JPH0564785B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material which has excellent sharpness and processing stability, and has improved light fastness of magenta dye images.

[Prior art]

In recent years, the image quality of silver halide color photographic materials (hereinafter referred to as color photographic materials) has improved significantly, but the sharpness is still not sufficient. In particular, in enlarged prints from small format negative color films (110 film, disk film, etc.), image roughness (granularity) and poor sharpness significantly reduce the level of print image quality. This is due to the fact that the sharpness of negative film has not yet reached a level that allows it to withstand high-magnification printing. Radiation (light) is reflected at the interface of media with different refractive indexes. In ordinary light-sensitive materials, reflection occurs at the interface between the protective layer and air, the interface between silver halide grains and the binder in the silver halide emulsion layer, the interface between the bottom layer and the support, the interface between the back surface of the support and air, etc. This is because the sharpness of the image is significantly impaired. Conventionally, various techniques for improving sharpness are known. One is light scattering prevention technology, and the other is edge effect improvement technology. The latter technique includes a method using a so-called DIR coupler and a method using an unsharp mask. Among these, the method using an unsharp mask has a practical limit because it may cause a decrease in sensitivity and deterioration of graininess. Many methods using DIR couplers are known, and useful DIR couplers include Japanese Patent Publication No. 55-34933, Japanese Patent Publication No. 57-93344, US Patent No. 3227554, US Pat.
There are compounds described in No. 3701783 and others. However, when using a DIR coupler to emphasize the edge effect, the MTF is
(modulation transfer function)
However, it cannot be expected to improve MTF in the high frequency range necessary for high magnification, and it also has undesirable side effects such as decreased sensitivity and decreased concentration. If you use DIR couplers such as diffusive DIR and timing DIR that have long-distance effects, you can reduce the decrease in sensitivity and density, but the area of MTF improvement shifts further to the lower frequency side and improves sharpness at high magnification. We cannot expect much improvement. On the other hand, as techniques for preventing light scattering, a method of adding a colored substance, a method of forming a thin film, etc. are known. The latter method involves a significant reduction in the amount of silver coated, but it also reduces the number of color spots, leading to deterioration in graininess. There is also a reduction in the amount of gelatin, coupler, coupler solvent, etc. in the coating solution, but all of these methods have their limitations as they result in a decrease in coating properties and coloring density. In the former case, attempts have been made for a long time to add colored substances to suppress light scattering and improve sharpness, including the following methods. (a) Antihalation layer This layer is always provided on the side of the emulsion layer away from the exposure source, between the emulsion and the film base, or on the back of the film base. The purpose of this layer is to avoid blurring by so-called "reflection halation" by allowing light to penetrate downward through the emulsion layer and be reflected at optical interfaces such as gelatin-support or support-air. The goal is to absorb it as completely as possible. An example can be found in West German Patent Publication No. 2711220. Therefore, the ideal color for this layer is black. That is, this layer should exhibit a strong and uniform absorption as far as possible over the pre-visible spectral region. (b) Dyeing of the emulsion layer Filter dyes are added directly to the emulsion in order to absorb the light scattered by the silver halide crystals and prevent so-called "scattering halation" from occurring. Staining is commensurate with the sensitivity of each layer, resulting in considerable loss of sensitivity and gradation. (c) Filter intermediate layer This layer serves both to improve color reproduction and to improve sharpness. Viewed from the exposure source, this layer is always below the layer whose sharpness is to be improved, so it acts as a layer to prevent halation due to reflection in the sense of (a), and also protects against halogens in the underlying emulsion layer. It acts as a protective layer against the light scattered back by the silveride crystals, thereby contributing to reducing halation due to scattering.
At the same time, this layer improves the color reproduction of the underlying emulsion layer, since it prevents unwanted exposure in spectral regions outside the sensitivity range reserved for recording information. The filter interlayer must therefore absorb as much light as possible in this area of interfering secondary sensitivity - viewed from the exposure source.
It must not absorb light in the spectral region where the highest sensitivity lies further away than the filter layer. An important example is correcting the undesirable blue sensitivity of an emulsion layer sensitized for green or red light,
This is a yellow filter layer of a color photosensitive material. The techniques using dyes as described above have problems in that the effect of improving sharpness is insufficient or the sensitivity decreases so much that a sufficient amount of dye cannot be used to improve sharpness. In addition, the MTF in the high frequency region mentioned above
At present, it is not possible to improve the value to a point where it can be put to practical use. As a result of intensive research on how to use dyes in multilayer color light-sensitive materials, the present inventors discovered that between the light-sensitive silver halide emulsion layer and the light source, there is at least one other light-sensitive silver halide emulsion layer. When a non-light-sensitive layer of It was previously proposed that the effect of improving sharpness is significantly greater for the same decrease in sensitivity. However, localization of the dye to the non-photosensitive layer and
Although sharpness is significantly improved by the edge effect or interimage effect by the DIR coupler, it has been found that this effect changes greatly due to fluctuations in the processing solution, especially PH fluctuations in the color developer. This is due to the interimage effect.
Since the improvement in MTF is amplified by the localized dye, it is thought that the effect is greatly affected by fluctuations in the processing solution. Therefore, there is a need for the development of a technique that improves sharpness while minimizing sensitivity loss by using dyes appropriately, and that is not affected by processing variations.

[Purpose of the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a negative color photosensitive material whose sharpness is significantly improved and whose sharpness is not affected by processing variations.

[Structure of the invention]

As a result of various studies to achieve the above object, the present inventors have found that deterioration in sharpness due to processing variations can be prevented by incorporating a specific magenta coupler into the green-sensitive silver halide emulsion layer. This discovery led to the present invention. That is, the above purpose is to provide a non-photosensitive layer (filter layer) containing a non-diffusing substance that absorbs green light and/or red light, and a blue-sensitive, green-sensitive and red-sensitive halogen layer on a support. a green-sensitive silver halide comprising a photographic constituent layer containing a silver emulsion, the filter layer being located on a side farther from the support than the silver halide emulsion layer that is sensitive to light absorbed by the filter layer; This was achieved using a color light-sensitive material in which the emulsion layer contains a magenta dye-forming coupler represented by the following general formula []. General formula [] In the formula, R ₁ represents a primary alkyl group, and R ₂ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Furthermore, surprisingly, the photobleaching properties of the magenta dye image formed by the magenta coupler of the above general formula [] were also improved. The present invention will be explained in more detail below. The non-diffusive substance that absorbs green light in the present invention refers to a so-called non-diffusible green light-absorbing dye, which has an absorption maximum at 500 to 600 nm (preferably 530 to 570 nm). Similarly, the non-diffusive substance that absorbs red light is a non-diffusive red light-absorbing dye, which has an absorption maximum at 600 to 700 nm (preferably 620 to 660 nm). In the present invention, the non-diffusible green absorption dye and the non-diffusible red absorption dye are added during the preparation of the non-photosensitive hydrophilic colloid layer during the manufacturing process of color photosensitive materials. Any material can be used as long as it exists substantially in the non-photosensitive hydrophilic colloid layer without being diffused. As an example of a non-diffusible dye, for example, by coexisting a diffusible acid dye and a polymeric mordant having a basic group in the same non-photosensitive hydrophilic colloid layer, the acid dye can be made non-diffusible and used. I can do it. The polymer mordant having a basic group is, for example, imidazole, pyridine, alkylaminoalkyl (meth)acrylate, or a quaternary salt thereof,
Examples include polymers containing aminoguanidine and the like. Preferably used basic polymeric mordants are described in detail in the following US patent specifications: US Pat. i.e. No. 2548564, No.
Nos. 2,675,316, 2,882,156, and 3,706,563, and among these, particularly preferred basic polymer mordants in the present invention are polyvinyl alkyls memorized in the US patent specifications of Patent Nos. 2,882,156 and 3,706,563. It is a condensation product of ketone or poly-N-oxoalkyl (meth)acrylamide and aminoguanidine. Next, representative examples of basic polymer mordants preferably used in the present invention are listed. [Mordant-1] n=500 [Mordant-2] n=500 [Mordant-3] n=300 [Mordant-4] n=300 Any acidic dye can be used as the dye used in combination with the basic polymer mordant, but acidic dyes having a sulfo group or a carboxy group are preferable, such as azo dyes, triphenyl dyes, etc. Acidic dyes such as methane-based, anthraquinone-based, styryl-based, benzylidene-based, merocyanine-based, and oxonol-based dyes can be used. Next, typical examples of acid dyes used in the present invention are listed. [Dye-1] [Dye-2] [Dye-3] [Dye-4] [Dye-5] [Dye-6] [Dye-7] [Dye-8] [Dye-9] The above acidic dye and basic polymer mordant can be synthesized by a known method and incorporated into the non-photosensitive hydrophilic colloid layer by a known method. Examples of preferred non-diffusible green absorbing materials for use in the present invention include reaction products of known magenta couplers and known color developing agents, and examples of preferred non-diffusible red absorbing dyes include known There are reaction products of cyan couplers and known color developing agents. Specific examples of the magenta couplers include pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indazolone couplers. Examples of such magenta couplers include U.S. Pat.
Same No. 3311476, Same No. 3419391, Same No. 3519429,
Same No. 3558319, Same No. 3582322, Same No. 3615506,
No. 3834908, No. 3891445, West German patent
No. 1810464, West German patent application (OLS) No. 2408665,
JP 2417945, JP 2418959, JP 2424467, JP 40-6031, JP 49-79027, JP JP 49-74028
No. 49-129538, No. 50-60233, No. 50-
No. 159336, No. 51-20826, No. 51-26541, No. 52
Examples include those described in No. 42121, No. 52-58922, No. 53-55122, and Japanese Patent Application No. 110943/1983. Further, examples of the cyan coupler include phenol or naphthol derivatives, and examples of such cyan couplers include, for example, U.S. Pat.
No. 2423730, No. 2474293, No. 2801171, No. 2895826, No. 3476563, No. 3737326,
Specification No. 3758308, No. 3893044, JP-A-47
−37425, No. 50-10135, No. 50-25228, No. 50-10135, No. 50-25228, No.
50-112038, 50-117422, 50-130441, etc., and JP-A-58-
The couplers described in Japanese Patent No. 98731 are preferred. The known color developing agent to be reacted with the above coupler is preferably an aromatic primary amine compound, particularly a p-phenylenediamine compound.
N,N-diethyl-p-phenylenediamine hydrochloride, N-ethyl-p-phenylenediamine hydrochloride, N,N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl -N-dodecylamino)-toluene, N-ethyl-N-(β
-methanesulfonamidoethyl)-3-methyl-
4-aminoaniline sulfate, N-ethyl-N-β
-Hydroxyethylaminoaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-
Methylaniline-p-toluenesulfonate,
N,N-diethyl-3-methyl-4-aminoaniline, N-ethyl-N-(β-hydroxyethyl)
-3-methyl-4-aminoaniline and the like can be mentioned. Examples of other preferred non-diffusible green absorbing dyes include known colored cyan couplers. Examples of known colored cyan couplers include compounds described in U.S. Pat. No. 2,521,908, U.S. Pat. Furthermore, U.S. Patent No. 3476563 and Japanese Patent Application Laid-Open No. 1983-10135
Colored cyan couplers of the type in which the dye flows out into the processing bath by reaction with the oxidation product of a color developing agent, such as those described in No. 50-123341, can also be used. A particularly preferred colored coupler is the following general formula (1)
-a to (2)-b. General formula (1)-a General formula (1)-b In general formulas (1)-a and (1)-b, R ₁ and R ₂ are each a hydrogen atom, a straight or branched alkyl group having 1 to 30 carbon atoms, a mono- or bicycloalkyl group (e.g. cyclohexyl ), terpenyl groups (e.g., norbornyl group), aryl groups (e.g., phenyl group, naphthyl group, etc.), heterocyclic groups (e.g., benzimidazolyl group, benzothiazoline group, etc.), or morpholine, necessary to form a heterocyclic group such as pyridine. represents a nonmetallic atom. The above alkyl group, aryl group and heterocyclic group may be substituted, and examples of the substituent include the following groups. Halogen atoms, nitro groups, hydroxy groups, carboxy groups (if the coupler has at least 12 carbon atoms or equivalent ballast group in the non-coupling position), amino groups, aryl groups, substituted amino groups, (alkylamino, dialkylamino) ,
anilino, N-alkylanilino, etc.), carboxylic acid ester groups (carbalkoxy, carbalyloxy, etc.), amide groups (acetamide, butyramide, ethylsulfonamide, N-methylbenzamide, N-propylbenzamide, 4-t-butyl benzamide, etc.), carbamyl group (carbamyl,
N-octadecylcarbamyl, N,N-dihexylcarbamyl, N-methyl-N-phenylcarbamyl, 3-pentadecylphenylcarbamyl, etc.),
Sulfamyl groups (N-propylsulfamyl, N-tolylsulfamyl, etc. when the coupler has at least 12 carbon atoms or an equivalent ballast group in the non-coupling position), alkoxy groups (ethoxy,
octadecyloxy), sulfo groups (if the coupler has at least 12 carbon atoms or equivalent ballast group in the non-coupling position), substituted sulfonyl groups (methylsulfonyl, octadecylsulfonylethoxysulfonyl, decyloxysulfonyl,
phenylsulfonyl, trisulfonyl, phenoxysulfonyl, etc.). ^R3 is represented by _-COR5 and _-COOR5 . (Here, R ₅ represents an alkyl group having 1 to 20 carbon atoms or a substituted alkyl group.), and R ₄ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. General formula (2)-a General formula (2)-b In general formula (2)-a and general formula (2)-b,
R ₁ is a hydrocarbon residue, R ₂ is an amino group, an alkyl group,
Indicates acylamino group, ureido group, alkoxycarbonyl group, substituted products thereof, carboxyl group, etc. -L- represents an alkyleneoxy group having 1 to 6 carbon atoms, and m represents 0 or 1. [DD] represents a diffusible dye residue, and indicates a diffusible dye residue having a known dye moiety such as azo, azomethine, indoaniline, indophenol, anthraquinone, etc. Preferable [DD] is represented by the following formula. n=1~2 Examples of other preferred non-diffusible dyes used in the present invention include compounds represented by the following general formula (3). General formula (3) Ball - (X) _o --Col where -Ball is an organic stable compound having a molecular size and configuration that renders the compound non-diffusible during development in alkaline processing compositions. represents a group. Examples of the above organic stabilizing groups include formulas (i) to (iii)
It is expressed as (i) In the formula, Z is a saturated carbon ring (5
Represents the necessary nonmetallic atomic group forming a 7-membered to 7-membered structure. Most preferably, Y is a hydrogen atom, but depending on the use and properties of the photographic element to which it is added, it may be a group whose bond with an oxygen atom is cleaved at a hydroxyl ion concentration of 10 ^-5 to 2 mol/. . Among the latter groups, the ones that give more favorable results are:

