JPH0477306B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to photographic materials. (Prior Art) In recent years, in silver halide photographic materials, improvements in sharpness and graininess have been strongly desired as small formats have become available. There is also a demand for highly sensitive silver halide photographic materials for indoor photography. In response to these demands, various studies are being conducted, such as increasing the quantum efficiency of silver halide grains contained in silver halide photosensitive materials, using monodispersed emulsions with less light scattering, and preventing light scattering by making films thinner. has been carried out with some success. However, although these technical measures have brought good results in many respects, the drawback of increasing sensitivity or thinning the film is that pressure fog is more likely to occur in photosensitive materials due to external physical pressure. . That is, during manufacturing, pressure fog is likely to occur due to pressure and abrasion during each process of coating and drying, cutting, and packaging, and during each operation process during photographing. The occurrence of fog due to pressure or scratching generally increases as the quantum efficiency of silver halide grains increases and as the absolute sensitivity increases, such as as the size of silver halide grains increases. As a method for preventing the pressure fog, for example, certain heterocyclic compounds (British Patent No. 738618),
Alkyl phthalate (US Pat. No. 738637), alkyl ester (US Pat. No. 738639), 2-pyrrolidone derivative (JP-A-48-24725) or certain hydrophilic compounds (US Pat. No. 2,960,404, US Pat. No. 3,520,094), A method has been proposed in which an organic high-boiling compound (JP-A-57-3928) or the like is added to a silver halide emulsion layer or a non-emulsion layer. However, if this method is used in an amount that is effective, it may cause excessive stickiness on the surface of the photosensitive material or may cause problems such as desensitization, sensitization, changes in gradation, fogging, etc. have a negative impact. In addition, the thinning of the sharpness improving means goes against the direction of absorbing and buffering the applied pressure, which goes against the purpose of preventing pressure fog. The current situation is that this is not the case. (Object of the Invention) Therefore, the first object of the present invention is to provide a silver halide photosensitive material with improved fogging caused by pressure or scratching. A second object of the present invention is to provide a silver halide photosensitive material which is less prone to fog due to pressure and scratching and has improved sharpness and graininess. A third object of the present invention is to provide a silver halide photographic material that has less fog caused by pressure or abrasion and is not sticky. (Structure of the Invention) As a result of intensive research in accordance with the object of the present invention, a high-sensitivity emulsion layer sensitive to pressure fog or abrasion fog has been developed using the general formula according to the present invention [],
By coating with a hydrophilic colloid layer containing at least one of the compounds represented by [], [], and [] in a manner that protects from external pressure and abrasion, the fog resistance is improved compared to a simple coating. It has been found that stickiness does not occur if the above-mentioned substances that cause stickiness are omitted and the compound represented by the above general formula is added. Based on this knowledge, the present invention achieves the object of the present invention, and provides a photosensitive material comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. In a silver halide photographic light-sensitive material in which at least one layer and at least one non-photosensitive layer are provided, the furthest position from the support is susceptible to external pressure or abrasion. Among the plurality of silver halide emulsion layers constituting the provided photosensitive layer, the silver halide emulsion layer that is particularly susceptible to the above-mentioned problems has the highest sensitivity and contains monodisperse silver halide grains with a monodispersity of 0.15 or less. emulsion layer,
The outside of the photosensitive layer (the side farther from the support)
It is constructed by providing a non-photosensitive layer containing at least one compound represented by the general formulas [] to []. In addition, the outside (the side farther from the support) of the non-photosensitive layer further containing the compound represented by the above general formula [] to []
Preferably, a non-photosensitive layer is provided. The effectiveness of the compounds represented by the general formulas [] to [] according to the present invention is further increased by including them in a protective dispersion in the non-photosensitive layer. Note that the non-photosensitive layer may be composed of multiple layers. Furthermore, the order of the layer structure of the emulsion layers in the photosensitive layer, which is composed of a plurality of silver halide emulsion layers having one color sensitivity and different sensitivities, is not particularly limited. It is preferable that the methods are provided in descending order of sensitivity from the outside to the inside (towards the support). In addition, in high-sensitivity multicolor color photographic materials, etc., the photosensitive layer is generally blue-sensitive, blue-sensitive,
A red-sensitive photosensitive layer is disposed adjacent to the green-sensitive and support. Next, the present invention will be explained in more detail. In the present invention, monodisperse silver halide grains refer to those whose standard deviation S divided by the average grain size r is 0.15 or less as defined by the following formula.
