JPH0548899B2 - - 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. Among the various performances that are desired to be improved, the present invention particularly improves the depiction of fine details (hereinafter referred to as "sharpness"), shortens the development processing time, and eliminates fog. This relates to a photosensitive material with improved coloring density. 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 sharpness is improved as the thickness of the protective colloid layer becomes thinner, and the layer thickness has been gradually reduced by improving coating methods, hardening agents for the protective colloid layer, and improving the protective colloid. . However, if the protective colloid layer is excessively reduced in order to make the layer thinner, the high boiling point solvent contained in the layer will gradually ooze out, so this breakthrough is desired. In order to prevent such oozing of the high boiling point solvent, it is necessary to increase the protective colloid layer according to the total weight of the coupler and high boiling point solvent contained in the protective colloid layer, and under this constraint, Research has been underway. As a result of this research, a method using a polymer coupler latex described in Japanese Patent Application Laid-Open No. 58-28745 has been proposed. As described in the specification of this publication, the polymer coupler latex was developed based on a number of previous studies, and has achieved certain results in thinning silver halide color photosensitive materials. listed. However, this result cannot be obtained for all polymer coupler latexes, but only for couplers with a very limited structure as described in the above-mentioned publication. Regarding this point,
It is described in detail in the specification of the above-mentioned publication, and is cited below. ``Polymer couplers added to gelatin silver halide emulsions in the form of latexes are described, for example, in US Pat. No. 4,080,211, UK Patent No. 1,247,688, and US Pat. patent
No. 2,725,591 and US Pat. No. 3,926,436 describe copolymerized latexes with competitive couplers, and US Pat. No. 3,767,412 describes polymeric cyan coupler latexes. However, although these polymer coupler latexes have many excellent advantages as described above, they also have the following problems that should be improved, and improvements are desired. 1 Poor color reproducibility due to broad absorption peak of magenta dye. 2. Due to the poor coupling reaction speed, the density of the produced dye is low. 3. The light fastness of the magenta image is very poor. 4. Color development tends to cause unnecessary fogging. 5. The wet heat fastness of the color image is poor. 6 Coupler monomer has low solubility and extremely low polymerizability. In particular, it has major drawbacks in color reproducibility, coupling reactivity, light fastness of magenta color images, storage stability of polymer coupler latex in film, and polymerizability of coupler monomers. No improvement is seen in the 2-equivalent magenta polymer coupler latexes described in German Patent No. 2,725,591 and US Pat. No. 3,926,436. This suggests that there is a significant difference in photographic properties between ordinary couplers and polymer couplers. ” Furthermore, when such polymeric couplers are used, the coloring efficiency is still not sufficient.
There has been a strong desire to develop a new technology that can improve sharpness without reducing color development efficiency. C. Purpose of the Invention The purpose of the present invention is to obtain a sufficiently large maximum image density (Dmax) even if the amount of coupler is reduced, thereby achieving a high image density and thinning the emulsion layer (in particular, improving sharpness). ), the development processing time can be shortened, and furthermore, fogging can be reduced and color density can be sufficiently improved. D. Structure of the invention and its effects: That is, the present invention provides a method for dissolving a coupler in a solvent,
It is a photographic light-sensitive material formed by applying a coating while being dispersed in a protective colloid solution, in which a low molecular weight coupler with a molecular weight of 250 to 450 is used as the coupler, and a boiling point of 175°C (1 atm) is used as the solvent. (lower) This relates to a photographic light-sensitive material characterized by using a phenolic high-boiling point solvent represented by the following general formula. general formula (However, R ²² and R ²³ are hydrogen atoms, or straight chain or branched alkyl groups having 1 to 20 carbon atoms, and R ²⁴ is straight chain or branched alkyl groups having 1 to 20 carbon atoms, or cycloalkyl groups. ) According to the present invention, the above-mentioned low molecular weight coupler is contained in the emulsion layer, 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 studied conventional photographic materials and found that, for example, coupler materials are prepared by dissolving a coupler in a high-boiling solvent and applying the dispersion in a protective colloid solution. 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. Furthermore, as a result of extensive studies, the inventors of the present invention have decided to use a phenolic high-boiling organic solvent as the oil for dissolving the coupler when the low molecular weight coupler is added in an oil dispersion to a silver halide emulsion layer consisting of a protective colloid. Therefore, we have discovered that the color density can be significantly improved without increasing fog, and have arrived at the present invention. Therefore, by using the above-mentioned high boiling point organic solvent, it is possible to further improve the sharpness by making the film thinner and to shorten the development processing time. During this process, the inventor confirmed the following.