[Formula] or

It is a group represented by [Formula]. Here, R ¹ represents an alkyl group having 1 to 18 carbon atoms, an alkyl group having 1 to 18 carbon atoms substituted with a halogen atom, a phenyl group, or a substituted phenyl group. B represents an organic group that makes the compound represented by the above general formula (3) non-diffusible in a color light-sensitive material, and the organic group includes a long-chain alkyl group; or an aromatic group such as a benzene-based or naphthalene-based group. or a long-chain alkyl group or a benzene-based or naphthalene-based aromatic group bonded to one end of a suitable divalent group. The long-chain alkyl group or aromatic group may be substituted, and suitable divalent groups include -O-; -S-;

[Formula] −SO ₂ −; −SO−;

[Formula] −CR ³ R ⁴ −; −CR ³ = CR ⁴ − (here, R ² represents a hydrogen atom, an alkyl group, or an aryl group, and R ³ and
R ⁴ each represents a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ); and 1 selected from the group consisting of substituted or unsubstituted aromatic divalent groups, non-aromatic carbocyclic groups, and non-aromatic heterocyclic groups.
It is a divalent group consisting of one of these constituents or a combination of two or more of these in an arbitrary linear chain. (ii) In the formula, W represents an organic group that makes the compound represented by the above general formula (3) non-diffusible in a color photosensitive material, and generally has an aliphatic group or an aromatic group having 8 to 20 carbon atoms. Examples include organic stabilizing groups having groups, alicyclic groups, and heterocyclic groups. In the compound of the present invention, these groups are bonded to the 5th or 6th position of the indole ring via a nitrogen atom, and examples of bonding via such a nitrogen atom include -NHCO- group, _-NHSO2- group, -
Examples include those via groups such as NR ₃ - group (R ₃ represents a hydrogen atom or an alkyl group). The organic stabilizing group is bonded to the 5th or 6th position of the indole ring, preferably the 5th position. In general formula (ii), R ₁ represents a monovalent organic group,
Examples of the group include alkyl groups and alkoxy groups, and alkyl groups and alkoxy groups having 1 to 3 carbon atoms are preferred. In general formula (ii), R ₂ represents a low-molecular group bonded via a carbon atom, and the group preferably has a substituent having 1 to 9 carbon atoms, for example, a substituent having 1 to 9 carbon atoms. Alkyl group, phenyl group and

[Formula] (R ₄ and R ₅ represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ₄ and R ₅
may form a ring at the same time. ). More preferably, _R2 is unsubstituted or substituted with a group selected from the group consisting of a halogen atom, an acetylamide group, a methylsulfonamide group, a nitro group, a carboxy group, a sulfo group, a methanesulfone group, an alkyl group, and an alkoxy group. and phenyl groups. In the formula, E is directly attached to the above 6-membered aromatic ring or

【formula】 【formula】

[Formula] (R' is an alkyl group), alkylene group (may be branched), -
O-, -S-, _-SO2- , a phenylene group (which may be substituted with an alkyl group, etc.), or a halogen atom or sulfo group bonded via a group formed by any combination thereof; Represents a heterocyclic group such as a carboxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a nitro group, an amino group, a cyano group, an alkylamino group, an arylamino group, a cyano group, an alkylthio group, a pyridyl group, etc. They may be the same or different. n represents an integer of 0 to 4. D represents a group represented by _-OR1 or _-NHR2 .
Here R ₁ is hydrogen atom or hydroxide ion concentration 10 ^-5 ~
Represents a group in which the bond between R ₃ and 0 is cleaved under the condition of 2 mol/h, preferably a hydrogen atom,

[Formula] or

It is a group represented by [Formula]. Here, R ₃ is an alkyl group, especially a carbon atom number of 1 to
18 alkyl groups. X in general formula (3) represents an appropriate divalent group,
-O-;-S-; as a suitable divalent group;

【formula】

[Formula] −SO ₂ −; −SO−; − NR ¹ CO−; −NR ¹ SO ₂ −; CR ² R ³ −; −CR ³ =
Examples include CR ^4- . (Here R ¹ is a hydrogen atom,
It represents an alkyl group or an aryl group, and R ² and R ³ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group. ) In the general formula (3), -Col represents a diffusible magenta or cyan dye component or a precursor component of these dyes. Such ingredients are well known to those skilled in the art and include azo, azomethine, azopyrazolone, indoaniline, indophenol, anthraquinone,
Applying dyes like triarylmethane, alizarin, merocyanine, nitro, quinoline, cyanine, indigoid, phthalocyanine, metal complexing dyes, etc., as well as different ambient environments such as leuco dyes, variation in PH value, reaction with complexing substances, etc. dye precursors, such as "shifted" dyes that shift hypsochromically or bathochromically when applied. -Col may also be a coupler component, such as phenol, naphthol, indazolone, pyrazolone, the compounds described in US Pat. No. 2,756,142, and the like. These components may have solubilizing groups as necessary. Examples of -Col include those represented by formulas (iv) to (ix). In formulas (iv) to (vi), Q is the 5th or 8th position with respect to G.
position, hydroxyl group or formula -NHCOR ³ or -
NHSO ₂ R ³ (in the formula, R ³ represents an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group having 1 to 6 carbon atoms, a benzyl group, a phenyl group, or a substituted phenyl group having 6 to 9 carbon atoms) , G is a hydroxyl group or a salt thereof or the formula