Further, it is preferable that the value is 0.10 or less because the effect of improving sharpness is large. S=√Σ(r-ri) ² ni ² /Σni S/r≦0.15 The average grain size here refers to the diameter of spherical silver halide grains, or the diameter of grains with shapes other than cubic or spherical. In this case, the average value of the particle size (diameter) when the projected image is converted into a circular image of the same area,
When the individual grain size is ri and the number is ni, it is defined by the following formula. =Σniri/Σni In the present invention, the preferred range is 0.3μ to 1.5μ. 2 different average particle sizes to widen exposure latitude
More than one type of emulsion may be mixed. In the present invention, the same effects as in the present invention can also be obtained when emulsions as defined above in which each monodisperse silver halide grain has been appropriately sensitized are used in combination. Therefore, in the present invention, two or more types of monodispersed silver halide grains having different average grain sizes may be used in combination. As a method for preparing the monodispersed silver halide grains of the present invention, grains of a desired size can be obtained by a double jet method while controlling P _Ag and PH. Further, for highly monodisperse silver halide emulsions, the method described in JP-A-54-48521 can be applied. A preferred embodiment of the method is a method in which potassium iodobromide, an aqueous gelatin solution and an ammoniacal nitric acid aqueous solution are converted into an aqueous gelatin solution containing silver halide seed grains and then added. In this case, the time function of addition rate, PH PAg temperature,
By appropriately selecting the temperature, etc., highly monodisperse silver halide can be obtained. In the present invention, the following general formula [], [], [] or [] is included in the non-photosensitive layer provided adjacent to the highly sensitive monodisperse silver halide emulsion layer of the photosensitive layer.
In the compound represented by the following general formula, the general formula [] General formula [] General formula [] General formula [] First, in the general formula [], R ¹ and R ² are hydrogen atoms,
represents an alkyl group or an aryl group, R ³ is an alkyl group, an aralkyl group or an alkenyl group, A
and B are respectively −CN, −SO ₂ R ¹⁵ , −
A group represented by COOR ¹⁶ , -CONR ¹⁷ R ¹⁸ -COR ¹⁹ (R ¹⁵ and R ¹⁶ each represent an alkyl group or an aryl group, R ¹⁷ and R ¹⁸ each represent a hydrogen atom, an alkyl group, or an aryl group, and ^R17 and
R ¹⁸ may be linked to each other to form a piperidino ring, a morpholino ring, a pyrrolidino ring or a piperazino ring. R ¹⁹ represents an alkyl group or an aryl group. Each of the above groups mentioned herein also includes those having a substituent. Furthermore, regarding the number of carbon atoms in the alkyl group mentioned above, R ¹ and R ² are 1 to 4;
R ³ is 1 to 6, and those substituted with a hydrophilic group such as carboxylic acid, sulfonic acid, or a salt thereof are particularly desirable. Preferred examples of aryl groups include unsubstituted or substituted phenyl groups. Typical examples of the alkyl group for R ¹ are methyl group, ethyl group, n-
Examples include propyl group and n-butyl group. R ¹
Typical examples of aryl groups include phenyl group,
Examples include tolyl group and xylyl group. Representative examples of the alkyl and aryl groups for R ² include the same examples as the alkyl and aryl groups for R ¹ . Typical examples of the alkyl group and aralkyl group for ^R3 are methyl group, ethyl group, sulfoethyl group,
Examples include benzyl group. Examples of alkenyl groups include allyl groups. Also, A and B are −CN, −SO ₂ R ¹⁵ −COOR ¹⁶
