JPH0549090B2 - - Google Patents

Description

[Detailed description of the invention]

B. Field of Industrial Application The present invention relates to a photographic light-sensitive material, particularly a silver halide color light-sensitive material. B. Prior Art Regarding silver halide color light-sensitive materials, it is desired to improve quality aspects such as image quality, sensitivity, and storage stability, as well as to shorten development time and improve simplicity, and various studies have been conducted for this purpose. It is. Above all,
As cameras become smaller and the screen size of one frame of photosensitive material becomes smaller, there is a strong desire to improve image quality. This is because, when obtaining color prints of the same size, image quality must be improved in proportion to the enlargement magnification of photographic photosensitive materials.
This is because the photograph will look grainy and the details will be blurred. The present invention relates to a light-sensitive material that achieves improved depiction of details (hereinafter referred to as "sharpness"), particularly among the various properties that are desired to be improved. In general, silver halide photosensitive materials contain a compound (hereinafter referred to as a "coupler") that produces a dye through a coupling reaction with an oxidized form of a developing agent produced during development of the photosensitive silver halide. It consists of a protective colloid containing The coupler is contained in the protective colloid layer in a state in which it is dissolved in a high boiling point solvent having a boiling point of 175° C. (under 1 atmosphere) or higher and is dispersed in the protective colloid layer. It is known that the sharpness is improved as the thickness of the protective colloid layer becomes thinner, and coating methods have gradually been made thinner by improving the hardening agent for the protective colloid layer and improving the quality of the protective colloid. Ta. however,
This breakthrough is desired because if the amount of protective colloid is excessively reduced in order to make the layer thinner, the high boiling point solvent contained in the layer will gradually ooze out. In order to prevent such oozing of high-boiling point solvents, it is necessary to increase the amount of protective colloid according to the total weight of the coupler and high-boiling point solvent contained in the protective colloid layer, and research is conducted under these constraints. has been progressing. As a result of this research,
A method using a polymer coupler latex described in JP-A-58-28745 has been proposed. However, when such polymeric couplers are used, the color development efficiency is still not sufficient, and there has been a strong desire to develop a new technology that can improve sharpness without reducing color development efficiency. On the other hand, it is known that using a polymer coupler latex can reduce the coating film thickness to some extent and improve the sharpness in the high frequency range to some extent, but it is still insufficient, especially in the low frequency range. Sharpness is insufficient. Therefore, some attempts have been made to improve the sharpness in the low frequency range by using a polymer coupler latex with a coupler that can release a diffusive development-inhibiting substance (see Japanese Patent Laid-Open No. 59-36249). Although some improvement is seen, it is still insufficient. C. Object of the Invention An object of the invention is to provide a photographic material that has sufficient sharpness over the entire range of high and low frequencies. D. Structure of the invention and its effects That is, the photographic light-sensitive material according to the present invention has a molecular weight of
This photographic light-sensitive material is characterized in that it contains a low molecular weight coupler having a molecular weight of 250 to 450 and a coupler that can release a development inhibitory substance having a degree of diffusivity of 0.4 or more through a coupling reaction. The photographic light-sensitive material of the present invention contains the above-mentioned low molecular weight coupler, but since this low molecular weight coupler has a small molecular weight of 250 to 450, compared to known couplers, when the number of moles is the same ( That is,
If Dmax is made to be about the same), the weight will be considerably smaller. Therefore, while maintaining a sufficient Dmax, the amount of coupler can be reduced, thereby reducing the amount of hydrophilic colloids such as gelatin (and the amount of high boiling point solvents), and improving sharpness by making the emulsion layer thinner. Furthermore, it is possible to prevent the phenomenon of sweating. In addition, the low molecular weight coupler used in the present invention has a faster coupling reaction rate than a polymer coupler latex, thereby providing sufficient color development efficiency and shortening the development processing time. The present inventor has studied conventional photographic light-sensitive materials. In order to prevent the coupler from moving, a group with a large atomic weight called a ballast group was required to make the coupler non-diffusive.
For this reason, the molecular weight of the coupler incorporated in the sensitive material is usually as large as 500 or more. The present inventor has particularly found that when the coupler core does not contain an alkali easily soluble group such as a carboxyl group or a sulfo group, the molecular weight (MW) of the coupler is
The present invention was achieved based on the discovery that both the coupler and the dye obtained by development are non-diffusible even when the number is 450 or less. However, if the MW is less than 250, the coupler will easily diffuse in the protective colloid layer, so the MW of the coupler should be 250 or more. In the present invention, if the molecular weight of the coupler is set to 300 to 400, the effects of the present invention can be achieved even better. Incidentally, the coupler having a molecular weight of 250 to 450 according to the present invention is referred to as a "low molecular weight coupler" in this specification. The improvement in sharpness by the low molecular weight coupler of the present invention greatly contributes to the sharpness in the high frequency region of the MTF curve. However, it is not only the MTF value in the high frequency region that affects visual sharpness.
The MTF value in the low frequency region also has a strong influence. According to the present invention, in addition to the low molecular weight coupler improving the sharpness mainly in the high frequency range, the coupler (hereinafter referred to as It has been found that by using a DIR coupler (referred to as a diffusive DIR coupler) in combination, sharpness in the low frequency range can be sufficiently improved, and sharpness can be improved over the entire frequency range. On the other hand, when a coupler that releases a non-diffusible development inhibiting substance is also used, the sharpness in the low frequency region is not improved. In this way, the effect of improving sharpness (especially in the low frequency range) due to the combined use of the diffusive DIR coupler of the present invention is due to the fact that the development inhibitor released during the coupling reaction diffuses and moves from the photosensitive area to the non-photosensitive area. This is thought to be due to the so-called edge effect. In the present invention, it is preferable that the above-mentioned low molecular weight coupler and diffusible DIR coupler are both contained in the silver halide emulsion layer. It is extremely effective. in this case,
A color photographic light-sensitive material having at least one blue-sensitive silver halide-containing protective colloid layer, at least one green-sensitive silver halide-containing protective colloid layer, and at least one red-sensitive silver halide-containing protective colloid layer. Preferably, at least one photosensitive silver halide-containing protective colloid layer contains a low molecular weight coupler and a diffusible DIR coupler. The low molecular weight coupler used in the present invention is preferably one represented by the following general formula. General formula: (However, Coup is a coupler core component; or atoms),
n is an integer of n≧1, and when n≧2, the plurality of Ys may be the same or different. ) In this general formula, examples of the coupler core include benzoylacetanilide, pivaloylacetanilide, 1-phenyl-5-pyrazolone, pyrazolobenzimidazole, pyrazolotriazole, cyanoacetylcoumarone, acetoacetonitrile, indazolone, phenol, Examples include naphthol. Specific examples of X include those listed below as X ¹ to X ⁶ . Examples of Y include R ¹ to R ⁷ , J-R ⁸ , R ⁹ ,
Among those exemplified as R ¹¹ to R ²¹ , atoms other than hydrogen atoms may be mentioned. Among the low molecular weight couplers represented by the above general formula, if the sum of the atomic weights of X is A, the sum of the atomic weights of Y is B, and the sum of the atomic weights of Coup is C, then (A-1) + (B-n )/C+(n+1)=0.1~2
.5 (where n indicates the number of Y) is particularly desirable in that the coupler is difficult to crystallize and the dye generated during development is difficult to move through the layer. Furthermore, in the above, B-n
> A-1, the dye produced by the reaction with the oxidized form of the color developing agent (CD), that is, CD=Coup-(Y) _o