Commonly used high-boiling organic solvents include a variety of phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, and the like. However, among these many high boiling point organic solvents, when the low molecular weight coupler of the present invention is dissolved and dispersed in the emulsion layer, only the phenolic high boiling point organic solvent can sufficiently increase the color density without increasing fog. I found out that it is possible.
Furthermore, even when a normal coupler (molecular weight of 500 or more) is dissolved in the phenolic high-boiling organic solvent used in the present invention and dispersed in the emulsion layer, the color density cannot be significantly improved as with other high-boiling organic solvents. I also realized that I couldn't do it. The phenolic high-boiling organic solvent used in the present invention preferably has a boiling point of 175° C. or higher under 1 atm, and specific examples thereof are shown below. 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 Y 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 to 2.5 (however, n indicates the number of Y), because the coupler is difficult to crystallize and the dye generated during development is difficult to move through the layer. Particularly desirable. Moreover, 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)n
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 fixed idea that all practical couplers contained in known protective colloids require large groups to be non-diffusive has led to the value of (A-1)+(B-n)/C+n+1. is large,
In addition, conventional coupler cores for practical use are structurally limited and have a coupler molecular weight larger than the range of the present invention, so that the protective colloid layer cannot be made thinner and no improvement in sharpness can be expected. 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 and prevent the high-boiling point organic solvent from seeping out, the ratio of the weight of the protective colloid used to the sum of the coupler weight and the high-boiling point solvent weight should be 0.5 to 1.5. is 0.8
A value of ~1.5 is desirable (however, from the viewpoint of sharpness, it is better to use a smaller amount of protective colloid). The improvement in color development is achieved regardless of the ratio of the weight of the high-boiling solvent to the weight of the coupler, and the color development 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. Look at it,
It's something unexpected. 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 material 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 1 or 2 containing a cyan coupler
It has a structure consisting of the above red-sensitive silver halide emulsion layer. 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 contrary, 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 determines the 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. Those having easily alkali-soluble groups such as , carboxyl group, and 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 ions. 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 one coupler has a coupling speed of 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 )max.) In other words, an emulsion containing a mixed coupler is exposed to light at various stages, and several pairs of D _A and D _B obtained by color development are plotted on two orthogonal axes log( 1-
The coupling activity ratio R _A /R _B can be determined from the slope of the straight line obtained by plotting as 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 can be separated by the reaction between the coupler of this general formula and the oxidized form 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, such as 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 thereof include a hydrogen atom, a halogen atom, and those represented by the following general formula. General formula:

【formula】

[Formula] In this general formula, A represents an oxygen atom or a sulfur atom, B represents a group of nonmetallic atoms necessary to form an aryl ring or a heterocycle, and E represents a 5- or 6-membered heterocycle together with a nitrogen atom. Represents a group of nonmetallic atoms necessary to form a ring. These rings may further be fused with an aryl ring or a heterocycle. D represents an organic group (for example, an alkyl group, an aryl group) or an atom (for example, a halogen atom), and b represents 0 or a positive integer. When b is plural, D may be the same or different. D is -O-, -S-, -COO-, -CONH-, _-SO2NH
−, −NHCONH−, −SO ₂ −, −CO−, −NHCO
-, -OCO-, _-NHSO2- , -NH-, and other linking groups may be included. Specific examples of the above yellow couplers are given below. y-1 [MW≒380] y-2 [MW≒368] y-3 [MW≒360] 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] Further, those 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), 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-11 [MW≒358] y-12 [MW≒386] y-13 [MW≒440] y-14 [MW≒442] y-15 [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 used in the present invention are those having a pyrozolotriazole core, particularly those having the general formula: (However, R ⁷ , -J-R ⁸ and R ⁹ are all the same as above.