-CONR ¹⁷ R ¹⁸ or COR ¹⁹ , preferably A and B are different groups. R ¹⁵ and R ¹⁶ are as described above, and typical examples of the alkyl group include methyl group, ethyl group, and n-butyl group, and examples of the aryl group include phenyl group, tolyl group, and t-butyl group. Examples include butylphenyl group and methoxyphenyl group. In addition, R ¹⁷ and R ¹⁸ are as described above,
Typical examples of alkyl groups include methyl, ethyl, n-butyl, n-hexyl, n-octyl, and n-dodecyl groups. Further, typical examples of the aryl group for R ¹⁷ and R ¹⁸ include a phenyl group, a tolyl group, a methoxyphenyl group, and the like. R ¹⁹ is as described above, and typical examples of the aryl group are R ¹⁷ ,
The same example can be given for the aryl group of ^R18 . In the general formula [], R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom or an alkyl group, R ⁸ represents an alkyl group, aryl group or allyl group, R ⁹ and
R ¹⁰ each represents a hydrogen atom, an alkyl group or an aryl group, and G represents an electron-withdrawing group. Each of the above-mentioned groups herein includes those having a substituent, and the alkyl group is preferably an alkyl group having 1 to 20 carbon atoms in total. Furthermore, a preferable example of the aryl group is an unsubstituted or substituted phenyl group. Representative examples of alkyl groups for R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include methyl group, ethyl group, n-propyl group and n-butyl group, and R ⁹ and R ¹⁰ are as described above. However, typical examples of alkyl groups include methyl group, ethyl group, i-propyl group, n-butyl group, and benzyl group. R ⁹ and R ¹⁰ are as described above, and representative examples of the aryl group include phenyl group, ethyl phenyl group, n-butylphenyl group,
Examples include chlorophenyl group. G is an electron-withdrawing group, for example CN or SO ₂
R (R is an alkyl group having 1 to 10 carbon atoms or an aryl group having 7 to 15 carbon atoms), and the like. In the general formula [], n=1 or 2, and n is 1
In the case of R ¹¹ and R ¹² may be the same or different from each other, and include a cyano group, an alkyl group having 1 to 10 carbon atoms having a substituted alkyl group (e.g., a cyanoalkyl group, an alkoxyalkyl group),
Represents an aryl group or cyclic alkyl group having 6 to 20 carbon atoms, including substituted aryl groups. Further, when n is 2, at least one of R ¹¹ and R ¹² represents an alkylene group or an arylene group, and when one is as described above, the other represents an alkyl group or an aryl group. G is an electron-withdrawing group, e.g.
CN or SO ₂ R (R is an alkyl group having 1 to 10 carbon atoms or an arylalkyl group having 7 to 15 carbon atoms); In the general formula [], R ¹³ is a hydrogen atom and has 1 carbon number
~5 lower alkyl, ^R14 has 1~5 carbon atoms
Indicates up to 20 alkyl groups. Specific compounds are shown below, but the present invention is not limited thereto. The compound represented by the general formula [][][][] (compound according to the present invention) is generally effective when added in an amount of 1 mg/m2 ^or more, but especially when the total amount is 5 mg to 600 mg/m2. ^m2 is preferred. The compound according to the present invention can be dissolved in water, an organic solvent miscible with water (e.g., methyl alcohol, ethyl alcohol, isopropyl alcohol, dioxane tetrahydrofuran, tetrafluoropropyl alcohol, dimethylformamide, dimethyl sulfoxide, etc.), or a mixture thereof. It may be added to a coating solution containing a hydrophilic colloid for forming a component layer. At this time, if necessary, use a mordant (for example, US Pat. No. 2,548,564, US Pat. No. 2,882,156).