will exhibit more non-diffusivity due to the presence of Y in the molecule. Therefore, the sharpness of the layer containing the low molecular weight coupler can be maintained at a higher level. The stereotype that all practical couplers contained in known protective colloids require large groups to be non-diffusive is that (A-1)+(B-n)/C+(n+1 ) is large, and conventional practical coupler cores are structurally limited and have a coupler molecular weight larger than the range of the present invention, which makes it impossible to make the protective colloid layer thinner, making it difficult to improve sharpness. I can't expect it at all. Since the low molecular weight couplers of the present invention require less weight to obtain the same color density than known internal couplers, they can achieve thinner layers, which is the object of the present invention. In addition, in order to obtain sufficient color development, the ratio of the sum of the coupler weight and the weight of the high boiling point solvent to the protective colloid should be 0.5 to 1.5, more preferably 0.8 to 1.5.
It is desirable to set it to 1.5. This improvement in color development is due to
This is achieved regardless of the ratio of the weight of the high-boiling solvent to the weight of the coupler, and considering that the generation of known internal couplers does not depend on the weight of the protective colloid relative to the weight of the coupler and the weight of the high-boiling solvent, this is an unexpected result. It is something. The color photosensitive material based on the present invention has a structure in which, on a support,
It consists of at least one protective colloid layer containing a photosensitive silver halide and a high boiling point solvent dispersed in a protective colloid in which the low molecular weight coupler of the present invention is dissolved. The improved sharpness achieved using low molecular weight couplers is obtained with respect to the image quality of the protective colloid layer containing the low molecular weight coupler as well as with respect to the image quality of other color image forming layers in color light-sensitive materials. In color photosensitive materials, it is known that light is reflected at the interface between the support and the protective colloid layer, and at the interface between the protective colloid layer and air. Reflection at the interface between the support and the air layer on the side where the color photosensitive layer is not coated is also added. Since the protective colloid layer according to the present invention is thin, light that once enters the color photosensitive material is repeatedly reflected (ie, multiple reflections) within the protective colloid layer and is attenuated. Therefore, deterioration of sharpness is effectively prevented, so that sharpness is improved in layers thinned using low molecular weight couplers and other layers. The photographic light-sensitive material according to the present invention preferably has one or more blue-sensitive silver halide emulsion layers containing a yellow coupler and one or more green-sensitive silver halide emulsion layers containing a magenta coupler. and one or more red-sensitive silver halide emulsion layers containing a cyan coupler. In this case, at least one of the blue-sensitive silver halide emulsion layers preferably contains a low molecular weight yellow coupler. In this case, the sharpness of both layers can be improved without improving the green-sensitive silver halide emulsion layer or the red-sensitive silver halide emulsion layer. Visually judging the print as a final image, the improvement in magenta image obtained with the green-sensitive silver halide emulsion layer is judged to be the most improved when the sharpness is improved to the same extent.
On the other hand, improvements in the blue-sensitive layer are not strongly perceived as improvements in the final image. Nevertheless, in the present invention, it is surprising that improvements in the blue-sensitive layer result in significant improvements in the final image. For the same reason, it is desirable that at least one of the green-sensitive silver halide emulsion layers contains a low molecular weight magenta coupler. By adopting such a structure, the sharpness of the dye image obtained not only by the green-sensitive silver halide emulsion layer but also by the red-sensitive silver halide emulsion layer located below it is further improved. Therefore, when a photographic light-sensitive material is composed of blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers, at least a blue-sensitive silver halide emulsion layer, more preferably a blue-sensitive silver halide emulsion layer. It is desirable that the low molecular weight coupler of the present invention be contained in the green-sensitive silver halide emulsion layers, and most preferably in all of the blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layers. Furthermore, when a silver halide emulsion layer having the same color sensitivity is composed of two or more layers, from the above point of view, it is desirable that at least the upper layer contains the coupler of the present invention. . On the other hand, in photographic materials, the technology of creating two or more of the same photosensitive layer in order to photograph subjects with a wide range of illuminance is widely known, and commercialization is also needed to meet the demand for higher sensitivity. It is used in silver halide color photosensitive materials. In this technique, the least sensitive layer contributes the most to the density of the image and often uses the most couplers. Usually, the weight of the coupler added to the layer controls the film thickness of the layer, so in such a case, if the low molecular weight coupler of the present invention is used in the lowest sensitivity emulsion layer, the effect of the present invention will be improved. be discovered. That is, from this point of view, at least the blue-sensitive silver halide emulsion layer is composed of two or more silver halide emulsion layers, and the silver halide emulsion layer with the lowest sensitivity among these silver halide emulsion layers It is preferable that a low molecular weight yellow coupler be contained in the yellow coupler. Further, at least the green-sensitive silver halide emulsion layer is constituted by two or more silver halide emulsion layers,
It is preferable that a low molecular weight magenta coupler be contained in the silver halide emulsion layer having the lowest sensitivity among these silver halide emulsion layers. The low molecular weight coupler of the present invention is not limited as long as it is a compound that can develop color by oxidative coupling with an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in color development treatment. However, those having an alkali easily soluble group such as a carboxyl group or a sulfo group may not be preferred. As this low molecular weight coupler, for example, as a magenta coupler,
There are pyrazolotriazole couplers, 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc. Cyan couplers include naphthol couplers and phenol couplers. The coupler may be either 4-equivalent or 2-equivalent to silver ion. Further, the photographic performance can be further improved by using two or more types of low molecular weight couplers of the present invention in combination. An example of a combination in this case is a method of using couplers in which the coupling speed of one coupler is 1.3 to 15 times the coupling speed of the other coupler. Here, the coupling speed of a coupler is defined as the rate of coupling in a color image obtained by mixing two types of couplers A and B, which give different dyes that can be clearly separated from each other, and adding the mixture to an emulsion for color development. By measuring the amount of each pigment,
It can be determined as a relative value. If we express the maximum density of coupler A (D _A ) max., and the color development of density D _A in the middle stage, and the color development of coupler B (D _B ) max., then the color development of D _B is expressed as The reaction activity ratio R _A /R _B is expressed by the following formula. R _A /R _B =log(1-D _A /(D _A )max.)/log(1-D _B
/ _{( D B} (1-
The coupling activity ratio R _A /R _B can be determined from the slope of the straight line obtained by plotting D/Dmax. The low molecular weight couplers used in the present invention will be explained in more detail. First, the low molecular weight coupler for yellow is preferably one having benzoylacetanilide as a core, especially the general formula: (However, R ¹ , R ² , R ³ , and R ⁴ are substituent components (substituents or atoms such as hydrogen atoms), and X ¹ is separated by the reaction between the coupler of this general formula and the oxidized product of the color developing agent. A yellow coupler represented by the following formula is preferable. However, in this general formula, R ¹ , R ² , R ³ , R ⁴
The sum of the atomic weights of and X ¹ is preferably 30 to 210, and 50
~165 is more desirable. In the above general formula, R ¹ , R ² , R ³ , and R ⁴ may be the same or different; for example, a hydrogen atom, a halogen atom, an alkyl group (such as a methyl group, an ethyl group,
isopropyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, methoxyethoxy group, etc.), aryloxy group (e.g., phenoxy group, etc.), acylamino group (e.g., acetylamino group,
trifluoroacetylamino group, etc.), sulfonamino group (e.g. methanesulfonamino group, benzenesulfonamino group, etc.), carbamoyl group,
Examples include sulfamoyl group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group, ureido group, and cyano group. X ¹ has the same meaning as X described above, and preferable examples include a hydrogen atom, a halogen atom, and those represented by the following general formula. General formula:

