JPH0321898B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material,
In particular, the present invention relates to a silver halide photographic material which improves the harmful effects of ultraviolet rays by incorporating an ultraviolet absorber into the material, has excellent static resistance, and has improved physical properties. Unlike its own photosensitivity, photosensitive silver halide emulsions have a property of being sensitive to ultraviolet rays, and this property can be a major obstacle depending on the purpose and use of the photosensitive material. In addition to preventing deterioration of color reproducibility in color photographs and reduction in contrast in black and white photographs due to exposure to ultraviolet rays, it is necessary to prevent ultraviolet rays during discharge, which is one of the causes of so-called static marks caused by static electricity during the production of photosensitive materials. Ultraviolet absorbing compounds are also useful for prevention. Lenses for general photography are coated with ultraviolet absorbers or equipped with filters, but these properties vary depending on the lens, so even if the same photosensitive material is used, the resulting color tones may vary. Sometimes it appears. Ultraviolet absorbing compounds used in photosensitive materials include:
Not only physical properties such as absorption spectrum characteristics and extinction coefficient in the necessary wavelength range, which are related to the essential action of absorbing ultraviolet rays, but also photographic properties such as sensitivity even when contained in photosensitive materials, or manufacturing and development Chemical characteristics such as those that do not adversely affect photographic processing are required. Conventionally, many ultraviolet absorbers suitable for photosensitive materials have been proposed. These include, for example, U.S. Pat.
No. 2241239, No. 2298731, No. 2500045, No. 2241239, No. 2298731, No. 2500045, No.
This is disclosed in the specifications of No. 2503717, No. 2691579, No. 2860977, or British Patent No. 761728. However, many of these are unsatisfactory in that they either diffuse into other layers from the layer they are included in during manufacturing coating or photographic processing, or they do not have desirable absorption spectra or low extinction coefficients. In general, the absorption spectrum needs to be sufficiently broad to effectively absorb ultraviolet light, but it also needs to be sharply cut as it extends to visible light (blue), which reduces sensitivity in this region. Unexamined Japanese Patent Publication No. 51-56620, No. 52-49029, No. 53-
No. 128333, No. 54-111826, and No. 56-27146 disclose useful ultraviolet absorbing compounds.
However, these compounds are undesirable in that they cause devitrification after photographic processing due to so-called perspiration development when the photographic material is stored, particularly when stored at high temperatures. An object of the present invention is to provide a silver halide photographic material whose physical properties are significantly improved in the effects of heat after coating and drying. A second object of the present invention is to provide a silver halide photographic material in which static marks caused by ultraviolet rays are prevented. A third object of the present invention is to provide a silver halide photographic material in which variations in color reproducibility due to differences in ultraviolet absorption of photographic lenses are improved. At least one of the ultraviolet absorbers represented by the following general formula [] and the following general formula [] and []
It has been found that the above object can be achieved by a silver halide photographic material containing at least one ultraviolet absorber selected from the ultraviolet absorbers shown below. General formula [] General formula [] General formula [] In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom,
Represents an alkyl group having 1 to 6 carbon atoms.