No. 3706563, No. 3709690, No. 3788855,
3795515, Special Publication No. 51-1418) can also be used together. If necessary, a substantially water-insoluble high-boiling organic solvent (e.g., dibutyl phthalate, dioctyl phthalate, triphenyl phosphate, tricresyl phosphate, triptyl acetyl citrate, N,N-diethyldodecanamide, N-dodecylpyrrolidone, octafluorobentyl dodecanoate, etc.), emulsified and dispersed, and added to the hydrophilic colloid layer. The ratio of the compound according to the present invention to the high boiling point solvent is preferably about 0.1 to 30 ml, more preferably 0.5 to 10 ml, per 1 g of the compound. Furthermore, the compounds according to the present invention can be incorporated into the coating solution after being emulsified and dispersed. More preferably, each compound is simultaneously dissolved in a high boiling point solvent and emulsion dispersed in an aqueous hydrophilic colloid solution. The silver halide photographic materials of the present invention include, for example, color negative photographic materials, black and white photographic materials, color aerial photographic films, X-ray photographic materials, printing photographic materials, color photographic papers, etc. that contain couplers in their photosensitive films. It can be applied to light-sensitive materials such as type silver halide color photographic light-sensitive materials, but is preferably useful for so-called color negative films for photography. The silver halide photographic material of the present invention has one or two types of coupler-containing silver halide emulsion layers on a support which has been subjected to corona discharge treatment, flame treatment, ultraviolet irradiation treatment, and subbing treatment as required. The above is an intermediate layer, a filter layer, an anti-halation layer,
It is provided in appropriate combination with a protective layer, etc. Advantageously used supports include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polycarbonate films, polystyrene films, and the like. Each of these supports is appropriately selected depending on the intended use of the silver halide photographic material. In the silver halide photographic material of the present invention,
Hydrophilic colloids which are advantageously used to prepare the emulsion of the light-sensitive layer include gelatin, colloidal albumin, agar, gum arabic, alginic acid, e.g. cellulose acetate hydrolyzed to an acetyl content of 19-26%. Cellulose derivative acrylamide, imidized polyacrylamide,
Zein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol-vinyl cyanoacetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate,
Included are polymers obtained by polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group. The silver halide grains used in the silver halide photographic material of the present invention may be obtained by any of the acid method, neutral method, and ammonia method. Alternatively, for example, a method may be used in which seed particles are produced using an acidic method, and then grown using an ammonia method, which has a faster growth rate, to grow to a predetermined size. When growing silver halide grains, the PH, EAg, etc. in the reaction vessel are controlled, and the amount is adjusted to match the growth rate of silver halide grains, as described in JP-A-54-48521, for example. It is desirable to implant and mix silver ions and halide ions sequentially and simultaneously. These silver halides include activated gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine; selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, etc. ,
polyamines, etc.; noble metal sensitizers, such as gold sensitizers,
Specifically, potassium aurithiocyanate, potassium chloroaurate, 2-oresulfo-2-methylbenzothiazolium chloride, etc.
Sensitizers of water-soluble salts such as palladium, platinum, ruthenium, rhodium, iridium, etc., specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these Depending on the size, it acts as a sensitizer or fog suppressant, etc.); etc. alone or in combination as appropriate (for example, a combination of a gold sensitizer and a sulfur sensitizer, a combination of a gold sensitizer and a selenium sensitizer, etc.) etc.) may be chemically sensitized. Furthermore, this silver halide can be optically sensitized to a desired wavelength range, for example, using cyanine dyes such as zeromethine dyes, monomethine dyes, dimethine dyes, trimethine dyes, or optical sensitizers such as merocyanine dyes alone. Optical sensitization can be performed separately or in combination (for example, superchromatic sensitization). This emulsion may also contain, for example, dihydroxyalkanes such as glycerin 1,5-pentanediol, esters of ethylene bisglycolic acid, bis-ethoxydiethylene glycol succinate, water-dispersible fine particulate polymer compounds obtained by emulsion polymerization, etc. It can contain wetting agents, plasticizers, film property improvers, etc., as well as ethyleneimine compounds, dioxane derivatives, oxypolysaccharides, dicarboxylic acid chlorides, matanesulfonic acid bisesters, and vinylsulfonyl-type hardeners. Various photographic additives such as film agents, saponins, coating aids such as sulfosuccinates, optical brighteners, antistatic agents, and antistain agents can be contained. The blue-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion used in the silver halide color photographic light-sensitive material of the present invention are optically processed using appropriate sensitizing dyes in order to impart photosensitivity to the desired wavelength range. Sensitized. Various sensitizing dyes can be used, such as cyanine dyes, merocyanine dyes, and composite cyanine dyes, and each sensitizing dye can be used singly or in combination of two or more. The coupler used in the silver halide color photographic light-sensitive material of the present invention may be either a Fisher type or an oil-soluble 4-equivalent coupler or a 2-equivalent coupler, and of course, a mixture of both may be used. . The coupler used in this case may be, for example, a colorless 2-equivalent or 4-equivalent coupler, or a so-called masking coupler having, for example, an arylazo group at the active site. Further, as the above couplers, the yellow coupler may be a benzoylacetanilide type or pivaloylacetanilide type coupler, and the magenta coupler may be a 3-acylamino-5-pyrazolone type or 3-anilino-5 type coupler. - It may be a pyrazolone type coupler or the like. In addition, a so-called group that forms a compound that exhibits a development inhibiting effect when detached from the active site of the coupler is introduced into the active site of the coupler.