R ¹ and X ³ have the same meaning as X ¹ above. ) is a magenta coupler. However, in this general formula, R ⁷ , -J-R ⁸ and R ⁹ and X
The total atomic weight with X ³ is desirably 150-340, more preferably 200-300. 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 hetero group residue, J is, for example, a bond, -O-, -S
-,

[Formula], R ¹⁰ represents a hydrogen atom or an alkyl group, and R ⁹ represents, for example, a hydrogen atom. As ^X3 , a hydrogen atom, a halogen atom, and a group of the following general formula are preferable. General formula:

[Formula] -S-R ¹² In this general formula, R ¹¹ is a halogen atom, an alkyl group (e.g. methyl group, ethyl group), an alkoxy group (e.g. methoxy group, ethoxy group), an acylamino group (e.g. acetamido group, benzamide group), an alkoxycarbonyl group (e.g. methoxy carbonyl group), anilino group (e.g. 2-chloroanilino group, 5-acetamidoanilino group),
N-alkylcarbamoyl group (e.g. N-methylcarbamoyl group), ureido group (e.g. N-methylureido group), cyano group, aryl group (e.g. phenyl group, naphthyl group), N,N-dialkylsulfamoyl group, nitro R 11 is a group or atom selected from a group, a hydroxy group, a carboxy group, an aryloxy group, etc., and when g is 2 or more, R ¹¹ may be the same or different. R ¹² represents a substituted or unsubstituted alkyl group (e.g., butyl group, methyl group, etc.), an aralkyl group (e.g., benzyl group, etc.), an alkenyl group (e.g., allyl group, etc.), or a cyclic alkyl group (e.g., cyclopentyl group, etc.), Substituents include halogen atoms, alkoxy groups (e.g. butoxy groups,
methyloxy group, etc.), acylamino group (e.g., acetamido group, tetradicanamide group, etc.),
Alkoxycarbonyl groups (such as methoxycarbonyl groups), N-alkylcarbamoyl groups (such as N-methylcarbamoyl groups), ureido groups (such as ethylureido groups), cyano groups, aryl groups (such as phenyl groups), nitro groups, alkylthio groups ( methylthio group, etc.), alkylsulfinyl group (ethylsulfinyl group, etc.), alkylsulfone group, anilino group, sulfonamide group (ethylsulfonamide group, etc.), N-alkylsulfamoyl group,
Selected from aryloxy groups and acyl groups (such as acetyl groups). Specific examples of this low molecular weight magenta coupler are as follows. m-1 [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] As a magenta coupler, in addition to the above, 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: General formula: Here, both R ¹³ and R ¹⁴ are the above-mentioned R ¹ ,
Moreover, X ⁴ has the same meaning as the above-mentioned X. The sum of the atomic weights of R ¹³ , (R ¹⁴ ) _f and X ⁴ is preferably 95 to 290, more preferably 140 to 245 in the general formula, and preferably 95 to 295, more preferably 145 in the general formula. ~245. In the above general formula, R ¹³ is, for example, an acylamino group (e.g., propaneamide group, benzamide group), anilino group (e.g., 2-chloroanilino group, 5-acetamidoanilino group), or ureido group (e.g., phenylureido group, butaneureido group). Examples of ^R14 include hydrogen atom, halogen atom, alkyl group, alkoxy group,
Examples thereof include a hydroxycarbonyl group, an alkoxycarbonyl group, a nitro group, an aryloxy group, a cyano group, and an acylamino group, and examples of X ⁴ include the same as the above-mentioned X ³ . f is an integer from 0 to 4, and when f is 2 or more, each R ¹⁴ may be the same or different. A specific example of this magenta coupler is as follows. m-16 [MW≒343] m-17 [MW≒425] m-18 [MW≒427] m-19 [MW≒430] m-20 [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. In particular, when used in combination with a phenolic high boiling point organic solvent, the color density is significantly improved. 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-diethylcarbamoyl, etc.),
It may be substituted with a sulfamoyl group (eg, N,N-diethylsulfamoyl, etc.), an alkoxy group (eg, ethoxy, butyloxy, octyloxy, etc.), an aryloxy group (eg, phenoxy, methylphenoxy, etc.), or the like. In addition to the above substituents, R ¹⁵ may contain commonly used 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-tolylfluoromethylphenyl, 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, benzothiazole amino, etc.),
Carbonamide group (for example, alkylcarbonamide group such as ethylcarbonamide group; phenylcarbonamide, 2,4,6-trichlorophenylcarbonamide, 4-methylphenylcarbonamide, 2-ethoxyphenylcarbonamide, etc.) Arylcarbonamide groups such as thiazolylcarbonamide, benzothiazolylcarbonamide,