R ₄ and R ₅ represent a hydrogen atom and a chlorine atom, respectively. R ₆ and R ₇ represent a hydrogen atom and an alkyl group, respectively, and R ₈ represents an alkyl group. A and B are respectively -CN, _{-SO2R18 ,} -
A group represented by COOR ₁₉ , -CONR ₂₀ R ₂₁ or -COR ₂₂ (R ₁₈ and R ₁₉ each represent an alkyl group or an aryl group, R ₂₀ and R ₂₁ each represent a hydrogen atom, an alkyl group or an aryl group,
R ₂₂ represents an alkyl group or an aryl group. )
represents. R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group, R ₁₃ represents an alkyl group,
R ₁₄ and R ₁₅ each represent a hydrogen atom, an alkyl group or an aryl group. In the general formula [], R ₆ is a hydrogen atom, an alkyl group or an aryl group, R ₇ is a hydrogen atom, an alkyl group or an aryl group, R ₈ is an alkyl group or an allyl group, A and B are respectively -CN and -SO ₂ R ₁₆ , −COOR ₁₉ ,
CONR ₂₀ A group represented by R ₂₁ or -COR ₂₂ (where R ₁₈ represents an alkyl group or an aryl group, R ₁₉ represents an alkyl group or an aryl group, R ₂₀ and R ₂₁ are a hydrogen atom, an alkyl group, aryl group, R ₂₂ represents an alkyl group or an aryl group). For example, the term "alkyl group" as used herein includes unsubstituted and substituted alkyl groups. Since the effect of the compound represented by the general formula differs depending on the number of carbon atoms in the alkyl group mentioned above (alkylene group constituting it in the case of a substituted alkyl group), R ₆ and R ₇ are 1 to 4, R ₈ is 1
R ₁₈ , R 19 , _{R 20 and} R ₂₁ are 1 to 6, especially those substituted with a hydrophilic group such as carboxylic acid or sulfonic acid or a salt thereof;
10 is desirable. Preferred examples of the above-mentioned aryl groups include unsubstituted or substituted phenyl groups. To be more specific, typical examples of the alkyl group for _R6 include methyl group, ethyl group,
Examples include n-propyl group, i-propyl group, n-butyl group, and the like. Representative examples of the aryl group for R ₇ include the same examples as the aryl group for R ₆ above. Typical examples of the alkyl group for _R8 include methyl group, ethyl group, i-propyl group, n-butyl group, n-hexyl group, sulfoethyl group, carboxyethyl group, sulfatoethyl group, hydroxypropyl group, sulfopropyl group. base,
Sulfobutyl group, 2-(2-sulfatoethoxy)
Examples include ethyl group, benzyl group, and sulfobenzyl group. Typical examples of the alkyl group for _R18 include methyl group, ethyl group, i-propyl group, n-butyl group, n-hexyl group, 2-ethylhexyl group, n-dodecyl group, benzyl group, etc. Can be done. Typical examples of the aryl group for R ₁₈ include phenyl, tolyl, ethyl phenyl, t-butylphenyl, methoxyphenyl, chlorophenyl, and the like. Typical examples of the alkyl group for _R19 are methyl group, ethyl group, n-butyl group, n-pentyl group, 2-ethylhexyl group, n-octyl group, n-
Examples include dodecyl group, 2-methoxyethyl group, 3-methoxy-3-methylpropyl group, 2-phenoxyethyl group, and benzyl group. _R19
Typical examples of the aryl group include phenyl group, tolyl group, t-butylphenyl group, octylphenyl group, di-t-amyl phenyl group, methoxyphenyl group, chlorophenyl group, and the like. Typical examples of the alkyl group for _R20 include methyl, ethyl, n-butyl, n-hexyl, n-octyl, and n-dodecyl groups. Representative examples of the alkyl group for R ₂₁ include the same examples as the alkyl group for R ₂₀ above. Typical examples of the aryl group for R ₂₁ include a phenyl group, tolyl group, methoxyphenyl group, chlorophenyl group, trifluoromethylphenyl group, and the like. Representative examples of the alkyl group for R ₂₂ include the same examples as the alkyl group for R ₂₀ above. Representative examples of the aryl group for R ₂₂ include the same examples as the aryl group for R ₂₁ above. Many of the compounds of this invention are
It shows an absorption maximum at 400 nm or less, and a desired absorption maximum can be selected by any combination of A and B. In this sense, the selection of the combination of A and B is important, and −CN, SO ₂ R ₁₈ , −
As already mentioned, it is selected from the groups represented by COOR ₁₉ , -CONR ₂₀ R ₂₁ or -COR ₂₂ , but it is more preferable that A and B are selected from different groups. Furthermore, one of A and B is −
More usefully, it is selected from the groups represented by CN or _-SO2R18 , in which _{case R6} and _R7
A more favorable effect can be obtained when both are hydrogen atoms. In the general formula [], R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group, R ₁₃ represents an alkyl group or an allyl group, and R ₁₄ and R ₁₅ each represent a hydrogen atom, an alkyl group or an allyl group. Represents an aryl group. For example, the alkyl group mentioned herein includes unsubstituted and substituted alkyl groups, and preferably has a total of 1 to 20 carbon atoms. Preferred examples of the above-mentioned aryl groups include unsubstituted or substituted phenyl groups. To be more specific, R ₉ , R ₁₀ , R ₁₁ ,