[Formula] or

[Formula] (wherein R ⁴ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a substituted phenyl group having 6 to 18 carbon atoms), and r represents a hydrolyzable acyloxy group. Represents an integer of 1 or 2, Z is a cyano group, trifluoromethyl group, fluorosulfonyl group, carboxy group, formula -COOR ⁴
(In the formula, R ⁴ represents the above), a nitro group at the 2nd or 8th position relative to the azo bond, a fluorine, chlorine or bromine atom, and a carbon atom number of 1
~8 alkyl- or substituted alkylsulfonyl groups, phenyl- or substituted phenylsulfonyl groups having 6 to 9 carbon atoms, alkylcarbonyl groups having 2 to 5 carbon atoms, formula -SO ₂ NR ⁵ R ⁶ (in the formula R ⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a substituted alkyl group, R ⁶ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted alkyl group, a benzyl group, a phenyl group, or a substituted alkyl group,
Benzyl group, phenyl group or carbon atom number 6-
9 substituted phenyl group, alkyl- or substituted alkylcarbonyl group having 2 to 7 carbon atoms, phenyl- or substituted phenylcarbonyl group having 7 to 10 carbon atoms, alkyl- or substituted alkylsulfonyl group having 1 to 6 carbon atoms group, number of carbon atoms 6~
9 represents a phenyl- or substituted phenylsulfonyl group, or R ⁵ and R ⁶ together with the choking atom to which they are attached represent a morpholine group or a piperidino group), or -CON (R ⁵ ) ₂ (in the formula, R ⁵ is the same or different,
represents a carbamoyl group of (representing the above),
Z ¹ represents hydrogen or Z, and R ¹ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom. , D is a cyano group, a sulfo group, a fluorosulfonyl group, a halogen atom, -
SO ₃ -phenyl group or substituted _C6-9 phenyl group, C1-8 alkyl or alkylsulfonyl group, C6-9 phenyl or substituted phenylsulfonyl group , alkyl- or substituted alkylsulfinyl group having 1 to 8 carbon atoms, 6 to 8 carbon atoms
9, a phenyl- or substituted phenylsulfinyl group of formula _-SO2NR5R6 , or a sulfamoyl group of formula -CON( ^R5 ) ² , where ^{R5 and R6} are each the same as _defined above for Z. represents a carbamoyl group of (represents), but there is no more than one sulfo group and no more than one carboxy group is present in the compound. In formulas (vii) to (ix), Y is a hydrogen atom,

[expression] or

Represents [formula]. Here, R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group, and R ₁₃ represents an acyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxyalkyleneoxyalkyl group,
Carboxyalkyl group, carboxyphenyl group,
It represents a carboxyalkylphenyl group, a hydroxyalkylphenyl group, an alkoxyphenyl group, or a group having the same meaning as the group represented by _R12 . W is -CO-
or -SO ₂ -, R ₇ has 1 to 6 carbon atoms
alkyl group, aryl group or

Represents [formula]. (Here, R ₁₄ and R ₁₅ represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. However, R ₁₄ and R ₁₅ cannot be hydrogen atoms at the same time.) R ₈ is the number of carbon atoms. It represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. R ₉ is hydrogen atom, halogen atom, number of carbon atoms is 1
~4 alkyl group, an alkoxy group having 1 to 8 carbon atoms, or a dialkylamino group having 1 to 8 carbon atoms, R ₁₀ is an alkyl group having 1 to 8 carbon atoms, and 1 to 8 carbon atoms.
Represents an alkylthio group having ~8, an arylthio group, a halogen atom, or an acylamino group having 1 to 10 carbon atoms. Here n is 0, 1 or 2. R ₁₁ represents an alkyl group having 1 to 6 carbon atoms or an aromatic group (for example, a phenyl group). Next, specific representative examples of the non-diffusible green absorption dye and the non-diffusible red absorption dye used in the present invention are shown, but the compounds used in the present invention are not limited to these. A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8 A-9 A-10 A-11 A-12 A-13 A-14 A-15 A-16 A-17 A-18 A-19 A-20 A-21 A-22 A-23 A-24 A-25 A-26 A-27 A-28 A-29 A-30 A-31 A-32 A-33 A-34 A-35 A-36 A-37 A-38 A-39 A-40 A-41 A-42 A-43 A-44 A-45 A-46 The non-diffusible dye of the present invention is synthesized by known methods. For example, JP-A-48-33826, JP-A No. 50-
No. 115528, No. 57-85055, No. 54-54021, U.S. Patent No. 4053312, JP-A-54-99431, No. 53-
It can be synthesized by the method described in No. 50736 and the like. Preferred non-diffusible green absorbing dyes and non-diffusible red dyes in the present invention include the dyes in a known high-boiling organic solvent such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, carbon tetrachloride, chloroform, etc. After dissolving in a representative low boiling point organic solvent, it is mixed with an aqueous gelatin solution containing a surfactant, and then a stirrer,
After emulsifying and dispersing it using a dispersing means such as a homogenizer, colloid mill, flow jet mixer, or ultrasonic dispersion device, it is used by adding it to a coating composition for a non-photosensitive hydrophilic colloid layer. Known high-boiling organic solvents that can be used include organic acid amides, carbamates, esters, ketones, urea derivatives, etc., particularly dimethyl phthalate, diethyl phthalate, di-propyl phthalate, di-butyl phthalate, di-n- Phthalate esters such as octyl phthalate, diisooctyl phthalate, diamyl phthalate, dinonyl phthalate, diisodecyl phthalate, tricresyl phosphate, triphenyl phosphate, tri-(2-ethylhexyl) phosphate, trisononyl phosphate Phosphate esters such as esters, sebacic acid esters such as dioctyl sebacate, di-(2-ethylhexyl) sebacate, diisodecyl sebacate, glycerin esters such as glycerol tripropionate, glycerol tributylate, others, adibate esters, glutar Phenol derivatives such as acid ester, succinate ester, maleate ester, fumarate ester, citric acid ester, di-tert-amylphenol, and n-octylphenol can be used singly or in combination of one or more of them. As the non-diffusible dye that absorbs green light and/or red light in the present invention, the above-mentioned oil-soluble dyes are preferred from the viewpoint of absorption spectrum sharpness and stable production. The preferred amount of the non-diffusive dye that absorbs green light and/or red light of the present invention is such that the density measured by green or red light in a non-scattering state is 0.01 to 0.30, more preferably 0.03 to 0.15. It is. In the present invention, a non-photosensitive layer (filter layer) containing a non-diffusible dye that absorbs green light and/or red light is a layer having substantially no effective sensitivity, and is a layer containing unsensitized silver halide particles. Also included are layers containing silver halide grains that do not contribute to density in the normal exposure range even if sensitized. The normal exposure range here refers to the exposure range in which the photosensitive material is most frequently used, and in the case of negative color film, it is the exposure range when the camera is set to the display sensitivity and is exposed to just the right amount of light. be. The color photosensitive material of the present invention can preferably have the following configuration. For example, a red-sensitive layer, a green-sensitive layer, a blue-sensitive layer, etc., which are formed by directly overlaying high- and low-sensitivity silver halide emulsion layers with the same color sensitivity as upper and lower layers, respectively, are layered from the support side. A non-photosensitive layer is arranged between each of the photosensitive layers having different color sensitivities;
A non-photosensitive layer is provided between each of these high-sensitivity layers and low-sensitivity layers. A silver halide emulsion layer with lower photosensitivity than that, a silver halide emulsion layer with even lower photosensitivity than the middle layer as the lower layer, and a layer with the highest photosensitivity on the side farthest from the support. Those having a photosensitive layer composed of three silver halide emulsion layers whose photosensitivity is successively lowered over time, or as described in Japanese Patent Publication No. 55-34932, A blue-sensitive layer, a high-sensitivity green-sensitivity layer, a high-sensitivity red-sensitivity layer, a low-sensitivity green-sensitivity layer, and a low-sensitivity red-sensitivity layer are arranged in this order from the far side, and a non-light-sensitive layer is arranged between these light-sensitive layers. Furthermore, from the side farthest from the support, a high-sensitivity blue-sensitive layer, a high-sensitivity green-sensitive layer, a high-sensitivity red-sensitive layer, a low-sensitivity blue-sensitive layer, and a low-sensitivity green-sensitive layer. For example, a photosensitive layer and a low-sensitivity red-sensitive layer are arranged in this order, and a non-photosensitive hydrophilic colloid layer is provided between these layers. As shown in the example of the preferred layer structure, the photosensitive layer closest to the exposure source is preferably blue-sensitive;
In the case of other photosensitive layers, the sensitivity and color reproducibility of the blue photosensitive layer are significantly degraded. Next, the magenta coupler represented by the general formula [] (hereinafter referred to as the magenta coupler of the present invention)
I will explain about it. Examples of the substituent represented by R ₂ in the general formula [] include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkyl group, an aryl group, a heterocyclic group, an acyl group, a sulfonyl group, and a sulfinyl group. group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclicoxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, heterocyclic thio group Examples include groups. Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred. The alkyl group represented by R ₂ has 1 carbon number
-32 is preferable, and as the alkenyl group and alkynyl group, those having 2 to 32 carbon atoms are preferable,
The cycloalkyl group and cycloalkenyl group preferably have 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkyl group, alkenyl group, and alkynyl group may be linear or branched. In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a hetero atom {specifically, hydroxy, alkoxy, aryloxy, heterocycles substituted via an oxygen atom such as oxy, siloxy, acyloxy, carbamoyloxy;
Nitro, amino (including dialkylamino, etc.),
Those substituted via a choking atom such as sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido, alkylthio,
