JPH10333274A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photographic sensitive material having a surface layer not causing fog, even if it is manufactured under high speed and high temperature drying conditions and keeping sufficient slidability and scratch resistance under high-speed conveyance and restrained from remarkable rise of a haze value by incorporating a specified compound in at least one photographic constituent layer. SOLUTION: The silver halide photographic sensitive material is provided on a support with at least one photosensitive silver halide emulsion layer and at least one of the photographic constituent layers contains the compound represented by the formula in which M is a divalent metal atom; and each of R1 and R2 is, independently, an alkyl group having the total C number of 24-100. This compound is used in a finely dispersed emulsion state, preferably, in a volume average particle diameter of <=1 μm, especially, <=0.5 μm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material having improved dry fog and improved surface properties.

[0002]

2. Description of the Related Art Photographic materials are generally prepared from a support such as cellulose triacetate, polyethylene terephthalate, paper or paper coated on both sides with a polyolefin, or on both sides directly or through an undercoat layer. The silver halide photographic emulsion layer and, if necessary, various layers such as an intermediate layer, a protective layer, a filter layer, an antistatic layer, an antihalation layer, and a backing layer are coated in various combinations.

Among these layers, silver halide photographic emulsion layers contain silver halide crystals having various grain sizes and shapes, sensitizing dyes and various other additives depending on the purpose. With the increase in sensitivity of materials, problems in the production of photographic materials have been increasingly highlighted. As one of them, coating and drying at higher speeds are constantly being considered by manufacturers to improve production efficiency.However, in order to produce at higher speed in limited equipment, drying is An increase in speed is required. However, when the layer containing the silver halide emulsion is rapidly dried, the binder rapidly undergoes volume shrinkage due to drying, causing stress concentration due to the volume shrinkage in the silver halide crystal, which causes so-called stress fogging. Many occurred. In order to alleviate the fogging phenomenon of silver halide crystals due to such stress concentration or residual stress, latex with a lower Tg is conventionally added, and although some improvement effect has been recognized, high-speed production requires higher temperature. In the present situation, the occurrence of fogging is still unavoidable when coating is performed under high-speed drying conditions.

Further, patents relating to drying conditions that do not cause dry fogging are disclosed in, for example, JP-A-2-247639 and JP-A-6-317874, and examples of the anti-drying-fogging agent are JP-A-6-273889. And polyhydric alcohols described in JP-A-2-247635 and JP-A-1-159635, and polyhydroxybenzenes described in JP-A-2-281251.

Although the above-described method may be effective under limited conditions, it is widely applied to the production of photographic materials under high-speed and high-temperature conditions as the object of the present invention. I couldn't do that.

On the other hand, in addition to the above-mentioned problem of dry fogging, there is a problem of generation of scratches accompanying the transportation of photographic materials. Since the photographic photosensitive material has the above-described configuration, various devices, machines, etc. are used in handling such as coating, drying, etc., as well as exposure, development, baking and the like in baking. The contact friction between the photosensitive material and the adhered portion of the photosensitive material, or the attached matter such as dust and fiber waste is often seriously adversely affected. For example, generation of scratches and abrasions on the photographic emulsion layer side, generation of film debris, and the like. In addition, recently, the use of photosensitive materials such as high-speed coating and rapid processing, the expansion of processing methods, and the diversification of the environment during use such as in a high-humidity and high-temperature atmosphere have made it possible to use photosensitive materials more than ever before. Due to severe handling, scratches and deterioration in transportability are likely to occur. Therefore, a photosensitive material having a surface quality that can sufficiently withstand such severe conditions is demanded.

Hitherto, as a means for improving the slipperiness and scratch resistance of the surface of a photographic light-sensitive material, a method of adding a lubricant to a protective layer has been used. As the lubricant, for example, Japanese Patent Publication No. 53-2
No. 92, polyorganosiloxanes as disclosed in U.S. Pat. No. 4,275,146, higher fatty acid amides as disclosed in U.S. Pat.
No. 41, British Patent No. 927,446, or JP-A-55-126238 and JP-A-58-90633.
Higher fatty acid esters such as those disclosed in Japanese Patent Application Laid-Open Publication No. H11-260, 1988 are known.