Typical examples of the alkyl group for _R12 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, etc. Typical examples of the alkyl group for _R13 include , methyl group, ethyl group,
i-propyl group, n-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n
-decyl group, sulfoethyl group, carboxyethyl group, hydroxyethyl group, methoxyethyl group,
Examples include sulfatoethyl group, sulfopropyl group, sulfobutyl group, 2-(2-sulfatoethoxy)ethyl group, benzyl group, and sulfobenzyl group. Typical examples of alkyl groups for R ₁₄ and R ₁₅ include methyl group, ethyl group, i-propyl group, n-butyl group, n-hexyl group, 2-ethylhexyl group, n-octyl group, n-decyl group. base,
Examples include n-dodecyl group and benzyl group. Typical examples of the aryl group for R ₁₄ and R ₁₅ include a phenyl group, an ethyl phenyl group, an n-butylphenyl group, a chlorophenyl group, a cyanophenyl group, a trifluoromethylphenyl group, and the like. Specific compound examples are shown below, but the present invention is not limited thereto. The amount of the compound of the invention is generally 1 mg/
Although the effect is observed when the amount of ultraviolet absorber is added in an amount of 5 mg/m ² or more, it is particularly preferable that the total amount of the ultraviolet absorber is 5 mg/m ² to 600 mg/m 2 . The compounds of the present invention can be used in water, water-miscible organic solvents (e.g. methyl alcohol, ethyl alcohol,
(isopropyl alcohol, dioxane tetrahydrofuran, tetrafluoropropyl alcohol, dimethylformamide, dimethyl sulfoxide, etc.)
Alternatively, it may be dissolved in a mixture thereof and added to a coating solution containing a hydrophilic colloid for forming a component layer. At this time, mordants (for example, U.S. Pat. No. 2548564, U.S. Pat. No. 2882156, U.S. Pat.
No. 3706563, No. 3709690, No. 3788855, No. 3706563, No. 3709690, No. 3788855, No.
3795515, Japanese Patent 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, acetyl tributyl citrate, N,N-diethyldodecanamide, N-dodecylpyrrolidone, octafluorobentyl dodecanoate, etc.), emulsified and dispersed, and added to the hydrophilic colloid layer. The ratio of the ultraviolet absorber of 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 ultraviolet absorber. Further, the compounds of the present invention can be incorporated into the coating solution after being emulsified and dispersed. More preferably,
This involves dissolving each compound simultaneously in a high-boiling point solvent and dispersing the emulsion in an aqueous hydrophilic colloid solution. Further, examples of combinations in which the compound of the present invention brings about good effects on the above-mentioned physical properties in such a dispersion method include at least one compound of the compound of the present invention represented by the general formula [] and the general formula [], the general formula [],
It is a combination of at least one compound represented by Preferably, the compound of the general formula [] and at least one compound represented by the general formula [] are combined, and more preferably the compound of the general formula [] and at least one compound of the general formula [] and the general formula [] are combined. It is to contain at least one compound of formula []. The layer containing the ultraviolet absorber of the present invention may be an emulsion layer or a non-photosensitive layer, but particularly effective are a surface protective layer, a back layer, and an antihalation layer, and preferably a surface protective layer, It is preferable to contain it in a layer close to the surface such as a back layer, and more preferably, it is contained in a layer far from the surface when the protective layer is composed of two layers. The silver halide color photographic light-sensitive materials according to the present invention include, for example, color negative light-sensitive materials, black-and-white photographic materials, color aerial photographic films, X-ray light-sensitive materials, printing materials, color photographic papers, etc. containing couplers in the light-sensitive film. It can be applied to light-sensitive materials such as internal silver halide color photographic light-sensitive materials, but so-called color negative films for photography are preferably useful. The silver halide color photographic light-sensitive material according to the present invention has one type of silver halide emulsion layer containing a coupler or 2
These layers are formed by appropriately combining these layers with an intermediate layer, a filter layer, an antihalation layer, 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 color photographic light-sensitive material. In the silver halide color photographic light-sensitive material according to the present invention, hydrophilic colloids that are advantageously used to prepare the light-sensitive emulsion include gelatin, colloidal albumin, agar, gum arabic, and alginic acid, such as acetyl content of 19 to 26%. cellulose derivatives such as cellulose acetate hydrolyzed to