DIR couplers (UK patent no. 953454 and US patent no.
3227554), etc., may be used. In addition, in order to improve photographic properties, couplers called so-called competing couplers, or compounds that release a development inhibitor according to the density of the image during development, so-called development inhibitor-releasing compounds, are used in combination with various couplers. (Compounds defined in Japanese Patent No. 2362752, Japanese Patent Application Laid-open No. 1977-77635, U.S. Patent No. 3632345, U.S. Patent No. 3297445, U.S. Patent No. 3379529, etc.)
may be contained. When the coupler used in the silver halide color photographic light-sensitive material according to the present invention is contained in the light-sensitive material, it can be contained in the coating solution of the constituent layer in various forms, such as the Fisher type. The coupler may be added in the form of a solution, and the oil-soluble coupler may be dissolved in a coupler solvent and contained in the form of an emulsion. The coupler solvents generally include di-n-butyl phthalate, benzyl phthalate, triphenyl phosphate, tri-o-
-cresyl phosphate, monophenyl di-p-
A high-boiling organic solvent that is immiscible with water, such as t-glylphenyl phosphate, is used. In the present invention, the method for coating the protective layer, silver halide emulsion layer, and other constituent layers of the light-sensitive material is as follows:
The selection is important to ensure uniformity of quality and productivity. For example, you can choose from dip coating, double roll coating, air knife coating, extrusion coating, curtain coating, etc. Among them, extrusion coating and curtain coating can apply two or more layers at the same time. is particularly useful. In addition, the coating speed can be selected arbitrarily, but from the viewpoint of productivity, it is set at 30m/
A speed of min or more is preferred. Also, for substances such as hardeners, which are so reactive that if added to the coating solution in advance, they will gel before coating, it is recommended to mix them using a static mixer or the like just before coating. preferable. (Examples) Next, the present invention will be explained in detail by examples, but the embodiments of the present invention are not limited thereto. In the examples, pressure fog of silver halide photosensitive emulsions due to scratching was evaluated by the following method. A load was applied to the unexposed sample from the photosensitive surface using a scratch hardness meter with a needle head of 0.3 mm, and the sample was processed according to the following processing steps to measure the load at which pressure fog occurred. Processing process (38℃) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing with water 3 minutes 15 seconds The composition of the processing solution used in each processing step is as follows. That's right. Color developer composition: 4-amino-3-methyl-N-ethyl-N-(β
Hydroxyethyl)-aniline sulfate 4.8g Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid 0.74g Anhydrous potassium carbonate 28.85g Anhydrous potassium bicarbonate 3.46g Anhydrous potassium sulfite 5.10g Potassium bromide 1.16g Sodium chloride 0.14g Nitrilotriacetic acid trisodium salt (monohydrate)
1.20g Potassium hydroxide 1.48g Add water to make 1. Bleach composition: Ethylenediaminetetraacetate iron ammonium salt
100.0g Ethylenediaminetetraacetic acid diammonium salt
10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0ml Add water to 1 and use ammonia water to make pH6.0
Adjust to. Fixer composition: Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to 1 and adjust to PH6.0 using acetic acid. Stabilizing liquid composition: Formalin (37% aqueous solution) 1.5ml Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.)
