GOUP+, and binds the coupling product generated by the coupling of COLIP+ with the oxidized form of a color developing agent into a strand in the light-sensitive material during or after the color development process. It is a group that provides mobility to flow out.

The coupler core represented by C0LJP1 may be any known or used in the art for forming a colored or colorless reaction product through a coupling reaction with an oxidized product of a color developing agent. The coupler core can be mentioned. For example, yellow dye-forming coupler nuclei are acylacetanilides, such as acetoacetanilides and benzoylacetanilides, and magenta dye-forming coupler nuclei are virazolones, pyrazolotriazoles, pyrazolobenzimidazoles, and indasilones. The coupler core for cyan dye formation includes phenols and naphthols.

BALL is a stabilizing group having a molecular size and shape that makes the compound of general formula (14) diffusion resistant;
14) Useful groups represented by BALL include, but are not limited to, alkyl groups having 8 to 32 carbon atoms, aryl groups, and heterocyclic groups as long as they impart diffusion resistance to the compound. It will be done. These groups represent unsubstituted or substituted groups, and as substituents, they increase the diffusion resistance of the compound of general formula (14), change the reactivity of the compound of general formula (14), or act as a cup. This is a group that causes a ring reaction and increases the diffusivity of BALL after being released. Furthermore, BALL is preferably bound to the coupling site of C0UP1 via a linking group. Typical linking groups include oxy (-0-) and thio (-8-).
), carbonyloxy (-0CO-), sulfonyloxy (-O20,-), 7mit' (-NHCO-), Su/L.

Examples include honamide (-NH8O2).

Preferred examples of BALL include an alkoxy group having an alkyl group and/or an aryl group having a total of 8 to 32 carbon atoms, an aryloxy group, a heterocyclic oxy group, an alkylthio group,
Arylthio group, heterocyclic thio group, arylazo group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, acylamim L alkylsulfonamide group, arylsulfonamide group, or nitrogen-containing heterocyclic group (virol, Pyrazole, imidazole, triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, phthalimide, succinimide, 2゜4-imidazolidinedione, 2,4-oxazolidinedione, 2,4-thiazolidinedione, triacylidine-3,5- dione, etc.).

The solubilizing group represented by SQL is a group that imparts mobility to a coupling product generated by a coupling reaction to the extent that it can flow out of the light-sensitive material system, such as an ionizable hydroxyl group, carboxyl group, sulfo group, and amino group. Examples include sulfonyl groups, ionizable salts thereof, ester groups, ether groups, and the like.

It is also preferred that one or more of these groups is bonded to the non-coupling site of GOUP+, or an alkyl group having an appropriate size, such as an alkyl group having 1 to 10 carbon atoms, or having 6 to 12 carbon atoms. Those in which the aryl group has one or more of the above-mentioned ionizable groups and a solubilizing group is bonded to the non-coupling site of C0LIP1 are also advantageously used.

Moreover, those bonded to the non-coupling site of C0UP1 via a linking group are also preferable. Typical linking groups include oxy (-0-), thio (-8-), carbonyl group, carbonyloxy group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group,
Mention may be made of sulfamoyl and aminosulfonyl groups.

Although useful solubilizing groups have been listed above, particularly preferred solubilizing groups are carboxyl groups, sulfo groups, or ionizable salts thereof directly bonded to the non-coupling site of GOUP1, or directly bonded to the non-coupling site of C0UP1. an alkyl group having 1 to 10 carbon atoms or 6 to 12 carbon atoms containing one or more carboxy groups, sulfo groups or ionizable salts thereof bonded or bonded via an amino group or a carbonyl group Examples include aryl groups having carbon atoms.

Further, the compounds according to the present invention capable of forming yellow, magenta and cyan dyes preferably used in the present invention have the following general formulas (15) to (20). an aryl group (e.g. phenyl group) or an alkyl group (especially a tertiary alkyl group, e.g. t-butyl group), R2 is the stabilizing group (BALL) mentioned above, and R
5 is the above-mentioned solubilizing group (SQL), R4 is a hydrogen atom or a halogen atom, an alkyl group or an alkoxy group, and n+1-5 (however, n≠0, m≠0, and n, m When is 2 or more, they may be the same or different).