Those substituted via a sulfur atom such as arylthio, heterocyclic thio, sulfonyl, sulfinyl, and sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl. Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1-hexylnonyl group, 1,1'-dipentylnonyl group, 2-chloro-t-butyl group,
Trifluoromethyl group, 1-ethoxytridecyl group, 1-methoxyisopropyl group, methanesulfonylethyl group, 2,4-di-t-aminophenoxymethyl group, anilino group, 1-phenylisopropyl group, 3- m-butanesulfonaminophenoxypropyl group, 3-4'-{α-[4″-(p-hydroxybenzenesulfonyl)phenoxy]dodecanoylamino}phenylpropyl group, 3-{4′-[α
-(2″,4″-di-t-aminophenoxy)butanamido]phenyl}propyl group, 4-[α-(o-
chlorophenoxy) tetradecaneamide phenoxy] propyl group, allyl group, cyclopentyl group,
Examples include cyclohexyl group. The aryl group represented by R ₂ is preferably a phenyl group, which may have a substituent (eg, an alkyl group, an alkoxy group, an acylamino group, etc.). Specifically, phenyl group, 4-t-butylphenyl group, 2,4-di-t-aminophenyl group, 4
-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4'-[α-(4''-t-butylphenoxy)tetradecanamido]phenyl group, etc. The heterocyclic group represented by _R2 includes: 5- to 7-membered ones are preferable, and may be substituted or condensed.Specifically, 2-furyl group, 2-membered group, etc.
-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc. Examples of the acyl group represented by R ₂ include acetyl group, phenylacetyl group, dodecanoyl group,
Alkylcarbonyl groups such as α-2,4-di-t-aminophenoxybutanoyl group, benzoyl group,
Examples include arylcarbonyl groups such as 3-pentadecyloxybenzoyl group and p-chlorobenzoyl group. Examples of the sulfonyl group represented by R ₂ include methylsulfonyl group, alkylsulfonyl group such as dodecylsulfonyl group, benzenesulfonyl group, p-
Examples include arylsulfonyl groups such as toluenesulfonyl groups. Examples of the sulfinyl group represented by R ₂ include ethylsulfinyl group, octylsulfinyl group, 3
- an alkylsulfinyl group such as a phenoxybutylsulfinyl group, a phenylsulfinyl group, m
Examples include arylsulfinyl groups such as -pentadecyl phenylsulfinyl group. Examples of the phosphonyl group represented by R ₂ include an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and a phenoxyphosphonyl group such as a phenoxyphosphonyl group. Examples include arylphosphonyl groups such as enylphosphonyl group. The carbamoyl group represented by R ₂ is an alkyl group,
Aryl groups (preferably phenyl groups) may be substituted, for example, N-methylcarbamoyl groups, N,N-dibutylcarbamoyl groups, N-(2
-pentadecyloctylethyl)carbamoyl group, N-ethyl-N-dodecylcarbamoyl group,
N-{3-(2,4-di-t-amylphenoxy)
propyl}carbamoyl group, and the like. The sulfamoyl group represented by R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-propylsulfamoyl group, an N,N-diersulfamoyl group, N
-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-phenylsulfamoyl group, and the like. Examples of the spiro compound residue represented by R ₂ include spiro[3,3]heptan-1-yl and the like. The bridged carbonized compound residue represented by R ₂ is:
For example, bicyclo[2.2.1]heptane-1-yl, tricyclo[3.3.1.1 ^3,7 ]decane-1
-yl, 7,7-dimethyl-bicyclo[2.2.
1] heptane-1-yl and the like. The alkoxy group represented by R ₂ may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group, a propoxy group,
Examples include 2-ethoxyethoxy group, pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like. The aryloxy group represented by R ₂ is preferably phenyloxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as phenoxy group,
Examples include pt-butylphenoxy group and m-pentadecylphenoxy group. The heterocyclic oxy group represented by R ₂ is 5
Those having a ~7-membered heterocycle are preferred, and the heterocycle may further have a substituent, for example,
Examples include 3,4,5,6-tetrahydropyranyl-2-oxy group and 1-phenyltetrazol-5-oxy group. The siloxy group represented by R ₂ may be further substituted with an alkyl group, and examples thereof include a trimethylsiloxy group, a triethylsiloxy group, a dimethylbutylsiloxy group, and the like. Examples of the acyloxy group represented by R ₂ include an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-
Examples include chloroacetyloxy group and benzoyloxy group. The carbamoyloxy group represented by R ₂ may be substituted with an alkyl group, an aryl group, etc.
For example, N-ethylcarbamoyloxy group, N,N
-diethylcarbamoyloxy group, N-phenylcarbamoyloxy group, and the like. The amino group represented by R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an ethylamino group, an anilino group,
Examples include m-chloroanilino group, 3-pentadecyloxycarbonylanilino group, and 2-chloro-5-hexadecaneamideanilino group. Examples of the acylamino group represented by _R2 include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have a substituent, specifically an acetamido group, α-ethylpropanamide group, N-phenylacetamide group, dodecanamide group, 2,4-di-t-amylphenoxyacetamide group, α-3-t-butyl 4-hydroxyphenoxybutanamide group, etc. can be mentioned. Examples of the sulfonamide group represented by R ₂ include an alkylsulfonylamino group and an arylsulfonylamino group, and may further have a substituent. Specifically, methylsulfonylamino group, pentadecylsulfonylamino group, benzenesulfonamide group, p-toluenesulfonamide group, 2-
Examples include methoxy-5-t-amylbenzenesulfonamide group. The imide group represented by R ₂ may be an open-chain one,
It may be cyclic and may have a substituent, such as a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, and the like. The ureido group represented by R ₂ may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as an N-ethylureido group, an N-methyl-N-decylureido group, an N-phenylureido group. , N-p-tolylureido group, and the like. The sulfamoylamino group represented by R ₂ is an alkyl group, an aryl group (preferably a phenyl group)
For example, N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc. may be substituted. The alkoxycarbonylamino group represented by R ₂ may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like. The aryloxycarbonylamino group represented by R ₂ may have a substituent, and examples thereof include a phenoxycarbonylamino group and a 4-methylphenoxycarbonylamino group. The alkoxycarbonyl group represented by R ₂ may further have a substituent, such as methoxycarbonyl group, butyloxycarbonyl group, dodecyloxycarbonyl group, octadecyloxycarbonyl group, ethoxymethoxycarbonyloxy group, benzyloxy Examples include carbonyl group. The aryloxycarbonyl group represented by R ₂ is
It may further have a substituent, such as a phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, and the like. The alkylthio group represented by R ₂ may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group. The arylthio group represented by R ₂ is preferably a phenylthio group and may further have a substituent, such as a phenylthio group, p-methoxyphenylthio group, 2-t-octylphenylthio group, 3-octadecylphenylphenylthio group, Examples include nylthio group, 2-carboxyphenylthio group, p-acetaminophenylthio group, and the like. The heterocyclic thio group represented by R ₂ is 5-
A 7-membered heterocyclic thio group is preferred, and may further have a condensed ring or a substituent. Examples include 2-pyridylthio group, 2-benzothiazolylthio group, and 2,4-diphenoxy-1,3,5-triazole-6-thio group. Examples of substituents that can be removed by reaction with the oxidized product of the color developing agent represented by and substituent groups. In addition to the carboxyl group, examples of groups substituted via a carbon atom include, for example, the general formula (R ₁ ′ and R ₂ ′ have the same meanings as R ₁ and R ₂ above, and R ₃ and R ₄ represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group.)
Examples include hydroxymethyl group and triphenylmethyl group. Examples of groups substituted via an oxygen atom include alkoxy groups, aryloxy groups, heterocyclic oxy groups, acyloxy groups, sulfonyloxy groups, alkoxycarbonyloxy groups, aryloxycarbonyloxy groups, alkyloxalyloxy groups, and alkoxyoxalyloxy groups. Examples include groups. The alkoxy group may further have a substituent,
Examples include ethoxy group, 2-phenoxyethoxy group, 2-cyanoethoxy group, phenethyloxy group, p-chlorobenzyloxy group, and the like. The aryloxy group is preferably a phenoxy group, and the aryl group may further have a substituent. Specifically, phenoxy group, 3-methylphenoxy group, 3-dodecylphenoxy group, 4
-methanesulfonamidophenoxy group, 4-[α
-(3′-pentadecylphenoxy)butanamide]
Phenoxy group, hexidecylcarbamoylmethoxy group, 4-cyanophenoxy group, 4-methanesulfonylphenoxy group, 1-naphthyloxy group, p
-methoxyphenoxy group and the like. The heterocyclic oxy group is preferably a 5- to 7-membered heterocyclic oxy group, which may be a condensed ring or may have a substituent. in particular,
Examples include 1-phenyltetrazolyloxy group and 2-benzothiazolyloxy group. Examples of the acyloxy group include alkylcarbonyloxy groups such as an acetomethoxy group and a butanoyloxy group, alkenylcarbonyloxy groups such as a cinnamoyloxy group, and arylcarbonyloxy groups such as a benzoyloxy group. Examples of the sulfonyloxy group include a butanesulfonyloxy group and a methanesulfonyloxy group. Examples of the alkoxycarbonyloxy group include an ethoxycarbonyloxy group and a benzyloxycarbonyloxy group. Examples of the aryloxycarbonyl group include phenoxycarbonyloxy group. Examples of the alkyloxalyloxy group include a methyloxalyloxy group. Examples of the alkoxyoxalyloxy group include an ethoxyoxalyloxy group. Examples of the group substituted via a sulfur atom include an alkylthio group, an arylthio group, a heterocyclic thio group, and an alkyloxythiocarbonylthio group. Examples of the alkylthio group include a butylthio group, a 2-cyanoethylthio group, a phenethylthio group, a benzylthio group, and the like. Examples of the arylthio group include phenylthio group, 4-methanesulfonamidophenylthio group, 4-dodecylphenethylthio group, 4-nonafluoropentanamidophenethylthio group, 4-carboxyphenylthio group, 2-ethoxy -5-t
-butylphenylthio group and the like. Examples of the heterocyclic thio group include 1-phenyl-1,2,3,4-tetrazolyl-5-thio group and 2-benzothiazolylthio group. Examples of the alkyloxythiocarbonylthio group include a dodecyloxythiocarbonylthio group. Examples of the group substituting via the nitrogen atom include the general formula