Heterocyclic carbonamide groups such as oxazolylcarbonamide, benzoxazolylcarbonamide, imidazolylcarbonamide, benzimidazolylcarbonamide, etc.), sulfonamide groups (such as butylsulfonamide, phenylethylsulfonamide, etc.) Alkylsulfonamide group; Arylsulfonamide group such as phenylsulfonamide, 2,4,6-trichlorophenylsulfonamide, 2-methoxyphenylsulfonamide, 3-carboxyphenylsulfonamide, etc.; Thiazolylsulfonamide , heterocyclic sulfonamide groups such as benzothiazolylsulfonamide, imidazolylsulfonamide, benzimidazolylsulfonamide, pyridylsulfonamide, etc.), sulfamyl groups (such as alkyl sulfonamide groups such as propylsulfamyl, octylsulfamyl, etc.) phamyl group; phenylsulfamyl,
2,4,6-trichlorophenylsulfamyl,
Arylsulfamyl groups such as 2-methoxyphenylsulfamyl; heterocycles such as thiazolylsulfamyl, benzothiazolylsulfamyl, oxazolylsulfamyl, benzimidazolylsulfamyl, pyridylsulfamyl groups, etc. sulfamyl group) and carbamyl groups (alkylcarbamyl groups such as ethylcarbamyl, octylcarbamyl, etc.; phenylcarbamyl, 2,
Arylcarbamyl groups such as 4,6-trichlorophenylcarbamyl and the like, and complex groups such as thiazolylcarbamyl, benzothiazolylcarbamyl, oxazolylcarbamyl, imidazolylcarbamyl, benzimidazolylcarbamyl and the like. cyclic carbamyl group, etc.). ^R18 , ^R17 , ^R20 and
Specific examples of R ²¹ include those listed for R ¹⁷ , and J represents a nonmetallic atom necessary to form a 5- and/or 6-membered ring as shown below. That is, a benzene ring, a cyclohexene ring, a cyclopentene ring, a thiazole ring, an oxazole ring, an imidazole ring, a pyridine ring, a pyrrole ring, etc., among which a benzene ring is preferred. X ⁵ and X ⁶ are preferably a hydrogen atom, a halogen atom, or a group bonded to the coupling position via -O-, -S-, -N=N- (eg, alkyl, aryl, heterocycle). 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−, substituents (e.g. alkyl,
aryl, heterocycle). Specific examples of cyan couplers are as follows. c-1 [MW≒361.5] 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. Next, the phenolic high-boiling organic solvent used in the present invention is preferably one that has a boiling point (under 1 atm) of 175°C or higher and a melting point of 50°C or lower and is liquid or solid at room temperature (25°C). Further, it is preferable that the phenol does not react with the oxidation product of the color developing agent, and in particular, with respect to the -OH group of phenol, it is preferable that the 4-position and even the 2-position are substituted with a group that does not leave in the coupling reaction. Preferred examples of the substituent include an alkyl group and a cycloalkyl group. Further, it is preferable that the total number of carbon atoms in the substituents is 6 to 24 so that the high boiling point solvent does not diffuse into the photographic light-sensitive material. Particularly preferred phenolic high boiling point organic solvents are those represented by the following general formula. General formula: In this general formula, R ²² and R ²³ are each a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms (for example, a methyl group, -butyl group, t-pentyl group, t-octyl group, dodecyl group, pentadecyl group, etc.). ^R24 is a straight chain or branched alkyl group having 1 to 20 carbon atoms (e.g. methyl group, t-butyl group, t-pentyl group,
t-octyl group, dodecyl group, pentadecyl group, etc.), or a cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, etc.). However, the total number of carbon atoms in the groups represented by R ²² , R ²³ and R ²⁴ is 6 to 24. Preferred specific examples of the phenolic high-boiling point organic solvent used in the present invention are shown below, but the invention is not limited thereto. (HBS-1) (HBS-2) (HBS-3) (HBS-4) (HBS-5) (HBS-6) (HBS-7) (HBS-8) (HBS-9) (HBS-10) (HBS-11) (HBS-12) (HBS-13) (HBS-14) (HBS-15) (HBS-16) (HBS-17) These phenolic high boiling point organic solvents are disclosed in, for example, US Patent No. 2835579, British Patent No. 1001947,
It is described in the same No. 1076054 etc. Two or more types of high boiling point organic solvents according to the present invention can also be used in combination. Further, the above phenolic high boiling point organic solvent can also be used in combination with other high boiling point organic solvents. In this case, phenols account for the total amount of high-boiling organic solvents.