[Magenta color patch-forming compound]

General formula [16] General formula [17] General formula [18] T? ! In the general formulas (16), (17) and (18), R2
has the same meaning as R2 in general formula (15), R5 represents a solubilizing group (SQL), R6 represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an amino group, and p≦5. When p≠0 and p is 2 or more, they may be the same or different.) R7
and one of R8 represents the above-mentioned solubilized W (SQL>, and the other represents a hydrogen atom, an alkyl group, an alkoxy group,
Represents an aryl group or an amino group.

R9 and R+o have the same meanings as R1 and R8 in general formula (17).

In the following margin [Cyan dye-forming compound] R2 General formula [20] In the following margin General formulas (19) and (20), R2 represents the general formula (
15), at least one of R11 and R12 is the above-mentioned solubilizing group (SQL), and the remainder represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or an alkylamido group, and q≦ 3 (However, q≠
0), and RI3 represents the above-mentioned solubilizing group (SQL>).

Unless otherwise indicated above, alkyl, alkoxy and alkylamido groups each contain 1 to 8 carbon atoms, aryl groups contain 6 to 10 carbon atoms, and amino groups contain 6 to 10 carbon atoms; Includes mono, primary and tertiary amino groups. These substituents and stabilizing groups (BAL
L) also includes those further substituted with halogen atoms, groups such as hydroxy, carboxy, amino, amido, carbamoyl, sulfamoyl, sulfonamide, alkyl, alkoxy and aryl.

In the colorless coupler according to the present invention, the compound that conforms to the above (2) has the following general formula (21). , RM represents a group that is bonded to the coupling site of GOUP2 and cannot be separated by the reaction between the coupler of general formula (21) and the oxidized product of the color developing agent.

The coupler core represented by C0UP2 has the general formula (
The coupler core mentioned in 14) can be mentioned.

Examples of the group represented by RM include an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an alkenyl group, and a cyano group.

The compound represented by the general formula (21) has an alkyl group, an aryl group, and a heterocyclic group having 8 to 32 carbon atoms via a linking group at the non-coupling site of the coupler core represented by coUP2. Diffusion is preferred. Typical linking groups include oxy (-0-),
Mention may be made of thio(-8), carbonyl group, carbonyloxy group, oxycarbonyl group, amino group, carbamoyl group, aminocarbonyl group, ureido group, sulfamoyl group, and aminosulfonyl group.

In the colorless coupler according to the present invention, the compound belonging to the above (3) can be represented by the following general formula (22).

General formula (22) In the formula, GOUP3 represents a coupler core that produces a substantially colorless product by a coupling reaction with the oxidized form of a color developing agent, and R+5 is bonded to the coupling site of COUP3 to form a color developing agent. Represents a group that can be separated from C0UP3 by a coupling reaction with an oxidized form of a developing agent.

Preferred leaveable groups include halogen atoms, alkoxy groups, aryloxy groups, heterocyclic oxy groups, alkylthio groups, heterocyclic thio groups, arylazo groups, acyloxy groups, alkylsulfonyloxy groups, arylsulfonyloxy groups, and nitrogen-containing groups. Examples include telocyclic group.

More preferable colorless couplers represented by general formula (22) are general formula (23) to % formula % general formula (23) Z C-X formula, where R15 is R +s in general formula (22). They are synonymous, and R+6 is a hydrogen atom, an alkyl group, a, lyl group, a halogen atom, an alkoxy group, an acyloxy group, or a heterocyclic group, and X is an oxygen atom, or = N + R
Represents 17. R17 represents an alkyl group, an aryl group, a hydroxy group, an alkoxy group or a sulfonyl group.