Included are polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, and polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups. As the silver halide used in the silver halide color photographic light-sensitive material according to the present invention, common silver halide photographic emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodobromide, etc. Includes anything used in These silver halide emulsions can be produced by various manufacturing methods including the usual manufacturing method, such as the direct mixing method, the simultaneous mixing method, or the method described in Japanese Patent Publication No. 46-7772, or the method described in U.S. Pat. No. 2,592,250. method as described,
That is, a so-called emulsion of silver salt grains consisting of at least some silver salts having higher solubility than silver bromide is formed, and then at least a part of these grains is converted into silver bromide salt or silver iodobromide salt. It can be prepared by any method such as a conversion emulsion method or a Lippmann emulsion method consisting of fine-grained silver halide having an average grain size of 0.1μ or less.
The silver halide emulsion may contain chemical sensitizers, such as sulfur sensitizers such as allylthiocarbamide, thiourea, allyl isothiocyanate, cystine, active or inactive selenium sensitizers, such as potassium chloroaurate, oleic acid, etc. Gold compounds such as chloride, potassium auricular thiocyanate, 2-aurothiabenzothiazole methyl chloride, palladium compounds such as ammonium chloroparadate, sodium chloroparadite, platinum compounds such as potassium chloroplatinate, ruthenium compounds, rhodium compounds , noble metal sensitizers such as iridium compounds, or combinations of such sensitizers. In addition to chemical sensitization, this emulsion can be reduced sensitized using a reducing agent, and is stable with triazoles, imidazoles, azaindenes, benzothiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. It is also possible to contain a thioale type, quaternary ammonium salt type or polyalkylene oxide type sensitizing compound. This emulsion can also contain, for example, glycerin, 1,
Dihydroxyalkanes such as 5-pentanediol, esters of ethylene bisglycolic acid, bis-ethoxydiethylene glycol succinate,
It can contain wetting agents such as water-dispersible particulate polymer compounds obtained by emulsion polymerization, plasticizers, film property improvers, etc. In addition, ethyleneimine compounds, dioxane derivatives, oxypolysaccharides, Various photographic additives such as dicarboxylic acid chloride, methanesulfonic acid bisester, etc. or vinylsulfonyl type hardeners, saponin, coating aids such as sulfosuccinates, optical brighteners, antistatic agents, antistain agents, etc. It is possible to contain an agent. The blue-sensitive emulsion, green-sensitive emulsion and red-sensitive emulsion used in the silver halide color photographic light-sensitive material according to the present invention are optically processed using appropriate sensitizing dyes in order to impart photosensitivity in 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 so-called development inhibitor-releasing compounds (compounds that release a development inhibitor depending on the density of the image during development) are used in combination with various couplers to improve photographic properties. German Patent No. 2362752, JP-A-49-77635, U.S. Patent No. 3632345, U.S. Patent No. 3297445
No. 3,379,529, etc.). When the coupler used in the silver halide photographic light-sensitive material according to the present invention is contained in the photographic light-sensitive material, it can be contained in the coating solution of the constituent layer in various forms, such as a Fisher type 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. As this coupler solvent,
Generally, di-n-butyl phthalate, benzyl phthalate, triphenyl phosphate, tri-
O-cresyl phosphate, monophenyl di-P
A water-immiscible high-boiling organic solvent such as -t-glyphenyl phosphate is used in an amount of 0.1 to 10 parts by weight per part by weight of the coupler. When the coupler used at this time is dissolved in an oil-soluble, water-immiscible, high-boiling organic solvent and incorporated in the form of an emulsion, the By increasing the proportion of the water-immiscible high-boiling organic solvent to the oil-soluble coupler, the influence of harmful gases such as formaldehyde gas can be further reduced, but this is not sufficient. In this case, increasing the proportion of the high boiling point solvent causes various problems, such as physical properties, so there is a limit to the proportion used.