【formula】 [MW≒380]

y-2 [MW≒368] y-3 [MW≒340] y-4 [MW≒434] y-5 [MW≒379] y-6 [MW≒405] y-7 [MW≒420] y-8 [MW≒410] y-9 [MW≒380] y-10 [MW≒361] y-11 [MW≒445] Further, yellow couplers having pivaloylacetanilide as a core are also preferred, and yellow couplers of the following general formula can be used in particular. General formula: Here, the sum of the atomic weights of R ⁵ , R ⁶ and X ² is 35 ~
230 is preferable, and 80-185 is more preferable. R ⁵ and R ⁶ have the same meaning as R ¹ and R ² described above, and may be the same or different, such as a hydrogen atom, a halogen atom, an alkyl group (such as a methyl group, an ethyl group, an isopropyl group, etc.), Alkoxy groups (e.g. methoxy, ethoxy, methoxyethoxy, etc.), aryloxy groups (e.g. phenoxy, etc.), acylamino groups (e.g. acetylamino, trifluoroacetylamino, etc.), sulfonamino groups (e.g. methanesulfonamino) (benzenesulfonamino group, etc.), carbamoyl group, sulfamoyl group, alkylthio group, alkylsulfonyl group, alkoxycarbonyl group, ureido group, and cyano group. X ² has the same meaning as the above-mentioned X ¹ , and the same ones are exemplified. Specific examples of yellow couplers of this general formula are as follows. y-12 [MW≒358] y-13 [MW≒386] y-14 [MW≒440] y-15 [MW≒442] y-16 [MW≒437] As the yellow coupler, a benzoylacetanilide type coupler is preferable because it has a high color density and can be made into a thinner layer. Preferred low molecular weight magenta couplers for use in the present invention are those having a pyrazolotriazole core, particularly those of the general formula: (However, R ⁷ , -J-R ⁸ and R ⁹ are all the above-mentioned R ¹
, and X ³ has the same meaning as X ¹ above. ) is a magenta coupler. However, in this general formula, it is desirable that the sum of the atomic weights of R ⁷ , -J-R ⁸ and R ⁹ and X ³ which is X is 150 to 340,
200-300 is more preferable. R ⁷ and R ⁸ are, for example, a hydrogen atom, an alkyl group that may have a substituent (e.g., methyl group, ethyl group, isopropyl group, propyl group, butyl group), an aryl group (e.g., phenyl group, naphthyl group), or Represents a heterocyclic residue, and J is, for example, a bond, -O-, -S-,

[MW≒269]

m-2 [MW≒333] m-3 [MW≒305] m-4 [MW≒333] m-5 [MW≒266] m-6 [MW≒375] m-7 [MW≒344] m-8 [MW≒302] m-9 [MW≒305] m−10 [MW≒293] m-11 [MW≒308] m-12 [MW≒269] m-13 [MW≒275] m-14 [MW≒326] m-15 [MW≒438] m-16 [MW≒431] In addition to the above, magenta couplers include 1
Those having -phenyl-5-pyrazolone or pyrazolobenzimidazole as a core are preferred, and those represented by the following general formulas are particularly preferred. General formula:

【formula】 General formula:

[MW≒343]

m-18 [MW≒425] m-19 [MW≒427] m-20 [MW≒430] m-21 [MW≒417] As the magenta coupler, a pyrazolotriazole type coupler as shown in the general formula is preferable because the dye obtained by development does not absorb unnecessary blue light, has a high color density, and can be made into a thinner layer. The cyan coupler that can be used in the present invention preferably has a phenol or naphthol core, and is particularly preferably one having the following general formula. General formula: General formula: In this general formula, R ¹⁵ to R ²¹ are all the same as R ¹ above, and X ⁵ and X ⁶ are all the same as X above. In the general formula, the sum of the atomic weights of R ¹⁵ , R ¹⁷ to ^{R 19} and X ⁵ is preferably 165 to 350, and 200
~300 is more preferred. Also, in the general formula,
The total atomic weight of R ¹⁶ to R ²¹ and X ⁶ is preferably 115 to 310, more preferably 160 to 265. Examples of R ¹⁵ include hydrogen atoms, aliphatic groups (e.g. alkyl groups such as methyl, isopropyl, acyl, cyclohexyl, and octyl), alkoxy groups (e.g. methoxy, isopropoxy, pentadecyloxy), aryloxy groups (e.g. phenoxy, β-tert-butylphenoxy group), an acylamide group, a sulfonamide group, a ureido group, or a carbamoyl group shown in the following general formula. -NH-CO-G -NH-SO ₂ -G -NHCONH-G In the formula, G and G' may be the same or different, and each is a hydrogen atom (however, G and G' are not hydrogen atoms at the same time), an aliphatic group having 1 to 8 carbon atoms,
Preferably, it represents a straight or branched alkyl group or cyclic alkyl group having 4 to 8 carbon atoms (eg, cyclopropyl, cyclohexyl, norbornyl, etc.), or an aryl group (eg, phenyl, naphthyl, etc.). Here, the above alkyl group and aryl group are halogen atoms (e.g. fluorine, chlorine, etc.), nitro group, cyano group, amino group (e.g. amino, alkylamino, dialkylamino, anilino, N-
alkylanilino, etc.), alkyl groups (such as those mentioned above), aryl groups (such as phenyl,
acetylaminophenyl, etc.), alkoxycarbonyl groups (e.g. butyloxycarbonyl, etc.),
Acyloxycarbonyl group, amide group (e.g., acetamide, methanesulfonamide, etc.), imide group (e.g., succinimide, etc.), carbamoyl group (e.g., N,N-diethylcarbamoyl, etc.), sulfamoyl group (e.g., N,N-diethylsulfonamide, etc.) moyl, etc.), alkoxy groups (e.g. ethoxy, butyloxy, octyloxy, etc.),
It may be substituted with an aryloxy group (eg, phenoxy, methylphenoxy, etc.). ^R15
may contain commonly used substituents in addition to the above-mentioned substituents. R ¹⁶ is selected from, for example, a hydrogen atom, an aliphatic group, especially an alkyl group, or a carbamoyl group represented by the above general formula. ^R17 , ^R18 ,
Examples of R ¹⁹ , R ²⁰ and R ²¹ include a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a heterocyclic group, an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, or a carbamyl group. Examples include groups.
Specific examples of R ¹⁷ include the following: Hydrogen atoms, halogen atoms (e.g. chloro, bromo, etc.), primary, secondary or tertiary alkyl groups (e.g. methyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, hexyl, 2-chlorobutyl, 2 -hydroxyethyl, 2-phenylethyl, 2-(2,4,6-trichlorophenyl)ethyl, 2-aminoethyl, etc.), alkylthio groups (e.g. octylthio, etc.), aryl groups (e.g. phenyl, 4-methylphenyl, 2, 4,
6-trichlorophenyl, 3,5-dibromophenyl, 4-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, naphthyl, 2-chloronaphthyl,
3-ethylnaphthyl, etc.), heterocyclic groups (e.g., benzofuranyl group, furanyl group, thiazolyl group, benzothiazolyl group, naphthothiazolyl group, oxazolyl group, benzoxazolyl group, naphthoxazolyl group, pyridyl group, quinolinyl group, etc.) , amino groups (e.g., amino, methylamino, diethylamino, phenylamino, tolylamino, 4-cyanophenylamino, 2-trifluoromethylphenylamino, benzothiazoleamino, etc.), carbonamide groups (e.g., alkyl groups such as ethylcarbonamide, etc.) Carbonamide group; Arylcarbonamide group such as phenylcarbonamide, 2,4,6-trichlorophenylcarbonamide, 4-methylphenylcarbonamide, 2-ethoxyphenylcarbonamide; thiazolylcarbonamide, Benzothiazolylcarbonamide, oxazolylcarbonamide, benzoxazolylcarbonamide, imidazolylcarbonamide,
Heterocyclic carbonamide groups such as benzimidazolylcarbonamide, etc.), sulfonamide groups (alkylsulfonamide groups such as butylsulfonamide, phenylethylsulfonamide, etc.; phenylsulfonamide, 2,4,6-trichloro) Arylsulfonamide groups such as phenylsulfonamide, 2-methoxyphenylsulfonamide, 3-carboxyphenylsulfonamide, etc.; thiazolylsulfonamide, benzothiazolylsulfonamide, imidazolylsulfonamide, benzimidazolylsulfonamide, Heterocyclic sulfonamide groups such as pyridylsulfonamide, etc.), sulfamyl groups (alkylsulfamyl groups such as propylsulfamyl, octylsulfamyl, etc.); phenylsulfamyl,
2,4,6-trichlorophenylsulfamyl,
Arylsulfamyl groups such as 2-methoxyphenylsulfamyl; heterocycles such as thiazolylsulfamyl, benzothiazolylsulfamyl, oxazolylsulfamyl, benzimidazolylsulfamyl, pyridylsulfamyl groups, etc. sulfamyl group, etc.) and carbamyl groups (alkylcarbamyl groups such as ethylcarbamyl, octylcarbamyl, etc.; phenylcarbamyl, 2,4,
Arylcarbamyl groups such as 6-trichlorophenylcarbamyl, and heterocyclic groups such as thiazolylcarbamyl, benzothiazolylcarbamyl, oxazolylcarbamyl, imidazolylcarbamyl, benzimidazolylcarbamyl, etc. carbamyl group, etc.). ^R18 , ^R17 , ^R20 and ^R21
Specific examples of R ¹⁷ can also be mentioned, and J represents a nonmetallic atom necessary to form a 5- and/or 6-membered ring as shown below. i.e. benzene ring, cyclohexene ring,
Cyclopentene ring, thiazole ring, oxazole ring, imidazole ring, pyridine ring, pyrrole ring, etc. Among these, a benzene ring is preferred. X ⁵ and X ⁶ are preferably a hydrogen atom, a halogen atom, or a group (eg, alkyl, aryl, heterocycle) bonded to the coupling position via -O-, -S-, -N=N-. Preferred examples of such groups include alkoxy, aryloxy, alkylthio, and arylthio groups. These groups further include -O-, -S-, -NH-, -CONH-, -
COO−, −SO ₂ NH−, −SO−, −SO ₂ − −CO
-,