2 is a 5- to 7-membered carbon ring (e.g. indanone, cyclopentane, cyclohexanone, etc.) or a heterocycle (e.g. piperidone, pyrrolidone, hydrocarbostyryl, etc.)
Represents a group of nonmetallic atoms necessary to form .

General formula (24) % formula % In the formula, R+5, R+6 and X are RI5. in general formula (23). R+6 has the same meaning as R+6 and represent.

General formula (25) % formula % In the formula, R15 has the same meaning as R 15 in general formula (22), Ras and R20 may be the same or different, and include an alkoxycarbonyl group, a carbamoyl group,
Represents an acyl group, a cyano group, a formyl group, a sulfonyl group, a sulfinyl group, a sulfimoyl group, an ammoniamyl group, or -Nλ. A represents a group of nonmetallic atoms necessary to form a 5- to 7-membered heterocycle (eg, phthalimide, triazole, tetrazole, etc.) together with the nitrogen atom.

General formula (26) In the formula, R15 has the same meaning as R15 in general formula (22),
R21 represents an alkyl group, aryl group, anilino group, alkylamino group or alkoxy group, and B represents an oxygen atom, sulfur atom or nitrogen atom.

Next, typical examples of the colorless coupler according to the present invention will be listed, but the invention is not limited thereto.

Below is an example compound belonging to general formula [14] S-(2) J n- ψ ψ1
%ノφ ω 8ψ
C/)
■C/)
C/)
C/)li
ψψ ν C/) ■C/)
CQ0wa
0 η ■ bri φ Ω ri
φS-(33) S-(34) NHCOOCaHI? S-(36) S-(37) Exemplary compound belonging to general formula [21] CnoS-(44) Exemplary compound belonging to general formula [22] J(Jfl S-(51) S-(52) S -(53) The colorless coupler according to the present invention is disclosed in JP-A-59-1134.
No. 40, No. 59-171955, No. 52-82423
British Patent No. 914,145, British Patent No. 1,284,64
No. 9, U.S. Patent No. 2,742,832, U.S. Patent No. 3.22
No. 7.550, No. 3,928,041, No. 3.958
, No. 993, No. 3,961,959, No. 4,046,
No. 574, No. 4,052,213, No. 4,149,8
It can be synthesized by the method described in No. 86, etc.

The silver halide emulsion used in the present invention includes conventional silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide, and silver chloride. Any material used in silver halide emulsions can be used, but silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferred.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, the halide ions and silver ions may be generated by sequentially and simultaneously adding the halide ions and silver ions while controlling the DH and pAQ in the mixing pot, taking into consideration the critical growth rate of the silver halide crystals. With this method,
Silver halide grains with a regular crystal shape and nearly uniform grain size can be obtained. Conversion methods may be used at any step in the formation of AQX to change the halogen composition of the particles.

Known silver halide solvents such as ammonia, thioether, thiourea, etc. can be present during the growth of silver halide grains.

During the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), and iron salts ( By adding metal ions using at least one selected from HMA), these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere. A reduction sensitizing liquid can be applied inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disclosure (Research D 1
(hereinafter abbreviated as RD) No. 17643■
It can be carried out based on the method described in Section.

The silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains may be such that the latent image is mainly formed on the surface, or may be such that the latent image is mainly formed inside the grain.

The silver halide grains may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape. In these particles, any ratio of the (100) plane to the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The size of silver halide grains is O, OS ~ 30μ,
Preferably, a vine with a diameter of 0.1 to 20 μm is used.

Silver halide emulsions having any grain size distribution may be used. An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion). A particle with a value of 0.20 or less when divided by the average grain size.The grain size is the diameter in the case of spherical silver halide, and the projection of the grain in the case of grains with a shape other than spherical. This indicates the diameter when the image is converted into a circular image with the same area.) may be used alone or in combination. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

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

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing fog during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added to the processing solution to harden the photosensitive material to the extent that it is not necessary to add a hardening agent.
It is also possible to add hardeners to the processing solution.