In such silver halide color photographic materials,
When the compound according to the present invention is added, the physical properties are not affected and the effect of preventing the influence of formaldehyde gas etc. can be increased. The silver halide photographic material according to the present invention includes:
Various formaldehyde scavengers well known in the art, such as dimedone, non-reducing or cyclic urea, 1,2-dihydroxynaphthalene, 4-equivalent yellow or magenta couplers, etc., can be used in the photosensitive layer affected with formaldehyde; They may be used in combination so that they are present in a layer closer to the surface. In the present invention, even if the above-mentioned compound is added during the manufacturing process of silver halide photographic light-sensitive materials, there will be no reduction in sensitivity or other problems, and there will be no reduction in color density due to harmful gases such as formaldehyde gas.
It is possible to increase the effect of preventing gamma reduction and capri increase. Although various types of curing agents can be used in the silver halide photographic material according to the present invention, formaldehyde-type curing agents are not desirable. As the curing agent, a vinylsulfonyl type curing agent as described in Japanese Patent Application No. 45-54236 is particularly preferred. Among these, the most satisfactory results are obtained when, for example, 1,2-divinylsulfonylethane is used. Example 1 A gelatin layer containing black colloidal silver was provided as a first layer on a triacetate film support as an antihalation layer. Exemplary coupler (C-1) and 1 as second layer
-Hydroxy-4-(2-ethoxycarbonylphenylazo)-N-[α-(2,4-di-t-amylphenoxy)butyl]-2-naphthamide-containing red-sensitive emulsion layer (8 moles of silver iodide) (containing 300g of gelatin per mole of silver iodobromide containing
m ² . A gelatin layer was provided as the third layer. Exemplary coupler (M-1) and 1 as the fourth layer
-(2,4,6-trichlorophenyl)-3-[3
- A green-sensitive emulsion layer containing -{α-(2,4-di-t-amylphenoxy)acetamide}anilino]-4-(methoxyphenylazo)-5-pyrazolone (an iodine containing 8 mol% silver iodide) A gel containing 350 g of gelatin per mole of silver oxide and sensitized using a sensitizing dye was provided so that the amount of silver coated was 31 mg/am ² . A filter layer made of gelatin containing yellow colloidal silver was provided as the fifth layer. A blue-sensitive emulsion layer containing an exemplary coupler (Y-1 below) as the sixth layer (containing 350 g of gelatin per mole of silver iodobromide containing 7 mol % of silver iodide and sensitized using a sensitizing dye) ) with a coating silver amount of 20 mg/am ²
It was set up so that A protective layer made of gelatin was provided as the seventh layer. A sample was prepared by applying an ultraviolet absorber to the above protective layer at a concentration of 1.50 g/m ² . Exemplary coupler (C-1): 1-hydroxy-N-[δ-(2,4
-di-t-amylphenoxy)butyl]-
2-Naphthamide (M-1): 1-(2,4,6-trichlorophenyl)-3-[3-(2,4-di-t-amylphenoxyacetamide)benzamide]
-5-pyrazolone (Y-1): α-pivalyl-α-(1-benzyl-
2-phenyl-3,5-dioxotriazolidin-4-yl)-2'-chloro-5'-[γ
-(2,4-di-t-amylphenoxy)
Butylamide] Acetanilide Exemplary Compounds (Table 1) 4g Dibutyl phthalate 4g Ethyl acetate 20ml Sodium dodecylbenzenesulfonate 0.4g 5% gelatin aqueous solution 100ml In other words, the exemplary compound was 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.