【formula】 [MW≒362]

c-2 [MW≒326] In the present invention, known couplers may be included in combination with the low molecular weight couplers of the above-mentioned colors. However, in this case, it is desirable to use the low molecular weight coupler according to the invention in an amount of 50 to 100 parts by weight per 100 parts by weight of the total amount of couplers. These couplers are generally added in an amount of 2 x 10 ^-3 mol to 5 x 10 -1 mol, preferably 1 x 10 ^-2 mol to 5 x ^{10 -1} mol, per mol of silver in the silver halide emulsion layer. . Next, the diffusible DIR coupler used in the present invention will be explained. This coupler provides sharpness in the low frequency range,
In other words, in order to increase the MTF value (especially to 1.15 or more), the same coupler has a coupling reaction,
It is desirable that a development inhibiting substance having a diffusivity of 0.4 or more, which will be described later, be released or separated directly or indirectly. The degree of diffusion of this development inhibiting substance is measured by the method described below. First, each layer having the following composition is sequentially provided on a transparent support to prepare a sample. 1st layer: Red-sensitive silver halide emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average size
0.4 μ) was given red sensitivity by using 6 x 10 ^-5 mol of sensitizing dye, which will be described later, per 1 mol of silver.
Emulsion and coupler A below per mole of silver
The gelatin coating solution containing 0.0015 mol of silver was
Coat at 1.8g/ ^m2 (film thickness 2μ). Coupler A: Second layer: A gelatin layer (silver content: 2 g/m ² , film thickness: 1.5 μm) containing the silver iodobromide emulsion used in the first layer before sensitization and polymethyl methacrylate particles (approximately 1.5 μm in diameter). Furthermore, each layer contains a gelatin hardening agent and a surfactant. A sample was prepared in the same manner as the sample except for the silver iodobromide emulsion in the second layer of the sample. After both samples were wedge exposed, they were developed as described below. Development processing (38℃) 1 Color development...2 minutes 10 seconds2 Innocence...6 minutes 30 seconds3 Washing...3 minutes 15 seconds4 Fixing...6 minutes 30 seconds5 Washing...3 minutes 15 seconds6 Stable... ...3 minutes 15 seconds Processing solution composition Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-ethyl-N-β-hydroxyethylamino) -2-Methyl-aniline sulfate 4.5g Development inhibitor Add enough water to half the sample concentration 1 Bleach solution Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt 130g Glacial acetic acid 14ml Add water 1 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer formalin 8.0ml Add water 1 Develop The diffusivity of the inhibitory substance was determined based on the rate of decrease in concentration of the sample. That is, the rate of decrease in concentration of the sample as a result of processing with a developer is defined as △n〓(%), and the rate of decrease in concentration of the sample as △n〓( %), the degree of diffusion of the development inhibiting substance is expressed as degree of diffusion = △n〓/△n〓. Below, the degree of diffusion of the development inhibiting substance is exemplified. Degree of diffusion of the development inhibiting substance

[Formula] 0.87

[Formula] 0.72

[Formula] 0.49

[Formula] 0.44

[Formula] 0.32

[Formula] 0.21 A (DIR) coupler capable of releasing a development inhibitor with a degree of diffusion of 0.4 or more is represented by the following general formula. General formula: A(-Y)m In this general formula, A represents a coupler component, and Y
is a development inhibitor or a group containing it, which is bonded to the coupling position of A, and m is 1 or 2.
represents. Here, A may be coupled with an oxidized form of a color developing agent, and it does not matter whether or not a dye is formed as a result of the coupling reaction. Y in the above general formula is preferably one represented by the following general formula a. General formula a: General formula b: General formula c: General formula d: General formula e: General formula XI: General formula XII: General formula: R ²² is an alkyl group, an alkoxy group, an acylamino group, a halogen atom, an alkoxycarbonyl group,
Aryloxycarbonyl group, thiazolylideneamino group, acyloxy group, carbamoyl group (N-
alkylcarbamoyl-N,N-dialkylcarbamoyl, etc.), nitro group, amino group, carbamoyloxy group (including N-arylcarbamoyloxy, N-alkylcarbamoyloxy, etc.), hydroxy group, sulfamoyl group, alkoxycarbonylamino group , an alkylthio group, an arylthio group, an aryl group, a heterocyclic group, a cyano group, an alkylsulfonyl group or an aryloxycarbonylamino group. n represents 1 or 2, and when n is 2 or more
R ²² may be the same or different. n R ²²
The total number of carbon atoms contained in is 0 to 10. R ²³ represents an alkyl group, an aryl group or a heterocyclic group. The total number of carbon atoms in R ²³ is 1 to 15. R ²⁴ represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. R ²⁵ represents a hydrogen atom, an alkyl group, an aryl group, an allogen atom, an amino group, an acylamino group, an alkoxycarbonylamino group, an aryloxycarbonylamino group, an alkanesulfonamide group, a cyano group, a heterocyclic group, or an alkylthio group. The total carbon number of R ²⁴ and R ²⁵ is 1 to 15. When R ²² , R ²³ , R ²⁴ or R ²⁵ is an alkyl group,
It may be substituted or unsubstituted, chain or cyclic, and may have a substituent. Substituents include halogen atom, nitro group, cyano group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, carbamoyl group, hydroxy group, alkylsulfonyl group, arylsulfonyl group, alkylthio group. group, arylthio group, etc. When R ²² , R ²³ , R ²⁴ or R ²⁵ is an aryl group,
The aryl group may have a substituent. Examples of substituents include alkyl groups, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, halogen atoms, nitro groups, amino groups, sulfamoyl groups, hydroxy groups, carbamoyl groups, aryloxycarbonylamino groups, alkoxycarbonylamino groups, acylamino groups, Examples include cyano group and ureido group. When R ²² , R ²³ , R ²⁴ or R ²⁵ is a heterocyclic group,
The hetero atom is preferably a nitrogen atom, an oxygen atom, or a sulfur atom, preferably a 5- or 6-membered ring, and may be a fused ring. Examples of the heterocyclic group include a pyridyl group, a quinolyl group, a furyl group, a henzothiazolyl group, an oxazolyl group, an imidazolyl group, a thiazolyl group, a triazolyl group, a benzotriazolyl group, an imide group, and an oxazine group. may have. Examples of the substituent include those listed above for the aryl group. Another preferred Y in the general formula is represented by the following general formula. General formula: -T-DI In this general formula, the T group is a group that is bonded to the coupling position of A and can be cleaved by reaction with the oxidized product of the color developing agent, and the DI group represents a development inhibitor residue. . This compound indirectly releases a development inhibitor. That is, due to the reaction with the oxidized product of the color developing agent, cleavage occurs between AT and then the DI group is released in an appropriately controlled manner. As the T-DI group, those represented by the following general formulas to XI are preferred. General formula: General formula: General formula: General formula: General formula: General formula: General formula XI: R ²⁶ is a hydrogen atom, a halogen atom, an alkyl group,
(including aralkyl group), alkoxy group, alkenyl group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group, sulfonamide group, sulfamoyl group, carbamoyl group, aryl group, carboxy group, sulfo group , a hydroxy group, or an alkylsulfonyl group. R ²⁷ represents an alkyl group (including an aralkyl group), a cycloalkyl group, an alkenyl group, or an aryl group. B is an oxygen atom or