For example, aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (1,3,5 -triacryloylhexahydro-s-triazine, 1
．． 3-vinylsulfonyl-2-propatol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), etc. alone or in combination. It can be used as

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are the compounds described in RD 17643, section XII, A.

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 (e.g. vinyl acetate), acrylonitrile, olefin, ethylene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The emulsion layer of the photosensitive material contains a dye-forming agent that forms a dye through a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing. A coupler is used. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even if these dye-forming couplers are 4-isomer, in which 4 molecules of silver ions need to be reduced in order to form 1 molecule of dye, only 2 molecules of silver ions need to be reduced. Either 2-isomolar property is acceptable. Dye-forming couplers include colored couplers that have a color-correcting effect.

As the yellow dye-forming coupler, known acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous. Specific examples of yellow coloring couplers that can be used include, for example, U.S. Patent No. 2,87
No. 5,057, No. 3.265,506, No. 3.4
No. 08.194, No. 3,551,155, No. 3,
No. 582,322, No. 3.725.072, No. 3
．． No. 891,445, West German patent 1,547.868@,
West German Application No. 2,219,917, No. 2,261,3
No. 61, No. 2,414,006, British Patent No. 1,42
No. 5,020, Japanese Patent Publication No. 51-10783, Japanese Patent Publication No. 1977
-26133, 48-73147, 50-63
No. 41, No. 5G-87650, No. 50-123342
No. 50-130442, No. 51-21827,
These are described in No. 51-102636, No. 52-82424, No. 52-115219, No. 58-95346, etc.

As magenta dye-forming couplers that can be used in combination with the magenta coupler of the present invention, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, open-chain acylacetonitrile couplers, indacylon couplers, and the like can be used. Specific examples of magenta color forming couplers that can be used include, for example, U.S. Pat. No. 2,600,788, U.S. Pat.
No. 3,127.269, No. 3,311,47
No. 6, No. 3.419.391, No. 3.519.4
No. 29, No. 3,558,319, No. 3.582.
No. 322, No. 3,615,506, No. 3,834
, No. 908, No. 3,891, 445, West German Patent 1,
No. 810,464, West German Patent Application (OLS) 2,4
No. 08,655, No. 2,417,945, No. 2.
No. 417,945, No. 2.418.959, No. 2
, 424, 467, JP 40-6031, JP 49-74027, JP 49-74028, JP 49
-129538, 50-60233, 50-
No. 159336, No. 51-20826, No. 51-26
Examples include those described in No. 541, No. 52-42121, No. 52-58922, No. 53-55122, and Japanese Patent Application No. 110943/1983.

Phenol or naphthol couplers are commonly used as cyan dye-forming couplers. Specific examples of cyan color-forming couplers that can be used include, for example, U.S. Patent No. 2.42.
3.730@, same No. 2,474,293, same No. 2,8
No. 01,171, No. 2, 895, 826, No. 3,476, 563, No. 3.737.326, No. 3.758,308, No. 3.893.044 Japanese Patent Publication No. 47-37425, No. 50-10135
No. 50-25228, No. 50-112038, No. 50-117422, No. 5G-130441, etc., and JP-A-58-98731.
The couplers described in the above publication are preferred.

Among dye-forming couplers, colored couplers, DIR compounds, diffusible DIR compounds, image stabilizers, color capritic inhibitors, ultraviolet absorbers, optical brighteners, etc. that do not need to be adsorbed on the surface of silver halide crystals, Various methods can be used for the hydrophobic compound, such as a solid dispersion method, a latex dispersion method, and an oil-in-water emulsion dispersion method, and these methods can be selected as appropriate depending on the chemical structure of the hydrophobic compound such as the coupler. can.

For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 1.
Dissolve in a high boiling point organic solvent of 50°C or higher in combination with low boiling point and/or water soluble smvs if necessary, and add a surfactant to a hydrophilic binder such as a gelatin aqueous solution using a stirrer or homogenizer. After emulsification and dispersion using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic device, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high-boiling point solvents include organic compounds with a boiling point of 150°C or higher, such as phenol derivatives, phthalate alkyl esters, phosphate esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters, and trimesic acid esters, which do not react with the oxidized form of the developing agent. A solvent is used.