Examples include those represented by the formula. Here, R ₄ ′ and R ₅ ′ are a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, a sulfamoyl group, a carbamoyl group, an acyl group, a sulfonyl group,
It represents an aryloxycarbonyl group or an alkoxycarbonyl group, and R ₄ ' and R ₅ ' may be combined to form a heterocycle. However, R ₄ ′ and R ₅ ′ are not both hydrogen atoms. The alkyl group may be linear or branched, and preferably has 1 to 22 carbon atoms. Further, the alkyl group may have a substituent, and examples of the substituent include an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, an acylamino group, and a sulfonamide group. group, imino group, acyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkyloxycarbonylamino group, aryloxycarbonylamino group, hydroxyl group, carboxyl group, cyano group, halogen atom, etc. Specific examples of the alkyl group include ethyl group, oxytyl group, 2-ethylhexyl group,
Examples include 2-chloroethyl group. The aryl group represented by R ₄ ' or R ₅ ' has 6 to 32 carbon atoms, and is particularly preferably a phenyl group or a naphthyl group, and the aryl group may have a substituent. Examples of substituents for the alkyl group represented by ₄ ' or _R5 ' include those listed above and an alkyl group. Specific examples of the aryl group include phenyl group, 1-naphthyl group, 4
-methylsulfonylphenyl group. The heterocyclic group represented by R ₄ ′ or R ₅ ′ is 5 to
A 6-membered ring is preferred, and may be a fused ring,
It may have a substituent. Specific examples include 2-furyl group, 2-quinolyl group, 2-pyrimidyl group, 2-furyl group, 2-quinolyl group, 2-pyrimidyl group,
-benzothiazolyl group, 2-biridyl group, etc. The sulfamoyl group represented by R ₄ ' or R ₅ ' includes N-alkylsulfamoyl group, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N,N-diarylsulfamoyl group, These alkyl groups and aryl groups may have the substituents listed for the alkyl groups and aryl groups. Specific examples of the sulfamoyl group include N,N-diethylsulfamoyl group, N-methylsulfamoyl group, N
-dodecylsulfamoyl group and N-p-tolylsulfamoyl group. Examples of the carbamoyl group represented by R ₄ ' or R ₅ ' include N-alkylcarbamoyl group, N,N-dialkylcarbamoyl group, N-arylcarbamoyl group, N,N-diarylcarbamoyl group, etc. The alkyl group and aryl group may have the substituents listed for the alkyl group and aryl group. Specific examples of the carbamoyl group include N,N-diethylcarbamoyl group, N-methylcarbamoyl group, N-dodecylcarbamoyl group, Kp-cyanophenylcarbamoyl group, and Np-tolylcarbamoyl group. Examples of the acyl group represented by R ₄ ′ or R ₅ ′ include an alkylcarbonyl group, an arylcarbonyl group, and a heterocyclic carbonyl group, and the alkyl group, aryl group, and heterocyclic group have a substituent. You may do so. Specific examples of the acyl group include hexafluorobutanoyl group,
2,3,4,5,6-pentafluorobenzoyl group, acetyl group, benzoyl group, naphthoyl group,
Examples include 2-furylcarbonyl group. The sulfonyl group represented by R ₄ ′ or R ₅ ′ is
Alkylsulfonyl group, arylsulfonyl group,
A heterocyclic sulfonyl group may be mentioned, which may have a substituent, and specific examples include an ethanesulfonyl group, a benzenesulfonyl group, an octanesulfonyl group, a naphthalenesulfonyl group, a p-chlorobenzenesulfonyl group, and the like. The aryloxycarbonyl group represented by R ₄ ' or R ₅ ' may have any of the substituents listed above for the aryl group, and specific examples thereof include phenoxycarbonyl group and the like. The alkoxycarbonyl group represented by R ₄ ' or R ₅ ' may have a substituent listed for the alkyl group, and specific examples include a methoxycarbonyl group, a dodecyloxycarbonyl group, and a benzyloxycarbonyl group. etc. The heterocycle formed by combining R ₄ ' or R ₅ ' is preferably a 5- to 6-membered ring, and may be saturated or unsaturated, and may or may not have aromaticity. , or may be a fused ring. Examples of the heterocycle include N-phthalimide group, N-succinimide group, 4-N-urazolyl group, 1-N-hydantoinyl group, 3-N-2,4-dioxoxazolidinyl group, 2- N-1,1-dioxo-3-(2H)
-oxo-1,2-benzthiazolyl group, 1-pyrrolyl group, 1-pyrrolidinyl group, 1-pyrazolyl group, 1-pyrazolidinyl group, 1-piperidinyl group, 1-pyrrolinyl group, 1-imidazolyl group, 1
-imidazolinyl group, 1-indolyl group, 1-isoindolinyl group, 2-isoindolyl group, 2-
isoindolinyl group, 1-benzotriazolyl group, 1-benzimidalyl group, 1-(1,2,4
-triazolyl) group, 1-(1,2,3-triazolyl) group, 1-(1,2,3,4-tetrazolyl) group, N-morpholinyl group, 1,2,3,4-
Examples include a tetrahydroquinolyl group, a 2-oxo-1-pyrrolidinyl group, a 2-1H-pyridone group, a phthaladione group, a 2-oxo-1-piperidinyl group, and these heterocyclic groups include an alkyl group, an aryl group, an alkyloxy group, aryloxy group, acyl group, sulfonyl group, alkylamino group, arylamino group, acylamino group, sulfonamine group, carbamoyl group, sulfamoyl group, alkylthio group, arylthio group, ureido group, alkoxycarbonyl group, aryloxycarbonyl group , an imide group, a nitro group, a cyano group, a carboxyl group, a halogen atom, or the like. The most preferred substituent among these substituents represented by X is a halogen atom. In addition, the general formula [] and the general formula [] ~
If the substituent R ₂ on the heterocycle in [) is When it has a portion shown by (R ₁ ″, R ₂ ″ and X have the same meaning as R ₁ , R ₂ , and X in the general formula []), it forms a so-called screw type coupler, but of course Included in the present invention. Specific examples of the magenta coupler of the present invention are shown below, but the present invention is not limited thereto. M-1 M-2 M-3 M-4 M-5 M-6 M-7 M-8 M-9 M-10 M-11 M-12 M-13 M-14 M-15 M-16 Moreover, the synthesis of the coupler is carried out in the Journal of
The Chemical Society, Perkin I
(Journal of the Chemical Society Perkin I)
(1977), 2047-2052, US Pat. No. 3,725,067, JP-A-59-99437, JP-A-58-42045, etc. In the present invention, the coupler can be used generally in an amount of 1.times.10.sup. ^-3 mol to 1 mol, preferably 1.times.10.sup.- ² mol to 8.times.10.sup. ^-1 mol per mol of silver halide. The magenta coupler of the present invention can also be used in combination with other types of magenta couplers. That is,
The green-sensitive silver halide emulsion layer containing the magenta coupler of the present invention may contain a magenta coupler and/or a colored magenta coupler other than the present invention. However, the content of these magenta couplers and/or colored magenta couplers outside the present invention is preferably less than 30 mol% of the total amount of couplers, particularly preferably 15
Less than mol%. As magenta couplers that can be used in combination with the green-sensitive silver halide emulsion layer of the present invention, pyrazolone compounds, indazolone compounds, cyanoacetyl compounds, pyrazoloazole compounds other than the present invention, etc. can be used, and in particular pyrazolone compounds. Compounds are advantageous. Specific examples of magenta couplers that can be used include
No. 49-111631, No. 56-29236, No. 57-94752,
Special Publication No. 48-27930, U.S. Patent No. 2600788, same
There are those described in No. 3062653, No. 3408194, No. 3519429, and Research Disclosure No. 12443. As a colored magenta coupler that can be used in combination with the green-sensitive silver halide emulsion layer of the present invention, US patent
Examples include those described in No. 280171, No. 3519429, and Japanese Patent Publication No. 48-27930. When adding the magenta coupler of the present invention and other couplers, they can be incorporated into the green-sensitive silver halide emulsion layer by the above-mentioned oil protection dispersion or latex dispersion method. It may be added as a solution. The silver halide used in the present invention may be a polydisperse emulsion in which the average grain size is distributed over a wide range, but a monodisperse emulsion method is preferred. In a preferred embodiment of the present invention, the monodisperse silver halide grains contained in at least one of the blue-sensitive silver halide emulsion layer, the non-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer include two or more types of monodisperse silver halide grains. may be mixed, in which case their average particle size may be the same or different. Polydisperse silver halide grains may also be used in combination. The photosensitive material of the present invention may have a so-called normal layer structure as the structure of its photosensitive emulsion layer. In addition, the so-called reverse layer structure (Japanese Patent Application No. 19360, No. 59-1936,
No. 202065, etc.), and a remarkable effect can be obtained particularly in an inverted layer structure. However, when using the magenta coupler of the present invention, whereas conventional normal layer configurations could not necessarily suppress characteristic fluctuations (graininess fluctuations, etc.) in response to fluctuations in development processing conditions (PH fluctuations, etc.), The present invention is also extremely effective in such cases. The photosensitive silver halide emulsion layer of the present invention may be separated into two or more layers having different sensitivities. That is,
For example, in order from the side farthest from the support, the high-speed layer (BH) of the blue-sensitive silver halide emulsion layer, the low-speed layer (BL) of the blue-sensitive silver halide emulsion layer, and the high-speed layer of the green-sensitive silver halide emulsion layer. The layer (GH) is a low-speed layer (GL) of a green-sensitive silver halide emulsion layer, a high-speed layer (RH) of a red-sensitive silver halide emulsion layer, and a low-speed layer (RL) of a red-sensitive silver halide emulsion layer. or a high-speed layer (BH) of a blue-sensitive silver halide emulsion layer,
High sensitivity layer (GH) of insulating silver halide emulsion layer,
High-speed layer (RH) of red-sensitive silver halide emulsion layer, low-speed layer (BL) of blue-sensitive silver halide emulsion layer, low-speed layer (GL) of insulating silver halide emulsion layer, red-sensitive silver halide emulsion It is like the low sensitivity layer (RL) of the layer. For example, a high-speed layer (BH) of a blue-sensitive silver halide emulsion layer, a high-speed layer (GH) of a green-sensitive silver halide emulsion layer, a high-speed layer (RH) of a red-sensitive silver halide emulsion layer, especially in The silver halide contained in is the average grain size (average grain size)
is preferably 0.40 to 3.00 μm, more preferably 0.50
~2.50 μm. The present invention relates to, for example, the low-speed layer (BL) of a blue-sensitive silver halide emulsion layer, especially in
The average grain size of the silver halide contained in the low-speed layer (GL) of the green-sensitive silver halide emulsion layer and the low-speed layer (RL) of the red-sensitive silver halide emulsion layer is 0.20 to 1.50 μm. Preferably, it is more preferably 0.20 to 1.0 μm. In addition, the low-speed layer (BL) of the blue-sensitive silver halide emulsion layer, the low-speed layer (GL) of the green-sensitive silver halide emulsion layer, and the low-speed layer (RL) of the red-sensitive silver halide emulsion layer are called medium-speed layers. When separated into a low-sensitivity layer, the former preferably has a thickness of 0.30 to 1.50 μm, and the latter preferably has a thickness of 0.15 to 1.00 μm. The above-mentioned monodisperse silver halide grains in the blue-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, and red-sensitive silver halide emulsion layer of the present invention are:
When the emulsion is observed using an electron micrograph, most of the silver halide grains appear to have the same shape, are uniform in grain size, and have a grain size distribution as shown below. That is, the standard deviation of the particle size distribution s