Add 7.5ml water to make 1. Example 1 Following the layer structure adopted in the industry for high-sensitivity silver halide color photographic light-sensitive materials, a red-sensitive layer and a green-sensitive layer were formed from the support while interposing various auxiliary layers. and a blue-sensitive layer, a monodisperse high-sensitivity emulsion layer is disposed on the outermost side of the blue-sensitive layer, and a non-photosensitive layer containing the compound according to the present invention is further coated on the outer side to obtain the effects of the present invention. To verify this, we created 10 types of samples: Samples A, B..., I, and J. Layer 1: antihalation layer containing 0.4 g of black colloidal silver and 3 g of gelatin. Layer 2...1.5g of low-sensitivity red-sensitive silver iodobromide emulsion (AgI; 6 mol%), 1.6g of gelatin and
0.80 g of 1-hydroxy-4-(β-methoxyethylaminocarbonylmethoxy)-N-
[δ-(2,4-di-t-amylphenoxy)
butyl]-2-naphthamide [hereinafter referred to as cyan coupler (C-1). ], 0.028g of 1
-hydroxy-4-[4-(1-hydroxy-
8-acetamido-3,6-disulfo-2-
naphthylazo)phenoxy]-N-[δ-(2,
4-di-t-amylphenoxy)butyl-2
- Naphthamide disodium [hereinafter referred to as colored cyan coupler (CC-1). ] 0.4 g of tricresyl phosphate [hereinafter referred to as TCP]. ] A low-sensitivity red-sensitive emulsion layer containing Layer 3...1.1g of highly sensitive red-sensitive silver iodobromide emulsion (AgI; 7 mol%), 1.2g of gelatin and
0.23g cyan coupler (C-1), 0.020g
A high-sensitivity red-sensitive emulsion layer containing 0.15g of TCP in which colored cyan coupler (CC-1) is dissolved. Layer 4: 0.07 g of 2,5-di-t-octylhydroquinone [hereinafter referred to as antifouling agent (HQ-1). ] was dissolved in 0.04 g of di-n-butyl phthalate [hereinafter referred to as DBP]. ] and 1.2g
middle layer containing gelatin. Layer 5...1.6 g of low-sensitivity green-sensitive silver iodobromide emulsion (AgI; 5 mol%), 1.7 g of gelatin, and
0.30 g of 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamido)benzenamide]
-5-pyrazolone [hereinafter referred to as magenta coupler (M-1). ], 0.20 g of 4,4-methylenebis-11-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamido)benzenamide]-5 -Pyrazolone [hereinafter referred to as magenta coupler (M-2). ], 0.066g of 1-
(2,4,6-trichlorophenyl)-4-
(1-naphthylazo)-3-(2-chloro-5
−octadecenyl succinimide anilino)
-5-pyrazolone [hereinafter referred to as colored magenta coupler (CM-1). A low-sensitivity green-sensitive emulsion layer containing 0.3g of TCP in which three types of couplers are dissolved. Layer 6...1.5g of highly sensitive green-sensitive silver iodobromide emulsion (AgI; 7 mol%), 1.9g of gelatin and
0.093g magenta coupler (M-1),
0.094g magenta coupler (M-2),
0.049g colored magenta coupler (CM-
1) High-sensitivity green-sensitive emulsion layer containing 0.12g of dissolved TCP. Layer 7...0.2g yellow colloidal silver, 0.11g DBP in which 0.2g antifouling agent (HQ-1) was dissolved and
Yellow filter layer containing 2.1g of gelatin. Layer 8...0.95 g of low-sensitivity blue-sensitive silver iodobromide emulsion (AgI; 6 mol%), 1.9 g of gelatin, and
1.84 g of α-[4-(1-benzyl-2-phenyl-3,5-dioxo-1,2,4-triazolidinyl)]-α-pivaloyl-2-chloro-5-[γ-(2,4 -di-t-amylphenoxy)butanamide]acetanilide [hereinafter referred to as yellow coupler (Y-1). ]
A low-speed blue-sensitive emulsion layer containing 0.93 g of DBP dissolved in DBP. Layer 9: Contains 1.2 g of highly sensitive monodisperse blue-sensitive silver iodobromide emulsion (AgI; 7 mol %), 2.0 g of gelatin, and 0.23 g of DBP in which 0.46 g of yellow coupler (Y-1) is dissolved. Highly sensitive blue-sensitive emulsion layer. In addition, the monodispersity (S/) of the high-sensitivity monodisperse photosensitive silver iodobromide emulsion (AgI; 7 mol %) used in layer 9
was 0.10. Layer 10: A second protective layer made of gelatin was provided. The second protective layer was designated as Layer 10, and samples were prepared by coating various compounds as shown in Table 1 on this layer at a concentration of 0.1 g/m ² . Compound emulsion dispersion Compound (Table 1) 4g Dibutyl phthalate 4g Ethyl acetate 20ml Sodium dodecylbenzenesulfonate 0.4g 5% gelatin aqueous solution In other words, comparative and exemplary compounds were added to a mixed solvent of dibutyl phthalate and ethyl acetate and heated to 50°C. After heating, this solution was added to a 5% aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and emulsified and dispersed in a colloid mill for 20 minutes. Layer 11...first protective layer containing 2.3 g of zetatin.