Low boiling or water-soluble solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents 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 dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants and amphoteric surfactants can be used.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image. Compounds that can be preferably used are those described in RD No. 17643, Section 2 J.

Hydrophilic colloid layers such as protective layers and intermediate layers of photosensitive materials may contain ultraviolet absorbers to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

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

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change developability such as development accelerators and development delaying agents, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material. Compounds that can preferably be used as development accelerators are RD 1
The compound is a compound described in Section XXI B to D of No. 7643, and the development retardant is a compound described in Section XXI E of No. 17643. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The emulsion layer of photographic light-sensitive materials is made of polyalkyleneoxy 1 or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, and urethane derivatives for the purpose of increasing sensitivity, increasing contrast, or promoting development. , urea derivatives, imidazole derivatives, etc.

A fluorescent whitening agent can be used in the photosensitive material for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable. Compounds which can preferably be used as optical brighteners are described in section V of RD 17643.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are leached from the light-sensitive material or bleached during the development process. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like.

In the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material, reduction of gloss of the light-sensitive material, improvement of writeability,
A matting agent can be added for the purpose of preventing photosensitive materials from sticking to each other. Any matting agent can be used, but examples include silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, polymers of acrylic acid and methacrylic acid and their esters, polyvinyl resin, polycarbonate, and styrene. and copolymers thereof. The particle size of the matting agent is preferably 0.05μ to 10μ. The amount added is preferably 1 to 30G111J/f.

A lubricant can be added to the photosensitive material to reduce sliding friction.

Antistatic agents can be added to photosensitive forest materials for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for. Preferably used antistatic agents are the compounds described in RD 17643 x■.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may contain coating properties, antistatic properties, anti-scratch properties, emulsification and dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, film hardening, sensitization, etc.).

The support used in the photosensitive material of the present invention includes α-olefin polymers (e.g. polyethylene, polypropylene,
Flexible reflective supports such as paper laminated with ethylene/butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, etc. These include films made of , flexible supports made of these films with reflective layers, glass, full-reflection, ceramics, etc.

After subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be used directly or to improve the adhesion, antistatic properties, dimensional stability, abrasion resistance, hardness, etc. of the support surface.
1W to improve antihalation properties, FJtl properties, and/or other properties! It may be applied through an undercoat layer of J or more.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which have quick reactivity and will cause gelation if added to the coating solution before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

Examples of surfactants include, but are not limited to, natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine, and others. Cationic surfactants such as heterocycles, phosphoniums or sulfoniums, carboxylic acids, sulfonic acids,
Anionic surfactants containing acidic groups such as phosphoric acid, sulfuric esters, phosphoric esters, amino acids, aminosulfones 1
Amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino alcohols may be added.

Moreover, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. Alternatively, a bleach-fixing process can be performed using a 1-bath bleach-fixing solution, or a monobath process using a 1-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also carry out the process.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development treatment step, an activator treatment step may be performed in which a color developing agent or its precursor is contained in the material and the evening treatment is performed with an activator solution. Activator treatments can be applied.

Among these processes, typical processes are shown below. (These treatments are carried out as a final step, one of a water washing process, a water washing process, and a stabilization process.) - Color development process - bleaching process - constant fixation process - color development process - bleach-fixing process Processes: Pre-hardening process - Color development process - Stop fixing process - Washing process - Bleaching process Constant fixation process - Washing process - Post-hardening process - Color development process - Washing process - Supplementary information Color development process - Stop process - Bleach process Constant fixation process/activator process - Bleach-fix process/Activator process - Bleaching process Constant fixation process/Monobath process Processing temperature is usually 10°C It is selected in the range of ~65℃,
The temperature may exceed 65°C. Preferably from 25°C
Processed at 45°C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol derivatives and p-phenyrezine amine derivatives. These color developing agents can be used as salts of organic and inorganic acids, such as salt fR acid, sulfate, D-toluenesulfonate, subsulfurous acid, etc.
Acid salts, oxalates, benzenesulfonates, etc. can be used.