[Formula] (R ²⁷ has the same meaning as above). The DI group has the same meaning as in the general formulas a to e, XI, and XII, except for the number of carbon atoms. In general formulas a, b, c, e and XI, the number of carbon atoms contained in (R ²² )n is 1 to 32, and the number of carbon atoms contained in R ²³ in general formulas d and XII is 1 to 32, In the general formula, R ²⁴
and the total number of carbon atoms contained in R ²⁵ is 1 to 32. When R ²⁶ and R ²⁷ are an alkyl group, they may be chain or cyclic, and when R ²² to ^{R 25} are an alkyl group, they may have the substituents listed above. When R ²⁶ and R ²⁷ are an aryl group, the aryl group may have a substituent, examples of which include those listed when R ²² to ^{R 25} are an aryl group. k is an integer of 0 to 2, and l is an integer of 1 to 2. Among the above-mentioned diffusible DIR couplers, those having groups represented by general formulas a, b, or the like are particularly preferred. Yellow coupler residues represented by A include pivaloylacetanilide type, benzoylacetanilide type, malondiester type, malondiamide type, dibenzoylmethane type, benzothiazolylacetamide type, malone ester monoamide type, and benzothiazolyl. Residues of the acetate type, benzoxazolyl acetamide type, benzoxazolyl acetate type, malon diester type, benzimidazolylacetamide type or benzimidazolylacetate type, heterocycle-substituted acetamide or heterocycle substitution included in U.S. Pat. No. 3,841,880 Residues derived from acetate, US patent
No. 3770446, British Patent No. 1459171, West German Patent (OLS) No. 2503099, Japanese Published Patent No. 50-139738
No. or Research Disclosure No. 15737, residues derived from acylacetamides described in
Examples include heterocyclic residues described in US Pat. No. 4,046,574. The magenta coupler residue represented by A includes 5-oxo-2-pyrazoline nucleus, pyrazolo-
[1,5-a] Those having a benzimidazole nucleus or cyanoacetophenone type coupler residues are preferred. The cyan coupler residue represented by A is
Coupler residues with a phenol or alpha-naphthol core are preferred. Furthermore, the coupler residues in DIR couplers that couple with the oxidized form of a developing agent to release a development inhibitor but do not substantially form dyes include U.S. Pat.
Examples include the coupler residues described in No. 3632345, No. 3958993, and No. 3961959. Further, it is preferable that the diffusive DIR compound itself does not diffuse in the photosensitive material, but the coupling product of the coupler component of the diffusive DIR compound and the oxidized form of the developing agent may leak out into the processing solution during processing. good. In the general formula, A is general formula XII,
,,,,,,
may represent and. General formula XII: General formula: General formula: General formula: General formula: General formula: General formula: General formula: General formula: In these general formulas, R ²⁸ represents an aliphatic group, aromatic group, alkoxy group, or heterocyclic group, and R ²⁹ and R ³⁰ represent an aromatic group or a heterocyclic group. The aliphatic group represented by R ²⁸ preferably has 1 to 22 carbon atoms and may be either chain or cyclic,
It may have a substituent. Preferred substituents include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may further have a substituent. Specific examples of aliphatic groups useful as ^R28 include isopropyl, isobutyl, tert-butyl, isoamyl, tert-amyl, 11-dimethylbutyl,
1,1-dimethylhexyl group, 1,1-diethylhexyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, 2-phenoxyisopropyl group,
2-p-tert-butylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group, α-(succinimide)
Examples include isopropyl group, α-(phthalimido)isopropyl group, α-(benzenesulfonamido)isopropyl group, and the like. The aromatic group represented by R ²⁸ , R ²⁹ or R ³⁰ may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups, alkylsulfamoyl groups, alkylsulfonamide groups, and alkylureido groups. , an alkyl-substituted succinimide group, etc., and in this case, the alkyl group may have an aromatic group such as phenylene in the chain. phenyl group or aryloxy group,
It may be substituted with an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group portion of these substituents further has a total number of carbon atoms. is 1
Optionally substituted with one or more alkyl groups of ~22. The phenyl group represented by R ²⁸ , R ²⁹ or R ³⁰ may further include an amino group optionally substituted with a lower alkyl group having 1 to 6 carbon atoms, a hydroxy group, a carboxy group, a sulfo group, a nitro group, a cyano group, It may be substituted with a thiocyano group or a halogen atom. Further, R ²⁸ , R ²⁹ or R ³⁰ may be a phenyl group condensed with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a coumaranyl group, or a tetrahydronaphthyl group. These groups themselves may have substituents. When R ²⁸ represents an alkoxy group, the alkyl moiety is a linear or branched alkyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group,
It represents a cyclic alkyl group or a cyclic alkenyl group, which may be substituted with a halogen atom, an aryl group, an alkoxy group, or the like. When R ²⁸ , R ²⁹ or R ³⁰ represents a heterocyclic group, the heterocyclic group is the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or the amide group, respectively, through one of the carbon atoms forming the ring. Combines with nitrogen atoms. Such heterocycles include thiophene, furan, pyran, pyrrole,
Pyrazole, pyridine, pyrazine, pyrimidine,
Examples include pyridazine, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring. In the general formula, R ³² has a carbon number of 1 to
40, preferably 1 to 22 linear or branched alkyl groups (e.g. methyl, isopropyl, tert-
butyl, hexyl, dodecyl groups, etc.), alkenyl groups (e.g. allyl groups, etc.), cyclic alkyl groups,
(e.g. cyclopentyl group, cyclohexyl group,
norbornyl group, etc.), aralkyl group (e.g., benzyl, β-phenylethyl group, etc.), cyclic alkenyl group (e.g., cyclopentenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups,
Aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group , sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group,
It may be substituted with an anilino group, an N-arylanilino group, an N-alkylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, or the like. Furthermore, R ³² is an aryl group (e.g. phenyl group,
(α- or β-naphthyl group, etc.) may also be represented. The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkoxy group. group, aryloxy group, carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-alkylanilino group,
It may have an N-arylanilino group, an N-acylanilino group, a hydroxy group, a mercapto group, etc. More preferred as R ³² is phenyl in which at least one ortho position is substituted with an alkyl group, an alkoxy group, a halogen atom, etc., and this is because the coupler remaining in the film undergoes coloration due to light or heat. It is useful because there are few Furthermore, R ³² is a heterocyclic group (for example, a 5- or 6-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, a fused heterocyclic group, such as a pyridyl group, a quinolyl group, a furyl group, a benzothiazolyl group) oxazolyl, imidazolyl, naphthoxazolyl, etc.), heterocyclic groups substituted with the substituents listed for the above aryl groups, aliphatic or aromatic acyl groups, alkylsulfonyl groups, arylsulfonyl groups , an alkylcarbamoyl group, an arylcarbamoyl group, an alkylthiocarbamoyl group or an arylthiocarbamoyl group. R ³¹ is a hydrogen atom, a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, or cyclic alkenyl group having 1 to 40 carbon atoms, preferably 1 to 22 carbon atoms (these groups include the substituents listed for R ³² above). ), aryl groups and heterocyclic groups (which may have the substituents listed above for R ³² ), alkoxycarbonyl groups, (e.g. methoxycarbonyl groups, ethoxycarbonyl groups, stearyloxycarbonyl groups) ), aryloxycarbonyl groups (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.), aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.) ), aryloxy groups (e.g. phenoxy groups,
tolyloxy group, etc.), alkylthio group (e.g., ethylthio group, dodecylthio group, etc.), arylthio group (e.g., phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g., acetylamino group, 3-[(2,4- G-tert
-amylphenoxy)acetamide]benzamide group, etc.), diacylamino group, N-alkylacylamino group (e.g., N-methylpropionamide group, etc.), N-arylacylamino group (e.g., N-phenylacetamide group, etc.), Ureido groups (e.g. ureido, N-arylureido, N-