[Table] As mentioned above, after applying a load to the above coated sample from the photosensitive surface side using a scratch hardness tester with a needle head of 0.3 mm,
The sample was processed according to the above processing steps, and the load at which pressure fog occurred was measured.

[Table] Comparative compound-1: Dibutyl phthalate Comparative compound-2: 2-(2-hydroxy-5-
tert-Butyl) Phenylbenzotriazole It is clear from Table 2 that the samples (F to J) according to the present invention have significantly better resistance to pressure fog due to friction than samples A to E. Also, cut samples A to J into 5 cm square pieces.
After being stored for one day at 23°C and 180% RH (RH represents relative humidity), the protective layers of the same samples were brought into contact with each other, a load of 800 g was applied, and the samples were stored at 40°C and 80%
When the samples were stored in an atmosphere of %RH for 2 days and then peeled off to test their adhesion, samples B, C, and E
was fully adhered. In all other samples, the adhesive area was in the range of 0 to 15%, and no adverse effect on the adhesive properties of the present invention was observed. Comparative sample K was prepared by using a polydisperse emulsion (X) which was the same except that the monodispersity (S/) was 0.21 in place of the monodisperse emulsion in the ninth layer of samples A, D, G, and I. , L, M, and N were created. Furthermore, samples A and I
Similarly, Samples P and Q were prepared using the same comparative emulsion (Y) except that the monodispersity (S/) was 0.18. The load at which pressure fog occurs was similarly measured for the obtained sample, and the results are shown in Table 3 below. As can be seen from Table 3, the samples according to the present invention (F to J) have better pressure resistance than the comparative samples (K to Q).

[Table] Note that the samples according to the present invention provided images with good photographic characteristics.

Claims (1)

[Scope of Claims] 1. At least one light-sensitive layer and a non-light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. In a silver halide photographic light-sensitive material provided with at least one layer, the sensitivity is the highest among the plurality of silver halide emulsion layers constituting the photosensitive layer provided at the farthest position from the support. The silver halide emulsion layer having the highest concentration contains monodisperse silver halide grains represented by the following formula, and adjacent to the photosensitive layer and on the side opposite to the support, a layer having the following general formula [] ,
A silver halide photographic light-sensitive material, comprising a non-photosensitive layer containing at least one of the compounds represented by [ ], [ ] or [ ]. Formula Monodispersity=S/≦0.15 [S in the formula is standard deviation, is average particle size] General formula [] General formula [] General formula [] General formula [] [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, or an aryl group. R ³ is an alkyl group,
Represents an aralkyl group or an ^alkenyl group, and A and B are respectively -CN, _-SO2R15 , ^-COOR16 , -
CONR ¹⁷ R ¹⁸ or COR ¹⁹ (R ¹⁵ and
R ¹⁶ each represents an alkyl group or an aryl group, and R ¹⁷ and R ¹⁸ each represent a hydrogen atom, an alkyl group,
It represents an aryl group, and R ¹⁷ and R ¹⁸ may be linked to each other to form a piperidino ring, a morpholino ring, a pyrrolidino ring, or a piperazino ring. ^R19
represents an alkyl group or an aryl group. ^R4 , ^R5 ,
R ⁶ and R ⁷ each represent a hydrogen atom or an alkyl group, R ⁸ represents an alkyl group, aryl group, or alkenyl group, R ⁹ and R ¹⁰ each represent a hydrogen atom,
It represents an alkyl group or an aryl group, and G represents an electron-withdrawing group. n is 1 or 2, and when n is 1, R ¹¹ ,
R ¹² may be the same or different from each other,
It represents an alkyl group, an aryl group or a cyclic alkyl group, and when n is 2, at least one of R ¹¹ and R ¹² represents an alkylene group or an arylene group, and when one is the above, the other is an alkyl group or an aryl group. represents a group. R ¹³ is a hydrogen atom, with 1 or more carbon atoms
5 represents a lower alkyl group, and R ¹⁴ has 1 to 1 carbon atoms.
Represents up to 20 alkyl groups.