These compounds are generally about 0.0% in color developer 11.
1 to about 30 (l) concentration, more preferably color developer 1
i is used at a concentration of about 1 to about 15 g. 0.1g
A sufficient color density cannot be obtained if the amount added is less than .

Examples of the aminophenol-based developer include 0-aminophenol, p-aminophenol, 5-aminophenol,
Included are 2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful 1st m aromatic amine color developer is N-N'
-Dialkyl-p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N-N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-〇-phenylenediamine hydrochloride, and N-dimethyl-p-phenylenediamine hydrochloride.

N-dimethyl-〇-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino Aniline sulfate, N-ethyl-N-β-hydroxydiethylaminoaniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-
Examples include methylaniline-p-toluenesulfonate.

Further, the above color developing agents may be used alone or in combination of 2N or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

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 a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution used in the present invention may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. In addition, various additives such as benzyl alcohol, alkali metal halides, such as potassium bromide or potassium chloride, development regulators such as citrazic acid, preservatives such as hydroxylamine or sulfites, etc. May contain. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developing solution used in the present invention is usually 7 or more,
Preferably it is about 9-13.

In addition, the color developing solution used in the present invention may contain antioxidants such as diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, pentose, or hexose, pyrogallol-1,
3-dimethyl ether etc. may be contained.

Various chelating agents can be used in combination as metal ion sequestering agents in the color developing solution used in the present invention. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminopentaacetic acid, 1-
Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, 7-minobolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetralin M, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane1. Examples include phosphonocarboxylic acids such as 2.4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

Typhoon complex salts of organic acids are used as bleaching agents, such as polycarboxylic acids, aminopolycarboxylic acids, or organic acids such as oxalic acid and citric acid, coordinated with metal ions such as iron, cobalt, and copper. . Among the above n-acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and ethylenediamine-N-(β-oxyethyl)-
N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycincitric acid (or tartaric acid, ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid) Examples include acetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic 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 (J/l), more preferably 20-250 (J/l).

In addition to the above-mentioned bleaching agent, the bleaching solution may contain a sulfite salt as a preservative, if necessary. Alternatively, it may be a bleaching solution containing an ethylenediaminetetraacetate iron(m) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, lithium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. are also used. be able to.

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

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． It is used between 0 and 9.5, preferably between 4.5 and 8.0, and most preferably between 5.0 and 7.0.

A fixer having a commonly used composition can be used. As a fixing agent, a compound that reacts with silver halide to form a water-soluble complex salt, such as a thiosulfate such as potassium thiosulfate, sodium thiosulfate, or ammonium thiosulfate, or potassium thiocyanate, which is used in ordinary fixing processing, may be used. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thioether. These fixatives are 5
g/2 or more, and is used in the range that can be dissolved, but generally 70a to 250111#! Use with.

Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can also be contained in the fixing tank.

The bleaching solution and/or fixing solution may include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc.1) HiII
Agent I can be contained alone or in combination of two or more. In addition, various optical brighteners, antifoaming agents, or surfactants can be contained. or,
Preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohols and nitrates, hardening agents such as water-soluble aluminum salts, methanol , dimethyl sulfamide, dimethyl sulfoxide, and other specific solvents may be contained as appropriate.

The DH of the fixer is used at 3.0 or higher, but generally it is 4.
．． 5 to 10, preferably 5 to 9.5, 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 above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron(m) complex salt bleach and a small amount of a halide such as ammonium bromide other than the above-mentioned silver halide fixer, or conversely, a halogen such as ammonium bromide may be used. A special bleach-fix solution consisting of a combination of iron (I) ethylenediaminetetraacetate complex salt bleach and a large amount of a halide such as ammonium bromide. etc. can also be used. In addition to ammonium bromide, the halides include hydrochloric acid, hydrobromic acid,
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 included in the bleach-fixing solution include the fixing agents described in the above fixing process. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the fixing process described above.