(alkylureido group, etc.), urethane group, thiourethane group, arylamino group, (e.g. phenylamino, N-methylanilino group, diphenylamino group, N-acetylanilino group, 2-chloro-5
-tetradecanamide anilino group, etc.), alkylamino groups (e.g. n-butylamino group, methylamino group, cyclohexylamino group, etc.), cycloamino groups (e.g. piperidino group, pyrrolidino group, etc.), heterocyclic amino groups (e.g. -pyridylamino group, 2-benzoxazolylamino group, etc.),
Alkylcarbonyl group (e.g. methylcarbonyl group, etc.), arylcarbonyl group (e.g. phenylcarbonyl group, etc.), sulfonamide group (e.g. alkylsulfonamide group, arylsulfonamide group, etc.), carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group, etc.) group, N-
methyl-phenylcarbamoyl, N-phenylcarbamoyl, etc.), sulfamoyl group (e.g. N-phenylcarbamoyl), sulfamoyl group (e.g.
-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.),
Represents any one of a cyano group, a hydroxy group, a mercapto group, a halogen atom, and a sulfo group. R ³³ represents a hydrogen atom or a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group, and these represent the above-mentioned R ³² may have the substituents listed above. Further, R ³³ may represent an aryl group or a heterocyclic group, and these may have the substituents listed for R ³² above. Further, R ³³ is a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a sulfo group, a sulfamoyl group, a carbamoyl group, an acylamino group, a diacylamino group, Ureido group, urethane group, sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N -It may represent an acylanilino group, a hydroxy group or a mercapto group. R ³⁴ , R ³⁵ and R ³⁶ each represent a group used in a typical 4-equivalent phenol or α-naphthol coupler, and specifically R ³⁴ includes a hydrogen atom, a halogen atom, an aliphatic hydrocarbon residue, Acylamino group -O-R ³⁷ or -S-R ³⁷
(However, R ³⁷ is an aliphatic hydrocarbon residue),
When two or more R ^34s exist in the same molecule, the two or more R ^34s may be different groups, and the aliphatic hydrocarbon residues include those having substituents. R ³⁵ and R ³⁶ are aliphatic hydrocarbon residues,
Examples include groups selected from aryl groups and heterocyclic residues, one of which may be a hydrogen atom, and these groups include those having substituents. Further, R ³⁵ and R ³⁶ may jointly form a nitrogen-containing heterocyclic nucleus. l is 1
m is an integer of 1 to 3, and n is an integer of 1 to 5. The aliphatic hydrocarbon residue may be either saturated or unsaturated, and may be linear, branched, or cyclic. and preferably alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl,
groups such as t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl, cyclohexyl),
It is an alkenyl group (eg, aryl, octenyl, etc.). As an aryl group, a phenyl group,
There are naphthyl groups, etc., and heterocyclic residues include pyridinyl, quinolyl, thienyl, piperidyl,
Representative groups include imidazolyl and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms,
Nitro, hydroxy, carboxyl, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy,
Arylthio, arylazo, acylamino, carbamoyl, ester, acyl, acyloxy,
sulfonamide, sulfamoyl, sulfonyl,
Each group of a morpholino group is mentioned. R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ of the substituents of the coupler represented by general formula XII,
R ³⁵ and R ³⁶ may be bonded to each other, or either may be a divalent group to form a symmetrical or asymmetrical composite coupler. Next, the diffusible DIR coupler of the present invention will be illustrated, but not limited thereto. DC-1 DC-2 DC-3 DC-4 DC-5 DC-6 DC-7 DC-8 DC-9 DC−10 DC−11 DC−12 DC−13 DC−14 DC−15 DC−16 DC−17 DC−18 DC-19 DC−20 DC−21 DC−22 DC−23 DC−24 DC−25 DC−26 DC−27 DC−28 DC−29 DC−30 DC-31 DC−32 DC−33 DC−34 DC−35 DC−36 DC−37 DC−38 DC-39 DC−40 DC−41 DC−42 DC−43 DC−44 DC−45 DC−46 DC−47 DC−48 DC−49 DC−50 DC−51 DC−52 DC−53 DC−54 DC−55 DC−56 DC−57 DC−58 The diffusive DIR coupler described above is disclosed in U.S. Patent No.
No. 4234678, No. 3227554, No. 3617291, No.
No. 3958993, No. 4149886, No. 3933500, JP-A-Sho
57-56837, 51-13239, British Patent No. 2072363
No. 2070266, Research Disclosure
It can be easily synthesized by the method described in December 1981 No. 21228. In the present invention, the amount of the diffusible DIR coupler added is preferably 0.01 to 50 mol%, particularly preferably 1 to 5 mol%, based on silver. In the present invention, a conventionally known method may be used to incorporate a low molecular weight coupler or the like into the photosensitive silver halide-containing protective colloid layer.
That is, an anionic surfactant such as alkylbenzene sulfonic acid and alkylnaphthalene sulfonic acid and/or sorbitan sesquiolein is usually dissolved in a high boiling point organic solvent with a boiling point of about 175°C or higher, if necessary in combination with a low boiling point solvent. It is mixed with an aqueous solution containing a hydrophilic binder such as gelatin containing an acid ester and a nonionic surfactant such as sorbitan monouraphosphate, and then emulsified and dispersed using a high-speed rotating mixer, colloid mill, or ultrasonic dispersion device to make it hydrophilic. It may be added to the colloid. To be more specific, examples of high boiling point solvents include organic acid amides, carbamides, esters, ketones, urea derivatives, etc., especially dimethyl phthalate, diethyl phthalate, di-propyl phthalate, di-butyl phthalate. , di-n-octyl phthalate, diisooctyl phthalate,
Phthalic acid esters such as diamyl phthalate, dinonyl phthalate, diisodecyl phthalate, phosphoric acid esters such as tricresyl phosphate, triphenyl phosphate, tri-(2-ethylhexyl phosphate, triisononyl phosphate) , dioctyl sebacate, di-(2
Sebacilic acid esters such as -ethylhexyl) sebacate and diisodecyl sebacate, esters of glycerin such as glycerol tripropionate and glycerol tributyrate, 2,4-di-
Phenol compounds such as t-butylphenol, 2,4-di-t-amylphenol, 2,4-di-t-nonylphenol and 2,6-dimethyl-4-t-amylphenol, and other adipate esters , glutaric acid ester, succinic acid ester, maleic acid ester, fumaric acid ester, citric acid ester, etc. are used. Low boiling point solvents include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexanetetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethyl Ketone, diethylene glycol, monoacetate, acetylacetone,
Nitromethane, nitroethane, carbon tetrachloride, chloroform, etc. can be used. As protective colloid it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate starch derivatives; polyvinyl alcohol, A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can. As gelatin derivatives, various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds can be added to gelatin. The product obtained by the reaction is used. Specific examples include U.S. Patent Nos. 2,614,928, 3,132,945,
No. 3186846, No. 3312553, British Patent No.
It is described in No. 861414, No. 1033189, No. 1005784, and Special Publication No. 1973-26845. The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, and styrene. can be used. In particular, polymers with some degree of compatibility with gelatin, such as acrylic acid,
Graft polymers with polymers such as methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylate are preferred. Examples of these are U.S. Pat. No. 2,763,625, U.S. Pat.
It is described in the same No. 2956884 etc. Typical synthetic hydrophilic polymer substances are, for example, West German Patent Application Publication (OLS) No. 2312708, U.S. Patent No.
It is described in No. 3620751, No. 3879205, and Japanese Patent Publication No. 43-7561. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material according to the present invention. Preferred silver halide is silver iodobromide containing 15 mol% or less of silver iodide, and particularly preferred is silver iodobromide containing 15 mol% or less of silver iodide.
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of the silver halide grains in the photographic emulsion (the grain size is the grain diameter for spherical or approximately spherical grains, the edge length for cubic grains,
(expressed as an average based on the projected area) is not particularly limited, but is preferably 3 μm or less. The particle size distribution may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal shapes such as cubes or octahedrons, or may have irregular crystal shapes such as spherical or plate shapes, or may have irregular crystal shapes such as spherical or plate shapes. It may also have a complex shape. It may also consist of a mixture of particles of various crystalline forms. The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.
Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is described in Chimie et Physique Photographic by P. Glafkides.
Photographique (Paul Montel)
Montel Publishing, 1967), Photographic Emulsion Chemistry by G. F. Duffin.
Chemistry) (The Focal Plus)
Focal Prass, 1966), VL Zelikman et al.
Author: Making and Coating Photographic Emulsions
It can be prepared using the method described in Photographic Emulsion (The Focal Prass, 1964).
That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. . It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled double jet method can also be used. According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of forming or physically ripening silver halide grains, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. In order to remove soluble salts from the emulsion after precipitation or physical ripening, a Nudel water washing method in which gelatin is gelatinized may be used, and inorganic salts, anionic surfactants, anionic polymers (e.g. A precipitation method (flocculation) may be used using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.). Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example De Grundlagen der.
Die Grundlagen
der Photographischen Prozess mit
Silberhalogeniden
Verlagsgesellschaft), 1968) pages 675-734 can be used. Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, Reduction sensitization method using noble metal compounds (e.g., gold complex salts, complex salts of metals in the periodic table group such as Pt, Ir, and Pd) The noble metal sensitization methods used can be used alone or in combination. These specific examples are described in U.S. Patent No.
No. 1574944, No. 2410689, No. 2278947, No. 2728668, No. 3606955, etc.; regarding reduction sensitization methods, see U.S. Patent No. 2983609, No. 2419974,
No. 4054458, etc.; regarding the noble metal sensitization method, US Patent No. 2399083, US Patent No. 2448060, British Patent No.
It is described in each specification such as No. 618061. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material according to the present invention contains coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, high contrast, sensitization). Various surfactants may be included for various purposes such as. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol compounds, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols) Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate salt, alkyl phosphate ester, N-acyl-N-alkyl taurine, sulfosuccinic acid Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Surfactants; amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkyl sulfates or phosphoric esters, alkyl betaines, amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, Cationic surfactants such as heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. The photographic emulsion layer of the photographic light-sensitive material according to the present invention includes:
For the purpose of increasing sensitivity, increasing contrast, or accelerating development, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, etc. May include. For example, US Patent No. 2400532, US Patent No. 2423549, US Patent No.
Those described in No. 2716062, No. 3617280, No. 3772021, No. 3808003, British Patent No. 1488991, etc. can be used. The photographic light-sensitive material according to the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example alkyl(meth)acrylate, alkoxyalkyl(meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β
-Unsaturated dicarboxylic acid, hydrocoxylalkyl (meth)acrylate, sulfoalkyl (meth)
Polymers containing a combination of acrylate, styrene sulfonic acid, and the like as monomer components can be used. For example, US Patent No. 2376005, US Patent No. 2739137, US Patent No. 2853457, US Patent No. 3062674,
Same No. 3411911, Same No. 3488708, Same No. 3525620,
Same No. 3607290, Same No. 3635715, Same No. 3645740,
Those described in British Patent No. 1186699 and British Patent No. 1307373 can be used. For the photographic processing of layers comprising the photographic emulsion according to the invention, examples may be found, for example, in Research Disclosure No. 176, pages 28-30 (RD
-17643), any of the known methods and known treatment liquids can be applied. This photographic processing may be any photographic processing that forms a dye image (color photographic processing) depending on the purpose. Processing temperature is usually from 18℃
Temperature selected between 50℃ or lower than 18℃ or
The temperature may exceed 50°C. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixer may contain a water-soluble aluminum salt as a hardening agent. When forming a dye image, conventional methods can be applied.
For example, the negative-positive method (e.g., “Journal of the Society of Motion Picture and Television Engineers”)
and Television Engineers)”, Volume 61 (1953),
(described on pages 667-701). Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g. 4-amino-N',N-diethylaniline, 3-methyl-4-amino-N',N-
Diethylaniline, 4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-
4-Amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfamidoethylaniline, 4-amino-3-methyl-N-ethyl- N-
β-methoxyethylaniline, etc.) can be used. In addition, LFMnson (LFMnson)
Author “Photographic Processing Chemistry”
(Published by Focal Prass, 1966
), pp. 226-229, U.S. Patent No. 2193015, same no.
Those described in No. 2592364, JP-A-48-64933, etc. may be used. The color developer may also contain a PH buffer, a development inhibitor or an antifoggant. In addition, if necessary, curing agents, softeners, accelerators, organic solvents, development accelerators, dye-forming couplers, competitive couplers, fogging agents, auxiliary developers, viscosity-imparting agents, polycarboxylic acid chelating agents, and antioxidants are added. It may also include. Specific examples of these additives include Research Disclosure (RD-17643) and U.S. Patent No. 4083723.
No. 2622950, West German Patent Application Publication (OLS) No. 2622950, etc. The photographic emulsion layer of a color developer is usually bleached. Bleach agents include compounds of polyvalent metals such as iron (), cobalt (), chromium (), tin (),
Peracids, quinones, nitroso compounds, etc. are used. For example, ferricyanides; dichromates; organic complexes of iron () or cobalt ();
For example, complex salts of aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 1,3-diamino-2-propanoltetraacetic acid, or organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganese complex salts; nitrosophenols etc. can be used. Among these, potassium ferricyanide, ferric ethylenediaminetetraacetate () sodium and ethylenediaminetetraacetate iron ()
Ammonium is particularly useful. Bleach solutions include U.S. Pat. No. 3,042,520;
No. 3241966, Special Publication No. 1973-8506, Special Publication No. 1977-8836
In addition to the bleaching accelerator described in JP-A-53-65732 and the thiol compound described in JP-A-53-65732, various additives can also be added. Photographic emulsions according to the invention may be spectrally sensitized with methine dyes and others. For example, compounds specifically described as sensitizing dyes in the Examples below are used. Useful sensitizing dyes include, for example, German Patent No. 929080, US Patent No. 2493748, US Patent No. 2503776, US Pat.
Same No. 3656959, Same No. 3672897, Same No. 4025349,
This is described in British Patent No. 1242588 and Japanese Patent Publication No. 14030/1973. These sensitizing dyes may be used in a conventional manner, but a combination thereof may also be used, and combinations of sensitizing dyes are often used particularly for the purpose of color sensitization. Typical examples are U.S. Patent No. 2688545 and U.S. Patent No. 2977229.
No. 3397060, No. 3522052, No. 3522052, No. 3397060, No. 3522052, No.
No. 3527641, No. 3617293, No. 3628964, No. 3666480, No. 3672989, No. 3679428,
No. 3814609, No. 4026707, British Patent No.
No. 1344281, Special Publication No. 43-4936, No. 53-12375,
It is described in JP-A-52-110618 and JP-A-52-109925. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, a multi-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the force-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. Not only exposure times of 1/1000 seconds to 1 second used in cameras, but also exposure times shorter than 1/1000 seconds, such as 1/10 ⁴ to 1/10 ⁶ using xenon flash lamps and cathode ray tubes.