It is desirable that it accounts for 50% by weight or more. In addition, the total amount of the high boiling point organic solvent is 5 to 300 parts by weight based on 100 parts by weight of the coupler (when a low molecular weight coupler of the present invention and a coupler other than the present invention are used together, the sum of the amounts of both couplers). It is better. Other high boiling point organic solvents that can be used in combination include phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate),
benzoic acid esters (e.g. octyl benzoate),
Alkylamides (e.g. diethyl laurylamide, fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc.). For example, low-boiling organic solvents (such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexane, tetrahydrofuran, methyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl ethyl ketone, methyl isobutyl ketone, diethylene glycol monoacetate, acetylacetone, nitromethane, carbon tetrachloride, chloroform, etc.) or, if necessary, a mixture of these solvents.Alternatively, the coupler is dissolved in the above-mentioned low boiling point organic solvent. Then, a high boiling point organic solvent is added to this. Then, it is mixed with an aqueous gelatin solution containing a surfactant, and then dispersed using a dispersion means such as a stirrer, homogenizer, colloid mill, flow jet mixer, or ultrasonic dispersion device. After emulsification and dispersion, the silver halide emulsion used in the present invention can be prepared by adding the silver halide emulsion, but a step of removing the low-boiling organic solvent may be included after or simultaneously with the dispersion. In the present invention, the ratio of the high boiling point organic solvent to the low boiling point organic solvent is preferably 1:0.1 to 1:50, more preferably 1:1 to 1:20. Gelatin is used as the protective colloid. are advantageous, but other hydrophilic colloids can also be used, such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfate. sugar derivatives such as cellulose derivatives, sodium alginate starch derivatives, etc.; monomers such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl pyrazole, etc. A wide variety of synthetic hydrophilic polymeric substances such as monopolymers or copolymers can be used. Gelatin derivatives include gelatin, for example, acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfones, etc. Those obtained by reacting various compounds such as amides, maleimide compounds, polyalkylene oxides, and epoxy compounds are 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. A preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferred is
Silver iodobromide containing from 2 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 in the case of spherical or approximately spherical grains, the ridge length in the case of 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 written by P. Glafkides.
Chimie et Physique Photographique (Paul
Montel Publishing, 1967), by GF. Duffin
Photographic Emulsion Chemistry (The Focal
Prass, 1966), VLZelikman et al.
Making and Coating Photographic Emulsion
(The Focal Prass, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the methods for reacting the soluble silver salt and soluble halogen salt include one-sided mixing method, simultaneous mixing method,
Any combination thereof may be used. 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) using gelatin derivatives (eg, acylated gelatin, carbamoylated gelatin, etc.) may also be used. Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example H. Frieser ed. Die
Grundlagen der Photographischen Prozess
mit Silberhalogeniden (Akademische
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 amines, hydrazine derivatives, formamidine sulfine, silane compounds); Noble metal compounds (e.g. gold complexes, complex salts of periodic table metals such as P _t , I _r , _PD etc.); ) can be used alone or in combination. Specific examples of these include U.S. Pat.