When divided by the average particle diameter r, the value is 0.20 or less, more preferably 0.15 or less. The grain size here has the same meaning as the grain size described above regarding the average grain size, and in the case of spherical silver halide grains, its diameter, or in the case of grains with shapes other than cubic or spherical, its projection. This is the diameter when the image is converted into a circular image with the same area. The relationship between particle size distribution is described in "Empirical Relationship between Sensitometric Distribution and Particle Size Distribution in Photography," The Photographic Journal, Volume LXXIX (1949).
This can be determined using the method described in the paper by Tribel and Smith, pp. 330-338. Furthermore, it is also possible to use a mixture of two or more types of monodispersed emulsions in the low-speed layer. These silver halide emulsions contain activated gelatin;
Sulfur sensitizers Sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; Selenium sensitizers; Reduction sensitizers such as stannous salts, thiourea dioxide, polyamines, etc.; Noble metal sensitizers such as gold sensitizers sensitizers, specifically potassium auricyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride, etc., or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc. Examples include ammonium chloroparadate, potassium chloroplatinate, and sodium chloroparadate (some of these act as sensitizers or fog suppressants depending on the amount) alone or as appropriate. Chemical sensitization may be carried out by using a combination (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.). The silver halide emulsion according to the present invention is subjected to chemical ripening by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing hetero emulsion having at least one kind of hydroxytetrazaindene and a mercapto group is prepared. It may contain at least one kind of ring compound. The silver halide used in the present invention contains an appropriate sensitizing dye at a rate of 5 x 10 ^-6 per mole of silver halide in order to impart photosensitivity in the desired wavelength range.
Optical sensitization may be carried out by adding up to 3×10 ⁻³ mol. Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more. Examples of sensitizing dyes that can be advantageously used in the present invention include the following. That is, as sensitizing dyes used in the blue-sensitive silver halide emulsion layer, for example, West German Patent No. 929080, US Patent No. 2231658, US Patent No. 2493748, US Patent No. 2503776,
Same No. 2519001, No. 2912329, No. 3656959, Same No.
No. 3672897, No. 3694217, No. 4025349, No. 3672897, No. 3694217, No. 4025349, No.
No. 4046572, British Patent No. 1242588, Special Publication No. 1977-
Examples include those described in No. 14030 and No. 52-24844. In addition, examples of sensitizing dyes used in insulating silver halide emulsions include U.S. Pat.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2945763, British Patent No. 505979, and the like. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Pat.
Representative examples thereof include cyanine dyes, merocyanine dyes, and composite cyanine dyes as described in No. 2454629, No. 2776280, and the like. Furthermore, US Patent No. 2213995, US Patent No. 2493748
Cyanine dyes, merocyanine dyes or composite cyanine dyes such as those described in No. 2,519,001, West German Patent No. 929,080, etc. can be advantageously used in green-sensitive silver halide emulsions or red-sensitive silver halide emulsions. These sensitizing dyes may be used alone or in combination. The photographic material of the present invention may be optically sensitized in a desired wavelength range by a spectral sensitization method using cyanine or merocyanine dyes alone or in combination, if necessary. Representative examples of particularly preferred spectral sensitization methods include, for example, Japanese Patent Publications No. 43-4936, No. 43-22884, and No. 45 concerning the combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
-18433, 47-37443, 48-28293, 48-28293, 47-37443, 48-28293,
No. 49-6209, No. 53-12375, JP-A No. 52-23931
No. 52-51932, No. 54-80118, No. 58-
Examples include methods described in No. 153926, No. 59-116646, and No. 59-116647. In addition, regarding the combination of carbocyanine having a benzimidazole nucleus with other cyanine or merocyanine, for example, Japanese Patent Publication No. 45-25831
No. 47-11114, No. 47-25379, No. 48-
No. 38406, No. 48-38407, No. 54-34535, No. 55
-1569, JP-A No. 50-33220, JP-A No. 50-38526,
No. 51-107127, No. 51-115820, No. 51-135528
No. 52-104916, No. 52-104917, etc. Furthermore, regarding combinations of benzoxazolocarbocyanine (oxa-carbocyanine) and other carbocyanines, for example,
No. 32753, No. 46-11627, JP-A No. 1483-1983, and Japanese Patent Publication No. 1483-1983 regarding merocyanine.
-38408, 48-41204, 50-40662, JP-A-56-25728, 58-10753, 58-91445
No. 59-116645, No. 50-33828, etc. Regarding combinations of thiacarbocyanin and other carbocyanins, for example, Japanese Patent Publications No. 43-4932, No. 43-4933, No. 45-26470,
No. 46-18107, No. 47-8741, JP-A-59-
No. 114533, etc., and furthermore, the Special Publication No. 114533 using zeromethine or dimethine merocyanine, monomethine or trimethine cyanine, and styryl dye.
The method described in No. 6207 can be used advantageously. In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution is prepared in advance using, for example, methyl alcohol, ethyl alcohol, acetone, dimethyl formamide, or a fluorinated alcohol described in Japanese Patent Publication No. 40659/1983. It is used by dissolving it in a hydrophilic organic solvent. The additive may be added at any time such as at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening, and in some cases, it may be added at a step immediately before coating the emulsion. The light-sensitive material according to the present invention can have a blue-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer in addition to the insulating silver halide emulsion layer of the present invention. The blue-sensitive silver halide emulsion layer and the red-sensitive silver halide emulsion layer can each contain a coupler, that is, a compound capable of reacting with an oxidized product of a color developing agent to form a dye. It is generally preferred that the blue-sensitive silver halide emulsion layer of the present invention contains a coupler that forms a yellow dye, and the yellow coupler may be a known closed ketomethylene coupler. Among these, benzoylacetanilide and pivaloylacetanilide compounds can be advantageously used. Specific examples of yellow couplers are disclosed in Japanese Patent Application Laid-open No. 47-26133,
No. 48-29432, No. 50-87650, No. 51-17438,
No. 51-102636, Special Publication No. 45-19956, No. 46-
There are those described in US Pat. No. 19031, US Pat. No. 51-33410, US Pat. No. 51-10783, US Pat. As the cyan coupler used in the red-sensitive silver halide emulsion layer of the present invention, phenol compounds, naphthol compounds, etc. can be used. Specific examples are U.S. Patent Nos. 2423730 and 2474293.
No. 2895826, and Japanese Patent Application Laid-Open No. 117422/1983. A common colored cyan coupler can be used in combination with the red-sensitive silver halide emulsion layer of the present invention.
As a colored cyan coupler, Tokuko Sho 55-
Those described in No. 32461 and British Patent No. 1084480 can be used. In a preferred embodiment of the present invention, a compound (hereinafter referred to as a DIR compound) that releases a development inhibitor or its precursor by reacting with an oxidized form of a color developing agent is added to at least one of the photosensitive silver halide emulsion layers. More preferably, when the light-sensitive silver halide emulsion layer is composed of two or more layers having different sensitivities, the high-sensitivity layer of the blue-sensitive silver halide emulsion layer ( BH), the high-speed layer (GH) of the green-sensitive silver halide emulsion layer, and the high-speed layer (RH) of the red-sensitive silver halide emulsion layer. A typical DIR compound is one in which a group is introduced into the active site of the coupler that can form a compound that has a development inhibiting effect when released from the active site.
There are DIR couplers, such as British Patent No. 935454,
U.S. Patent No. 4095984, U.S. Patent No. 4149886, JP-A-57-
It is described in No. 151944 etc. The above-mentioned DIR coupler has the property that, when subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler core forms a dye while releasing a development inhibitor. In addition, in the present invention, U.S. Patent No. 3852345, U.S. Patent No. 3928041, U.S. Patent No. 3958993
No. 39614959, No. 4052213, Japanese Unexamined Patent Publication No. 1973-
It also includes compounds that release development inhibitors but do not form dyes when they undergo a coupling reaction with oxidized color developing agents, such as those described in Nos. 110529, 54-13333, and 55-161237. It can be done. Furthermore, Japanese Patent Application Publication Nos. 54-145135 and 56-114946
When reacted with an oxidized color developing agent such as that described in No. 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group undergoes an intramolecular nine-nucleus substitution reaction or The present invention also includes so-called timing DIR compounds, which are compounds that release a development inhibitor through an elimination reaction. In addition, as described in JP-A-58-160954 and JP-A-58-162949, the above timing group is present in the coupler core that produces a completely diffusible dye when it reacts with an oxidized color developing agent. It also includes bound timing DIR compounds. More preferred DIR compounds used in the present invention can be represented by the following general formulas (4) and (5), and among these, the most preferred DIR compound is a compound represented by the following general formula (5). General formula (4) Coup-inhibitor In the formula, Coup is a coupler component (compound) that can couple with the oxidized form of a color developing agent, such as open chain ketomethylene compounds such as acylacetanilides and acylacetate esters, pyrazolones, etc.
These are dye-forming couplers such as pyrazolotriazoles, pyrazolinobenzimidazoles, indazolones, phenols, and naphthols, and coupling components that do not substantially form dyes such as acetophenols, indanones, and oxazolones. Further, the inhibitor in the above formula is a component (compound) that is released by reaction with a color developing agent and inhibits the development of silver halide. Preferred compounds include benzotriazole, 3-octylthio-1,
There are heterocyclic compounds and heteromercapto compounds such as 2,4-triazole and the like. Examples of the heterocyclic group include a tetrazolyl group, thiadiazolyl group, oxadiazolyl group, thiazolyl group, oxazolyl group, imidazolyl group, triazolyl group, and the like. Specifically, 1
-Phenyltetrazolyl group, 1-ethyltetrazolyl group, 1(4-hydroxyphenyl)tetrazolyl group, 1,3,4-thiazolyl group, 5-methyl-1,3,4-oxadiazolyl group, benzothiazolyl group group, benzoxazolyl group, benzimidazolyl group, 4H-1,2,4-triazolyl group, etc. In addition, in the above general formula (4), the inhibitor is bound to the active site of Coup. General formula (5) Coup-TIME-inhibitor In the formula, the inhibitor is the same as defined in general formula (4) above. Coup also includes a coupler component that generates a diffusive dye, similar to that defined in general formula (4). TIME is the general formula below
(6), (7), (8), and (9), but are not limited to these. General formula (6) In the formula, X represents an atomic group necessary to complete the benzene ring or naphthalene ring. Y is -O-,
-S-,