Exposures of seconds can be used, or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Alternatively, exposure may be performed with light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. The emulsion layer may also contain a colored coupler that has a color correction effect. Examples of colored couplers include US Pat. No. 3,476,560 and US Pat.
No. 2521908, No. 3034892, Special Publication No. 44-2016,
No. 38-22335, No. 42-11304, No. 44-32461,
Those described in JP-A No. 51-26034, JP-A No. 52-42121, and OLS No. 2415959 can be used. The photographic light-sensitive material according to the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer. In the photographic material according to the present invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a cationic polymer or the like. For example, British Patent No. 685475,
U.S. Patent No. 2675316, U.S. Patent No. 2839401, U.S. Patent No.
No. 2882156, No. 3048487, No. 3184309, No. 3445231, OLS No.
Polymers described in JP-A No. 1914362, JP-A No. 50-47624, JP-A No. 50-71332, etc. can be used. The light-sensitive material according to the present invention may contain a color antifoggant. The photosensitive material according to the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups, 4-
Thiazolidone compounds, benzophenone compounds, cinnamic acid ester compounds, butadiene compounds, benzoxazole compounds, and ultraviolet absorbing polymers can be used. These ultraviolet absorbers may be fixed in the hydrophilic colloid layer. Specific examples of ultraviolet absorbers are given in U.S. Patent No.
No. 3533794, No. 3314794, No. 3352681, JP-A-46-2784, U.S. Patent No. 3705805, No.
It is described in No. 3707375, No. 4045229, No. 3700455, No. 3499762, West German Patent Application Publication No. 1547863, etc. The photosensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. When implementing the present invention, an anti-fading agent may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. The light-sensitive material according to the present invention can also be used for black and white (in this case, a known black coupler may be added), and can also be used not only for photographic film but also for photographic paper. E. Examples Examples of the present invention will be described in more detail below. Example 1 A multilayer color light-sensitive material was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support (however, the sensitizing dyes will be shown later). 1st layer: Antihalation layer Gelatin layer containing black colloidal silver 2nd layer: Intermediate layer 3rd gelatin layer: Red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide: 5 mol%) (average grain size 0.5μ)... Silver coating amount 1.79 g/m ² Sensitizing dye... 6 x 10 ^-5 mol per mol of silver Sensitizing dye... 1.5 x 10 ^-5 mol per mol of silver Coupler A... 1 mol of silver Coupler C: 0.003 mol per mol of silver Coupler D: 0.003 mol per mol of silver Tricresyl phosphate coating amount: 0.3 cc/m ² 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol% average grain size 0.7μ)...Silver coating amount 1.4 g/ ^m2 Sensitizing dye...3 x 10 ^-5 mol per 1 mol of silver Sensitizing dye...silver 1 1.2×10 ^-5 mole per mole Coupler F...0.0125 mole per mole of silver Coupler C...0.0016 mole per mole of silver Tricresyl phosphate coating amount 0.2cc/m ² 5th layer: Intermediate Layer 6th layer same as 2nd layer: green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide: 4 mol% average grain size 0.5μ)...Silver coating amount 1.0g/ ^m2 Sensitizing dye...Silver 1 3 x 10 ^-5 mol per mol Sensitizing dye...1 x 10 ^-5 mol per mol of silver Coupler B...0.08 mol per mol of silver Coupler M...0.008 mol per mol of silver Coupler D ...0.0015 mol per 1 mol of silver Tricresyl phosphate coating amount 1.4 cc/m ² 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion (Silver iodide: 5 mol % Average grain size 0.75 μ )... Silver coating amount 1.6 g/m ² Sensitizing dye... 2.5 x 10 ^-5 mol per mol of silver Sensitizing dye... 0.8 x 10 ^-5 mol per mol of silver Coupler B-1... 1 mol of silver Coupler M: 0.003 mole per mole of silver Coating amount of tricresyl phosphate: 0.8 cc/m ² 8th layer: Yellow filter layer A gelatin layer containing yellow colloidal silver in an aqueous gelatin solution. 9th layer: blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide: 6 mol% average grain size 0.7μ)...silver coating amount 0.5 g/ ^m2 Coupler Y-1...0.125 per mol of silver Mole Tricresyl phosphate coating amount 0.3 cc/m ² 10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion (silver iodide: 6 mol% average grain size 0.8 μ)...Silver coating amount 0.6 g/m m ² Coupler Y-1...0.04 mol per 1 mol of silver Tricresyl phosphate coating amount 0.1 cc/m ² 11th layer: Protective layer Polymethyl methanoacrylate particles (diameter
Apply a gelatin layer containing 1.5μ). The coupler in each layer was prepared by adding the coupler to a solution of tricresyl phosphate and ethyl acetate, adding sodium p-dodecylbenzenesulfonate as an emulsifier, dissolving it by heating, and mixing it with a heated 10% gelatin solution. The emulsified product was used. In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. Sample 1 (comparative example) was prepared as above.
And so. <Compounds used to prepare the sample> Sensitizing dye: anhydro-5,5'-dichloro-
3,3'-di-(γ-sulfopropyl)-9-ethyl-thiacarbocyanine hydroxide pyridium salt sensitizing dye: anhydro-9-ethyl-3,3'-
Di-(γ-sulfopropyl)-4,5,4',5'-
Dibenzothiacarbocyanine hydroxide
Triethylamine salt sensitizing dye: anhydro-9-ethyl-5,5'-
Dichloro-3,3'-di-(γ-sulfopropyl)
Oxacarbocyanine sodium salt sensitizing dye: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di-
(β-[β-(γ-sulfopropoxy)ethoxy]
Ethylimidazolocarbocyanine hydroxide sodium salt coupler A [MW≒461]: Coupler B-1 [MW≒700]: Coupler C [MW≒922]: Coupler D [MW≒850]: Coupler E [MW≒651]: Coupler F [MW≒533]: Coupler M [MW≒979]: Coupler Y-1 [MW≒748]: Coupler PM (polymer coupler): (The weight ratio is former unit: latter unit =
53:47) Next, couplers B-1 and Y used in sample 1
-1 was changed to coupler PM and the coupler of the present invention, and the amount added was 0.5 of the comparative coupler (sample 1).
The amount of tricresyl phosphate was changed to 0.1 times, and the ratio of the total amount of coupler and tricresyl phosphate to the amount of gelatin in each layer was kept constant (0.8). Samples of the present invention were prepared by changing the amounts as shown in Table 1 so that the maximum color density was the same as Comparative Sample 1. The obtained sample was exposed to white light through a pattern for MTF measurement, and then subjected to the following color development process. The development process used here was carried out at 38°C as described below. 1 Color development... 3 minutes 15 seconds 2 Bleaching... 6 minutes 30 seconds 3 Washing... 3 minutes 15 seconds 4 Fixing... 6 minutes 30 seconds 5 Washing... 3 minutes 15 seconds 6 Stabilization... 3 minutes 15 seconds each The composition of the treatment liquid used in the process was as follows. Color developer: Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4-(N-Ethyl-N-β-hydroxyethylamino)-2-methyl-aniline sulfate Salt 4.5g Add water 1 Bleach solution: Ammonium bromide 160.0g Aqueous ammonia (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt
130g Glacial acetic acid 14ml Add water 1 Fixer: Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer: Formalin 8.0ml Add water 1 Measure the MTF of each color image of these processed samples,
Table 1 below shows that the spatial frequency is 5 cycles/mm, 20
Cycles/mm and MTF of 35 cycles/mm were listed.

【table】

[Table] From the above results, it can be seen that when the low molecular weight coupler and diffusive DIR coupler of the present invention are used, the sharpness is significantly improved over the entire frequency range. In the sample of the present invention, in the layer below the layer using the coupler of the present invention, especially in the high frequency range,
The rate of increase in MTF value increases. Moreover, not only this, but improvements can also be seen in the color image of the layer containing the coupler of the present invention. It is presumed that the addition of the coupler of the invention had an additional effect on the lower layer.

Claims (1)

[Claims] 1. A photographic light-sensitive material comprising a low molecular weight coupler having a molecular weight of 250 to 450 and a coupler having a degree of diffusivity of 0.4 or more and capable of releasing a development inhibiting substance through a coupling reaction.