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: Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium , heterocyclic quaternary ammonium salts such as imidazolium, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles. 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, hydroxyalkyl (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℃ but 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, negative-positive method (e.g. “Journal of the
Society of Motion Picture and Television
Engineers, Vol. 61 (1953), pp. 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. , for example, phenylenediamines (e.g. 4-amino-N',N-diethylalinine, 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, “Photographic” by LFMnson
Processing Chemistry” (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 are available from Research. In addition to disk closure (RD-17643), US 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, nitokoso 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
Bleaching accelerator described in JP-A-53-65732, etc.
In addition to the thiol compounds described in this issue, 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. 3672898, 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 selected arbitrarily as needed. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different compositions 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 with 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. In addition, the emulsion layer contains colored couplers that have a color correction effect, or couplers that release a development inhibitor during development (so-called DIR couplers).
It's okay if there is. In addition to DIR couplers,
The products of the coupling reaction may be colorless and include colorless DIR coupling compounds that release development inhibitors. Colored couplers include, for example, U.S. Pat. No. 3,476,560, U.S. Pat.
No. 3034892, Special Publication No. 44-2016, No. 38-22335,
No. 42-11304, No. 44-32461, JP-A No. 1973-
Those described in Specification No. 26034, Specification 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 listed in the U.S. patent.
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 agent as a filter dye or for various purposes such as prevention of irradiation. In carrying out the present invention, the following known anti-fading agents 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 The present invention will be described in more detail with reference to Examples below. Example 1 On a cellulose triacetate film provided with an undercoat layer, a photosensitive silver iodobromide emulsion layer (film thickness: 2μ) was provided to prepare each sample. Each sample obtained was exposed to gradation light and 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 with water...3 minutes 15 seconds 4 Fixing...6 minutes 30 seconds 5 Washing with water...3 minutes 15 seconds 6 Stability...3 minutes 15 seconds The composition of the treatment liquid used in each step 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-βhydroxyethylamino)-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 The photographic performance obtained is shown in Table 1.

[Table] Here are couplers B-2, B-3, m-2, m-
For 3, m-5, m-15, use 200 ml of high boiling point organic solvent per 70 g of coupler,
For -1, y-2, y-7, y-9, and Y-2, 80 ml of high-boiling organic solvent was used per 120 g of coupler. The above results show that the use of the coupler of the present invention and the high boiling point organic solvent of the present invention increases the maximum color density without increasing fog. As a result, it was found that according to the present invention, it is possible to make the layer thinner and shorten the processing time while obtaining the same maximum color density. Further, when a coupler having a lower molecular weight than the coupler of the present invention was used, the maximum color density showed a low value because the coupler flowed out into the processing solution during processing. Similar effects were also observed when other high boiling point organic solvents according to the present invention were used. Example 2 On a support, per mole silver, iodine containing 0.1 mole of various couplers from Table 2 below, 20% by weight of the couplers a high boiling organic solvent (HBS-13) and various amounts of gelatin. Samples were prepared with silver oxide emulsion layers containing the same amount of silver, and changes in maximum color density were observed when the ratio (R) of the sum of the coupler weight and the high boiling point solvent weight to the gelatin amount was changed. . The results are shown in Table 2 below.