[Formula] (where R ³ represents a hydrogen atom, an alkyl group, or an aryl group), and is bonded to the coupling position. Also, R ¹ and R ² are
Each represents the same group as R ³ above,

The group [Formula] is substituted in the ortho or para position to Y and is bonded to a heteroatom contained in the inhibitor. General formula (7) In the formula, W is a group having the same meaning as Y in the general formula (6), and R ⁴ and R ⁵ are also each a group having the same meaning as Y in the general formula (6).
It is a group having the same meaning as R ¹ and R ² . R ⁶ is a hydrogen atom, an alkyl group, an aryl group, an acyl group, a sulfone group,
an alkoxycarbonyl group, a heterocyclic residue,
R ⁷ represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acylamido group, a sulfonamide group, a carboxy group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group. Then, couple this tanning group with W.
binds to the coupling position of

[Formula] is attached to the heteroatom of the inhibitor. Next, an example of a tamping group that releases an inhibitor through an intramolecular nucleophilic substitution reaction is shown by general formula (8). General formula (8)

[Formula] In the formula, Nu is a nucleophilic group having an electron-rich oxygen, sulfur, or nitrogen atom, and is bonded to the coupling position of Coup. E is an electrophilic group having an electron-poor carbonyl, thiocarbonyl, phosphinyl, or thiophosphinyl group and is bonded to the heteroatom of the inhibitor. V relates Nu and E three-dimensionally and is Coup
After Nu is released from the binding group, it undergoes an intramolecular nucleophilic substitution reaction with the formation of a 3-membered ring or a 7-membered ring, and thereby releases the inhibitor. General formula (9) Coup-OCH ₂ -inhibitor Coup and inhibitor have the same meanings as above. The above inhibitors have the same meanings as above. The above DIR compound is preferably added to the light-sensitive silver halide emulsion layer. In the present invention, two or more types of DIR compounds may be included in the same layer. Also, the same DIR compound can be used with two different
These DIR compounds, which may be included in more than one layer, generally contain silver in the emulsion layer.
2×10 ⁻⁴ to 5×10 ⁻¹ mol per mole is preferred;
More preferably, 2×10 ⁻⁴ to 5×10 ⁻² mol is used. The pyrazolotriazole type of the present invention, such as a non-diffusible coupler or a polymer coupler, which reacts with the oxidized form of a developing agent to form a diffusible dye that appropriately bleeds into the silver halide emulsion layer of the present invention and other photographic constituent layers. Couplers other than magenta couplers may be used in combination. Non-diffusible couplers that react with the oxidized form of these developing agents to form diffusible dyes that bleed moderately are described in Japanese Patent Application No. 193611/1982, and polymer couplers are described in Japanese Patent Application No. 172151/1982. You can refer to each. The method of adding the DIR compound and the like is substantially the same as that for the magenta coupler of the present invention. That is, in order to incorporate the above-mentioned DIR compound etc. into the coating solution for silver halide emulsion and other photographic constituent layers according to the present invention, if the DIR compound etc. is alkali-soluble, it may be added as an alkaline solution. If the coupler is oil-soluble, the coupler or the like is dissolved in a high boiling point solvent (HBS) in combination with a low boiling point solvent (LBS) if necessary, according to the method described in the above-mentioned US patent specification, and fine particles are prepared. It is preferable to add it to the silver halide agent by dispersing it in a uniform form. At this time, other hydroquinone derivatives, ultraviolet absorbers, anti-browning agents, etc. may be used in combination as necessary. Also 2
It is also possible to use a mixture of more than one DIR compound. Furthermore, to explain in detail the preferred method of adding DIR compounds, etc. in the present invention, one or more of the DIR compounds, etc. may be added to other couplers, etc. as necessary.
Along with hydroquinone derivatives, anti-browning agents, ultraviolet absorbers, etc., organic acid amides, carbamates, esters, ketones, urea derivatives, ethers, hydrocarbons, etc., especially the high boiling point solvent (HBS), and/or the above-mentioned Dissolved in a low boiling point solvent (LBS), mixed with an aqueous solution containing the anionic surfactant and/or nonionic surfactant and/or hydrophilic binder, and dispersed into an emulsion using a high-speed rotating mixer, etc.
Added to silver halide emulsions. In addition, the DIR compounds and the like may be dispersed using the latex dispersion method described above. The color light-sensitive material of the present invention may contain various other photographic additives, such as color stain preventive agents described in JP-A No. 46-2128 and U.S. Pat. No. 2,728,659; magazine
Antifoggants, stabilizers, as described in No. 17643;
Ultraviolet absorbers, color stain inhibitors, optical brighteners, color image browning inhibitors, antistatic agents, hardeners, surfactants, plasticizers, wetting agents, and the like can be used. In the color light-sensitive material of the present invention, the hydrophilic colloids used to prepare the emulsion include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose derivatives, carboxylic Any of cellulose derivatives such as methyl cellulose, starch derivatives, single or copolymer synthetic hydrophilic polymers such as polyvinyl alcohol, polyvinylimidazole, and polyacrylamide are included. Examples of supports for color photosensitive materials include transparent supports such as glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate, polyamide films, polycarbonate films, and polystyrene films. The material is appropriately selected depending on the intended use of the material. Various coating methods such as dip coating, air doctor coating, curtain coating, and hopper coating can be used to coat the emulsion layer and other constituent layers used in the present invention. Also US patent
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 2761791 and No. 2941898. There are no particular limitations on the method of processing photographic materials using the silver halide emulsion according to the present invention, and any processing method can be applied. For example, typical methods include a method in which a protein fixing treatment is performed after color development, followed by further washing and/or stabilization treatment if necessary; a method in which bleaching and fixing are performed separately after color development; A method of further washing with water and/or stabilizing treatment; or a method of performing pre-hardening, neutralization, color development, stop-fixing, washing with water, bleaching, fixing, washing with water, post-hardening, washing with water, color development, washing with water, and supplementation. A method in which color development, stopping, bleaching, fixing, washing, and stabilization are performed in this order, and a development method in which the developed silver produced by color development is bleached with halogenation, and then color development is performed again to increase the amount of pigment produced. Any method may be used. The color developing solution used for processing the silver halide emulsion of the present invention is not limited to, but preferably has a pH of 8 or higher, more preferably Hz.
is an alkaline aqueous solution of 9 to 12. This aromatic primary amine developing agent as a color developing agent is
It is a compound that has a primary amino group on an aromatic ring and has the ability to develop exposed silver halide,
Furthermore, a precursor for forming such a compound may be added as necessary. The color developing agent mentioned above is typically p-phenylenediamine type, and the following are preferred examples. 4-amino-N,N-diethylaniline, 3-
Methyl-4-amino-N,N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-β-hydroxyethylaniline, 3-methyl-
4-Amino-N-ethyl-N-β-methoxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methoxy-4-amino-N-ethyl- N
-β-hydroxyethylaniline, 3-methoxy-4-amino-N-ethyl-N-β-methoxyethylaniline, 3-acetamido-4-amino-
N,N-dimethylaniline, N-ethyl-N-β
-[β-(β-methoxyethoxy)ethoxy]ethyl-3-methyl-4-aminoaniline, N-ethyl-N-β-(β-methoxyethoxy)ethyl-
These include 3-methyl-4-aminoaniline and salts thereof such as sulfates, hydrochlorides, sulfites, p-toluenesulfonates, and the like. Furthermore, for example, JP-A-48-64932, JP-A No. 50-
No. 131526, No. 51-95849, and those described in the Journal of the American Chemical Society, (J.Am.Chem.Sec.), Vol. 73, pp. 3100-3125 (1951) by Bent et al. are also representative. It is mentioned as something like that. The amount of these aromatic primary amino compounds to be used can be determined to determine the level of activity of the developer, but in order to increase the activity, it is preferable to increase the amount used. The amount used is 0.002 mol/
It is used in the range from 0.7 mol/ to 0.7 mol/. Moreover, two or more compounds can be used in appropriate combination depending on the purpose. For example, 3-methyl-4
-amino-N,N-diethylaniline and 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline and 3-methyl-4-amino-
Combinations such as N-ethyl-N-β-hydroxyethylaniline can be freely used depending on the purpose. The color developing solution used in the present invention further contains various commonly added components, such as alkaline agents such as sodium hydroxide and sodium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, development accelerators, and the like can also be optionally included. Examples of additives other than those mentioned above that are added to the color developing solution include bromides such as potassium bromide and ammonium bromide, alkali iodide, nitrobenzimidazole, mercaptobenzimidazole, 5-
Methyl-benzotriazole, 1-phenyl-5
- Compounds for rapid processing solutions such as mercaptotetrazole, as well as anti-stain agents, anti-sludge agents, preservatives, interlayer effect promoters, chelating agents, etc. Bleaching agents used in bleaching solutions or bleach-fixing solutions in the bleaching process are generally known to be those in which metal ions such as iron, cobalt, and copper are coordinated with aminopolycarboxylic acids or organic acids such as oxalic acid and citric acid. There is. The following are representative examples of the above aminopolycarboxylic acids. Ethylenediaminetetraacetic aciddiethylenetriaminepentaacetic acidpropylene diaminetetraacetic acidnitrilotriacetic acidiminodiacetic acid ethyl etherdiaminetetraacetic acidethylenediaminetetrapropionateethylenediaminetetraacetic acid disodium saltdiethylenetriaminepentaacetic acid pentasodium saltnitrilotriacetic acid sodium salt Bleach solution is used with the above bleaching agent It may contain various additives. When a bleach-fixing solution is used in the bleaching step, a solution containing a silver halide fixing agent in addition to the bleaching agent is used. Further, the bleach-fix solution may further contain a halogen compound such as potassium bromide. Then, as in the case of the bleach solution mentioned above, various other additives such as PH buffers, antifoaming agents, surfactants, preservatives, chelating agents, stabilizers, organic solvents, etc. are added and contained. Good too. Examples of silver halide fixing agents include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiourea, thioether, etc., which react with silver halide and become water-soluble. Compounds that form silver salts can be mentioned. The processing temperature of various processing steps such as color development, bleach-fixing (or bleaching, fixing), washing with water, stabilization, drying, etc. performed as necessary for the color photosensitive material of the present invention is carried out at 30°C or higher from the viewpoint of rapid processing. Preferably. The color photosensitive material of the present invention is disclosed in Japanese Patent Application Laid-open No. 58-14834,
No. 58-105145, No. 58-134634 and No. 58-
No. 18631 and Japanese Patent Application No. 58-2709 and No. 59-89288
Stabilization treatment as an alternative to water washing may be performed as shown in No.