【table】

[Table] These coated samples were conditioned to 55% RH, sealed, and heat treated at a temperature of 70°C for 2 days, and then subjected to color development according to the following processing steps. The turbidity of each sample after treatment was measured using a Poitzk integrating sphere turbidimeter manufactured by Nippon Seimitsu Kogaku Co., Ltd. The results are shown in Table 2. Processing process (38 c.c.) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water washing 3 minutes 15 seconds The processing solution composition used in each processing step is It is as follows. 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 Chloride Sodium 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 Ice Vinegar Acid 10.0ml Add water to 1 and adjust pH using ammonia water
Adjust to 6.0. 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.

[Table] * Numbers indicate ppm.
The numerical values in Table 2 indicate the change in turbidity of the developed sample due to heat treatment, and the larger the numerical value, the greater the devitrification of the film. As is clear from Table 2, samples other than those of the present invention showed large changes in turbidity, but samples using the combination of the present invention had small changes in turbidity, and a decrease in sweat development was observed. Example 2 The following static tests were conducted on Samples A to S described in Example 1. Sample A with a rubber roller near ±0 in the charging series
~ J in a dark room 20 times on the protective layer side to generate discharge light. These were developed in the same manner as in the examples, and the maximum density portion of the static mark was measured using blue light. The results are shown in Table-3.

[Table] As shown in Table 3, it is clear that the combination of the present invention reduces the occurrence of static marks. Example 3 For Samples A to S described in Example-1, ultraviolet transmittance was measured as a method for measuring changes in color balance of photographic materials due to differences in camera models using lenses with different ultraviolet transmittances. Using a camera with a good lens and a filter that cuts out the following wavelengths of light, we photographed a gray chart, and after processing, we measured the differences in the density of red, green, and blue light for both.

[Table] As can be seen from Table 4, in the samples of the present invention, the photographic light-sensitive materials show little change in blue density and are not affected by changes in ultraviolet transmittance.

Claims (1)

[Claims] 1. A halogen containing at least one ultraviolet absorber represented by the following general formula [] and at least one ultraviolet absorber selected from the ultraviolet absorbers represented by the following general formula [] and [] It has been found that the above object can be achieved by a silver oxide photographic material. General formula [] General formula [] General formula [] [In the formula, R ₁ , R ₂ and R ₃ are each a hydrogen atom,
Represents an alkyl group having 1 to 6 carbon atoms.
R ₄ and R ₅ represent a hydrogen atom and a chlorine atom, respectively. R ₆ and R ₇ each represent a hydrogen atom or an alkyl group, and R ₈ represents an alkyl group. A and B are respectively -CN, _{-SO2R18 ,} -
A group represented by COOR ₁₉ , -CONR ₂₀ R ₂₁ or -COR ₂₂ (R ₁₈ and R ₁₉ each represent an alkyl group or an aryl group, R ₂₀ and R ₂₁ each represent
It represents a hydrogen atom, an alkyl group or an aryl group, and R ₂₂ represents an alkyl group or an aryl group. ). R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom or an alkyl group, R ₁₃ represents an alkyl group,
R ₁₄ and R ₁₅ each represent a hydrogen atom, an alkyl group or an aryl group. 2. The silver halide photographic light-sensitive material according to claim 1, which has at least one light-sensitive silver halide emulsion layer and at least one light-insensitive hydrophilic colloid layer on a support. . 3. A non-photosensitive colloid layer containing at least one ultraviolet absorber represented by the general formula [] and at least one ultraviolet absorber selected from the general formulas [] and [] A silver halide photographic material according to claim 2.