The pH of the bleach-fix solution is used at 4.0 or higher, generally 5.0 to 9.5, preferably 6.0 to 8.5.
5, most preferably 6.5 to 8.5.

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

In all the examples below, the addition port in the silver halide photographic light-sensitive material is 112, unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver.

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

Sample 1st layer: Antihalation H (HC-1) gelatin layer containing black colloidal silver.

2nd layer; middle 115 (1, L,) 2.5-G[-octylhydroki A gelatin layer containing an emulsified dispersion of non-alcoholic acid.

3rd layer; low sensitivity red-sensitive silver halide emulsion layer (RL-1) average grain size (lower) 0.30 μm, Ag 16 mol%
Monodisperse emulsion (emulsion I) consisting of AgBr1 containing...Silver coating amount: 1.8 g/f Sensitizing dye ■... 5X10-5 mole sensitizing dye ■... per 1 mole of silver ... 1.0 x 10-5 mole cyan coupler (C-1) per mole of silver...0.06 mole colored cyan coupler (CC-1> per mole of silver) DIR compound (D-I): 0.0015 mol per mol of silver DIR compound (D-IF): 0.003 mol per mol of silver 002 mol 4th layer: High sensitivity red-sensitive silver halide emulsion layer (RH-1) Average grain size (r) 0.5 μm, Ag1 7.0
Monodispersed emulsion (emulsion ■) consisting of Aa Br I containing mol%...Silver coating amount 1.3Q/f Sensitizing dye I...3X10-5 mol sensitizing dye per 1 mol silver ■・・・・・・1.0×10-5 mole cyan coupler (C-1) for 1 mole of silver・・・0.02 E for 1 mole of silver
Calado Cyan Cobra (CC-1) 0.0015 mol per mol of silver DIR compound (D-I[[)...0.001 mol per mol of silver 5th layer; middle Layer (1, L,) Same as the second layer, gelatin wide.

6th house: Low-sensitivity green-sensitive silver halide emulsion layer (GL-1> Emulsion - ■... Coated silver m 1.5 g/v2 Sensitizing dye ■... For 1 mole of silver 2.5X10-5 mole sensitizing dye...
... 1.2X10-5 mole magenta coupler (M-1) for 1 mole of silver... o, o for 1 mole of silver
somol colored magenta coupler (CM-1) 0.009 mol DIR compound (D-rV) per 1 mol of silver 0.0010 mol DIR compound (D-V) per 1 mol of silver ...... 0.0030 mol per 1 mol of silver 7th layer: Highly sensitive green-sensitive silver halide emulsion layer (GH-1) Emulsion - ■... Coated silver fit 1. 'll /
v' sensitizing dye ■... 1.5 x 10-5 mol sensitizing dye ■... per 1 mol of silver
... 1.0 x 10-5 mole magenta coupler (M-1) for 1 mole of silver...0.020 for 1 mole of silver
Mol colored magenta coupler (CM-1) 0.002 mol per mol of silver DIR compound (D-Vl) 0.0010 mol per mol of silver 8th layer: Yellow filter layer ( YC-1) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone.

9th layer: Low-speed blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (emulsion ■) consisting of Afl 3r I, average grain size Q, 48 tlm, and containing 16 mol% of Ag...Silver coated grain: 0 .9Q/f Sensitizing dye V...1.3XIQ-5 mole per mole of silver Yellow coupler (Y-1)...0.29 mole DIR per mole of silver Compound (D-■)... 0.0015 mol per mol of silver 10th layer: Highly blue-sensitive emulsion layer (BH-1) Average grain size 0
．． 8 μl, A (JB) containing 15 mol% Act I
Monodisperse emulsion consisting of rI (emulsion ■)... Silver coating station: 0.5 g/12 Sensitizing dye V...... 1.0 x 10-5 mol Yellow coupler (Y-1) per 1 mol of silver ...0.08 per mole of silver
Mol DIR compound (D-■)... 0.0015 mol per mol of silver 111i: 1st Preservation Nm (Pro-1) Silver iodobromide (A
g11 mol% average particle size 0.07 μm) Silver coating opening 0.50/m' Gelatin layer containing ultraviolet absorbers LIV-1 and UV-2.