【Example】

The details of the present invention will be explained below with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 On a subbed cellulose triacetate support, the following layers were sequentially coated from the support side to prepare a multilayer color film sample (1). 1st layer: Antihalation layer (HC) Antihalation layer consisting of black colloidal silver and gelatin (dry film thickness 2.5 μm). Second layer: First intermediate layer (IL-1) Intermediate layer made of gelatin (dry film thickness 1.0 μm). 3rd layer: Red-sensitive, low-sensitivity lower silver halide emulsion layer (RL) Silver iodobromide emulsion with an average grain size of 0.5 μm and containing 6 mol% of silver iodide (contains 0.5 mol of silver halide and 30 g of gelatin per 1 kg of emulsion) 500 g of this emulsion was chemically sensitized with gold and sulfur sensitizers, and anhydrous 9-ethyl-3,3'-di(3-sulfopropyl)-4,5 was added as a red-sensitive dye. ，
4',5'-Dibenzothiacarbocyanine hydroxide, anhydrous 5,5'-dichloro-9-ethyl-
Add 3,3'-di(3-sulfopropyl)thiacarbocyanine hydroxide and anhydrous 5,5'-dichloro-3',9-diethyl-3-(4-sulfobutyl)oxythiacarbocyanine hydroxide, then 4-hydroxy-6-methyl-
0.25 g of 1,3,3a,7-tetrazaindene was added. An emulsion coating solution prepared by adding 420 ml of the following dispersion (D-1) to 500 g of an emulsion sensitized to red sensitivity was applied to the dry film thickness.
It was applied to a thickness of 3.0 μm. 4th layer: Red-sensitive high-sensitivity silver halide emulsion layer (RH) Silver iodobromide emulsion with an average grain size of 0.6 μm and containing 7 mol% of silver iodide (contains 0.5 mol of silver halide and 30 g of gelatin per 1 kg of emulsion) After chemically sensitizing and spectrally sensitizing the emulsion in the same manner as the third layer emulsion, 185 ml of dispersion (D-1) was added to 500 g of this emulsion and coated to a dry film thickness of 1.5 μm. Fifth layer: Second intermediate layer (IL-2) Intermediate layer consisting of 2.5-di-t-octylhydroquinone and gelatin (dry film thickness 0.8 μm). 6th layer: Green-sensitive, low-sensitivity silver halide emulsion layer (GL) Silver iodobromide emulsion with an average grain size of 0.5 μm and containing 6 mol% of silver iodide (contains 0.5 mol of silver halide and 40 g of gelatin per 1 kg of emulsion) 500 g of this emulsion was chemically sensitized with gold and sulfur sensitizers, and then anhydrous 5, 500 g was added as a green-sensitive sensitizing dye.
5'-dichloro-9-ethyl 3,3'-di-(3-
sulfopropyl)oxacarbocyanine hydroxide, anhydrous 5,5'-diphenyl-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide, anhydrous 9-ethyl-
3,3'-di(3-sulfopropyl)-5,6,
Add 5',6'-dibenzoxacarbocyanine hydroxide followed by 0.25 4-hydroxy-6-methyl-1,3,3a,7-tetosazaindene.
I also added g. An emulsion coating solution prepared by adding 380 ml of the following dispersion (D-2) to 500 g of an emulsion sensitized to green sensitivity was applied to the dry film thickness.
It was coated to a thickness of 3.7 μm. 7th layer: Green-sensitive high-sensitivity silver halide emulsion layer (CH) Silver iodobromide emulsion with an average grain size of 0.6 μm and containing 7 mol% of silver iodide (contains 0.5 mol of silver halide and 40 g of gelatin per 1 kg of emulsion) After chemically sensitizing and spectrally sensitizing the emulsion in the same manner as the sixth layer emulsion, 85 ml of dispersion (D-2) was added to 500 g of this emulsion and coated to a dry film thickness of 1.5 μm. 8th layer: Yellow filter layer (YC) A filter layer (dry thickness: 1.0 μm) consisting of yellow colloidal silver, 2,5-di-t-octylhydroquinone, and gelatin. 9th layer: Blue-sensitive, low-sensitivity silver halide emulsion layer (BL) Silver iodobromide emulsion with an average grain size of 0.5 μm and containing 7 mol% of silver iodide (contains 0.5 mol of silver halide and 80 g of gelatin per 1 kg of emulsion) After chemically sensitizing 500 g of this emulsion, 1350 ml of the following dispersion (D-3) was added to prepare an emulsion coating solution and coated to a dry film thickness of 3.0 μm. 10th layer: Blue-sensitive high-sensitivity silver halide emulsion layer (BH) Silver iodobromide emulsion with an average grain size of 0.8 μm and containing 7 mol% of silver iodide (contains 0.5 mol of silver halide and 80 g of gelatin per 1 kg of emulsion) was chemically sensitized in the same manner as the ninth layer emulsion, and 550 ml of dispersion (D-3) was added to 500 g of this emulsion to give a dry film thickness of 2.0 μm.
It was coated to give a thickness of m. 11th layer: Third intermediate layer (IL-3) Intermediate layer consisting of ultraviolet absorber and gelatin (dry film thickness 1.2 μm). 12th layer: Protective film (PL) Protective layer consisting of matting agent and gelatin (dry film thickness 0.7 μm). Each dispersion contains the coupler (and DIR compound) as tricresyl phosphate (abbreviated as TCP).
and ethyl acetate (abbreviated as EA) mixture,
It was added to a 10% aqueous gelatin solution containing sodium triisopropylnaphthalene sulfonate (PNS) and emulsified and dispersed in a colloid mill to give a constant amount. D-1 (Cyan coupler acid fraction) Composition Coupler C-1 30.0g Coupler C-2 3.0g DIR-1 0.3g DIR-2 0.7g TCP 33g EA 198g 10% gelatin 440ml PNS 2.0g 1000ml using distilled water Prepared to. D-2 (Magenta coupler dispersion) Composition Coupler M-a 40.0g Coupler M-b 8.0g DIR-3 2.5g TCP 4.8g EA 145g 10% gelatin 400ml PNS 4.5g Adjust to 1000ml using distilled water. D-3 (Yellow coupler dispersion) Composition Coupler Y-1 50.0g TCP 5.0g EA 165g 10% gelatin 370ml PNS 4.0g Adjusted to 1000ml using distilled water. As shown in Table 1, for sample (1) prepared in this manner, the coupler in dispersion (D-2) was changed to the coupler of the present invention, the DIR compound was also changed, and the non-diffusive dye of the present invention was added. Samples (2) to (10) were prepared in the same manner except that they were added to the 8th layer and the 12th layer.

【table】

[Table] C-1 C-2 M-a M-b Y-1 DIR-1 DIR-2 DIR-3 DIR-4 A-1 A-2 Mordant-2 n=500 dye-7 A-3 These samples were each subjected to wedge exposure using white light and then processed according to the following processing steps to obtain dye images. Processing process (38℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Please note that the color development processing solution PH were treated with the following changes. Treatment liquid 1 (standard) PH10.02 Treatment liquid 1 (low PH) PH9.82 Treatment liquid 3 (high PH) PH10.22 The composition of the treatment liquid used in each treatment step is as follows. Color developer 4-amino 3-methyl-N-ethyl-N(β-hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 0.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium sulfite 5.10g Anhydrous potassium bicarbonate 3.46g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate)
12.0g Potassium hydroxide 1.48g Add water to make 1. Bleach ethylenediaminetetraacetate iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide 150.0g glacial acetic acid 10.0ml Add water and use ammonia water to pH
Adjust to 5.0. Fixer Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.5g Sodium metasulfite 2.3g Add water and adjust to pH 6.0 using acetic acid. Stabilizing liquid formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. The sensitivity and sharpness of the dye image of each sample thus obtained were measured. The results are shown in Table 2. Note that the sensitivity is a relative value when the sensitivity of the cyan image of sample (1) exposed to white light is taken as 100, and the evaluation of image sharpness is calculated by calculating the MTF and setting it at 90% and 50%.
This was done using the spatial frequency of Low frequency region (MTF90% resolution) and high frequency region (MTF50
% resolution), the higher the spatial frequency, the better the sharpness. Furthermore, the dye image was measured using a xenon fade meter.
After exposure for 120 hours, the concentration after exposure (D) and the concentration before exposure (Do) were measured and macenta dye residual rate (D/Do×
100).

[Table] As is clear from Table 2, samples (3) to 1 according to the present invention
(10) all have improved sharpness compared to the comparative samples, and this effect hardly changes even if the processing liquid changes. It can also be seen that the light clarity of the magenta dye image is also improved. Example 2 Multilayer color film samples (11) to (20) were prepared in the same manner as in Example 1 except that the layer structure was different. Layer order First layer: Antihalation layer (HC) Same as the first layer of Example 1. Second layer: first intermediate layer (IL-1) Same as the second layer of Example 1. Third layer: red-sensitive low-sensitivity emulsion layer (RL) Same as the third layer of Example 1. Fourth layer: Second intermediate layer (IL-2) Same as the fifth layer of Example 1. 5th layer: green-sensitive low-sensitivity emulsion layer (GL) Same as the 6th layer of Example 1. Sixth layer: Third intermediate layer (IL-3) Same as the fifth layer of Example 1. 7th layer: Blue-sensitive low-speed emulsion layer (BL) Same as the 9th layer in Example 1. Eighth layer: Fourth intermediate layer (IL-4) Same as the fifth layer of Example 1. 9th layer: red-sensitive high-sensitivity emulsion layer (RH) Same as the 4th layer of Example 1. 10th layer: 5th intermediate layer (IL-5) Same as the 5th layer of Example 1. 11th layer: Green-sensitive high-sensitivity emulsion layer (GH) Same as the 7th layer in Example 1. 12th layer: Yellow filter layer (YC) Same as the 8th layer of Example 1. 13th layer: Blue-sensitive high-sensitivity emulsion layer (BH) Same as the 10th layer of Example 1. 14th layer: 5th intermediate layer (IL-6) Same as the 11th layer of Example 1. 15th layer: Protective layer (PL) Same as the 12th layer of Example 1. Note that the non-diffusible dye was added to the 15th layer. The above samples were subjected to the same processing as in Example 1, and the sensitivity, sharpness, and dye image light resistance were evaluated, and good results were obtained for all samples according to the present invention.

Claims (1)

[Scope of Claims] 1. A non-photosensitive layer (filter layer) containing a non-diffusing substance that absorbs green light and/or red light, and a blue-sensitive, green-sensitive and red-sensitive layer on a support. a photographic constituent layer including a silver halide emulsion layer, the filter layer being located on a side farther from the support than the silver halide emulsion layer that is exposed to light in a wavelength range absorbed by the filter layer, and A silver halide color photographic light-sensitive material, wherein the green-sensitive silver halide emulsion layer contains a magenta dye-forming coupler represented by the following general formula []. General formula [] [In the formula, R ₁ represents a primary alkyl group, and R ₂ represents a hydrogen atom or a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. ] 2 The filter layer is a layer that absorbs green light,
2. The halide color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion layer sensitive to green light is a green-sensitive emulsion layer. 3. The filter layer is a layer that absorbs red light,
The silver halide color photographic light-sensitive material according to claim 1, wherein the silver halide emulsion layer that is sensitive to red light is a red-sensitive emulsion layer. 4. The silver halide color photographic light-sensitive material according to claim 1, wherein the filter layer is located on a side farther from the support than the photosensitive silver halide emulsion layer furthest from the support. 5. The silver halide color photographic light-sensitive material according to claim 1, wherein the light-absorbing non-diffusive substance is an oil-soluble substance.