【table】

[Table] From the above results, when using the coupler of the present invention and a high boiling point organic solvent, unlike when using a conventional coupler, the ratio of the sum of the coupler weight and the weight of the high boiling point solvent to the gelatin amount ( By changing R), Dmax changes, especially when the ratio is 0.5
~1.5 Furthermore, in the case of 0.8~1.5, Dmax is large,
It can be seen that no sweating phenomenon occurred. Example 3 A multilayer color light-sensitive material sample 1 (comparison) was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support (however, the sensitizing dyes are shown below). 1st layer: Anti-halation 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%) ...Silver coating ( Average particle size 0.5μ) Amount 1.79g/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...For 1 mol of silver 0.06 mol coupler C...0.003 mol coupler D...0.003 mol tricresyl phosphate coating amount per 1 mol silver 0.3 cc/m ² 4th layer: red-sensitive high-sensitivity emulsion layer iodobromide Silver emulsion Silver iodide: 4 mol% Average grain size 0.7 μ...Silver coating amount 1.4 g/ ^m2 Sensitizing dye...3 x 10 ^-5 mol per mol of silver Sensitizing dye...1.2 per mol of silver ×10 ^-5 mole Coupler F...0.0125 mole per mole of silver Coupler C...0.0016 mole per mole of silver Coating amount of tricresyl phosphate 0.2cc/ ^m2 5th layer: Intermediate layer Same layer as the 2nd layer 6th layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.5 μ...Amount of coated silver 1.0 g/m ² Sensitizing dye...3 x 10 ^-5 per mole of silver Molar sensitizing dye...1 x 10 ^-5 mole coupler B-1...0.08 mole per mole of silver Coupler M...0.008 mole per mole of silver Coupler D...0.0015 mole trichrome per mole of silver Resyl phosphate coating amount 0.4cc/m ² 7th layer: Green sensitive high sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol % Average grain size 0.75 μ...Coating silver amount 1.6 g/m ² Sensitization 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...0.02 mol per mol of silver Coupler M...per 1 mol of silver 0.003 mol tricresyl phosphate coating amount 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 0.7 μ...Amount of coated silver 0.5 g/m ² Coupler Y-1... 0.125 mol trichrome per mol of silver Resyl 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...Coating silver amount 0.6 g/m ² Coupler Y -1...0.04 mole tricresyl phosphate coating amount per mole of silver 0.1cc/m ² 11th layer: Protective layer Trimethylmethanoacrylate particles (diameter
Apply a gelatin layer containing 1.5μ). The couplers in each layer are 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 then mixing it with a heated 10% gelatin solution to form a colloid. It was emulsified in a mill and used. In addition to the above composition, a gelatin hardener and a surfactant were added to each layer. The sample prepared as described above was designated as Sample 1. Compound sensitizing dye used to prepare the sample: anhydro-5,5'-dichloro-
3,3'-(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 F [MW≒533] Coupler M [MW≒929] Coupler Y-1 [MW≒748] Coupler B-2 [MW≒108] Coupler B-3 Coupler Y-2 Next, couplers B-1 and Y used in sample 1
-1 was changed to the coupler of the present invention, and the high boiling point organic solvent: tricresyl phosphate was changed to the coupler of the present invention.
HBS-5 and HBS-13 were used, and the amount added was changed to 0.5 times the coupler and 0.1 times the high boiling point organic solvent to sample 1, and the total amount of the coupler and high boiling point organic solvent to the amount of gelatin in each layer. The sample of the present invention was prepared with a constant ratio (0.8) so that the maximum color density was the same as that of the comparative sample. The obtained sample 1 was exposed to white light through a pattern for MTF measurement, and developed in the same manner as in Example 1. Each color image of these processed samples measures the MTF,
Table 3 below shows that the spatial frequency is 5 cycles/mm, 20
Cycles/mm and MTF of 35 cycles/mm were listed.

[Table] From the above results, it can be seen that the sharpness is significantly improved when the coupler of the present invention and the high boiling point organic solvent are used. In the samples of the present invention, not only is there a greater rate of increase in MTF values in the layers below the layer using the couplers of the present invention, but there is also an improvement in the color image of the layers containing the couplers of the present invention; This is presumed to be due to the fact that two photosensitive silver halide emulsion layers each having the same color sensitivity and the addition of the coupler of the present invention to the upper layer have an additional effect on the lower layer.

Claims (1)

[Scope of Claims] 1. A photographic light-sensitive material formed by dissolving a coupler in a solvent and applying the dispersion in a protective colloid solution, wherein the coupler is a low molecular weight coupler having a molecular weight of 250 to 450. A photographic light-sensitive material characterized in that the solvent is a phenolic high-boiling solvent having a boiling point of 175° C. (under 1 atmosphere) or more and represented by the following general formula. general formula (However, R ²² and R ²³ are hydrogen atoms, or straight chain or branched alkyl groups having 1 to 20 carbon atoms, and R ²⁴ is straight chain or branched alkyl groups having 1 to 20 carbon atoms, or cycloalkyl groups. ).