12th layer; second protected Fi (Pro-2) polymethyl methacrylate particles (diameter 1.5 μm) and formalin scavenger (H8-1
) In addition to the above composition, a gelatin hardening agent (H-1) and a surfactant were added to each layer.

The compounds contained in each layer of the sample are as follows.

Sensitizing dye I: Anhydro-5,5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide Sensitizing dye ■: Anhydro 0-9-ethyl-3゜3 '-di(3-sulfopropyl)-4,5,4',5'-dibenzothiacarbocyanine hydroxide sensitizing dye ■; anhydro-5,5'-diphenyl-9-
Ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sensitizing dye ■: Anhydro-9-ethyl-3°3'-di(3-sulfopropyl) -5,6,5', 6 ' -dibenzoxacarbocyanine hydroxide sensitizing dye ■: Anhydro 3,3'-di(3-sulfopropyl)-4,5-benzo5'-methoxythiacyanine with a margin below Q and = :) - one or more D-I to D-■ in various samples prepared in the same way.
DIR compounds, and compounds that do not form dyes by coupling reaction with oxidized developing agents (colorless couplers)
The type, addition position, and addition quality are as shown in Table-1.

Margin below In the table, - indicates that the compound is not included.

The addition M of S is Q/f.

DIR compounds for comparison> D-(a) D-(b) D-(a >, o-(b) are DIR compounds that do not have so-called diffusivity. After exposure using white light, the following development treatment was performed.

Processing steps (38°C) Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds washing 3 minutes 15 seconds fixing 6 minutes 30 seconds washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying The composition of the processing solution used in each processing step is as follows. It is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl) 1 aniline sulfate 4.75 (+ anhydrous sodium sulfite 4.250 hydroxylamine 1/2 sulfate 2 .0g anhydrous potassium carbonate
37.51j Sodium Bromide
1.3g nitrilotriacetic acid trisodium salt (monohydrate) 2.50 Potassium hydroxide Add 1.0g water and make 1
Set it to 2.

[Bleach solution] Ethylenediaminetetraacetic acid iron ammonium salt ioo aEthylenediaminetetraacetic acid diammonium salt 10.01; Ammonium monobromide 150.00 Ice vinegar @
10. Add water to pH 11 and adjust pH to 6.0 using aqueous ammonia.
Fall.

[Fixer] Ammonium thiosulfate 175. O(]
Anhydrous 1-lium oxide 8.5q Sodium metasulfite 2.3g Add water to 1
t, and adjust the pH to 6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5t12
Konidax (Konishiroku Photo Industry Co., Ltd. H) 7. Add SvQ water to make 11.

For each sample obtained, the sharpness (MTF) and RMS were measured using white light (W). The results are shown in Table-2. The sharpness improvement effect is due to the M T of the dye image.
F (Modulation TransferFu
nction) was determined and expressed as a relative value of MTF at 30 lines/mm (specimen N001 is taken as 100).

The RMS value is the density of the minimum density + 1, 2 with the aperture scanning area of 25
It is expressed as a value 1000 times the standard deviation of the variation in concentration value that occurs when scanning with a 0 μV microdecimometer.

Margin Table 2 below From the results in Table 2, it is clear that the present invention has a great effect on improving image quality (M removal and graininess) by combining a diffusive DIR compound and a colorless coupler. .

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one hydrophilic colloid layer on a support, a compound that reacts with an oxidized form of a developing agent to release a diffusible development inhibitor or development inhibitor precursor (diffusible DIR) A silver halide photographic light-sensitive material characterized by containing both a compound (compound) and a compound (colorless coupler) that undergoes a coupling reaction with an oxidized form of a developing agent but does not form a dye.