However, although the use of these known methods can certainly improve the slipperiness and scratch resistance of photographic materials, they are not satisfactory under severe conditions such as recent high-speed transport processes. For example, when silicone is used as a slipping agent for the surface layer, the added silicone may have an adverse effect upon application of the photographic emulsion, and may significantly impair coating properties such as repelling and wetting. In addition, when silicone, higher fatty acid, higher fatty acid polyhydric alcohol ester, higher fatty acid amide, higher fatty acid ester of higher fatty acid, etc. are used as a slip agent for the surface layer, considerable slipperiness and scratch resistance are initially obtained. Despite showing the properties, they have disadvantages such as deterioration over time, the slipping agent being eluted or diffused and dropped off during the development process, losing their effect, and causing processing solution contamination. Furthermore, when the above-mentioned lubricant is introduced into the photographic light-sensitive material, when the support is required to be transparent like a film,
Even if a small amount is added, the transmittance of the film is significantly reduced, and particularly when added to the surface layer of the photosensitive surface, light at the time of exposure is irregularly reflected on the surface, so that image quality is significantly reduced. Problem has occurred. This is particularly noticeable when various laser beams are used as a light source, and has caused a problem.

[0009]

Accordingly, an object of the present invention is to produce a silver halide photographic light-sensitive material under high-speed and high-temperature drying conditions without fogging, and furthermore, sufficient sliding under high-speed transport conditions. Provided is a silver halide photographic material having a surface layer which retains properties and scratch resistance and which does not significantly increase the haze value.

[0010]

According to the present invention, there is provided a silver halide photographic material having at least a photosensitive silver halide emulsion layer on a support, wherein at least one layer constituting the photographic material comprises: This has been achieved by a silver halide photographic light-sensitive material containing a compound represented by the following general formula.

[0011]

Embedded image

In the chemical formula 2, M represents a divalent metal. R
₁ and R ₂ represent an alkyl group, the total number of carbon atoms is 24 or more and 100 or less, and R ₁ and R ₂ may be the same or different.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Preferable examples of the divalent metal M in the compound of the above formula 2 include calcium, magnesium, zinc, iron, cobalt, nickel, copper and the like. Calcium and zinc have the least effect on the photographic properties and storability of the material. In addition, when the compound of the formula (2) is used by adding it to a coating solution as a dispersion, it is difficult to disperse. Calcium and zinc are also preferred. Particularly in the case of zinc, a great effect is exhibited for the purpose of the present invention.

The total number of carbon atoms of the alkyl group in Chemical formula 2 needs to be 24 or more in order to obtain sufficient slipperiness. On the other hand, if the total number of carbon atoms exceeds 100, dispersibility and applicability become difficult. More preferably 30 or more and 1 as the total number of carbon atoms
00 or less. Further, R ₁ and R ₂ are each an alkyl group having 10 or more and 70 or less carbon atoms in order to have sufficient scratch resistance and to suppress deterioration of slipperiness under various use conditions. (In the formula, R ₁ and R ₂ may be the same or different.)

[0015] In Formula 2, as a particularly preferred example of the alkyl group represented by R ₁ and R ₂ are the case where the ease of synthesis R ₁ and R ₂ represent the same alkyl group, having 12 carbon An alkyl group having a carbon number of 50 or less from the dodecyl group is preferable, and the alkyl group may be branched as well as linear.

[0016] For ease of availability, commercially available stearates are mentioned as examples. For example, Chukyo Yushi Co., Ltd. sells calcium stearate and zinc stearate as aqueous dispersions.

The compound of the above formula (2) can be easily dispersed directly in an aqueous phase or a hydrophilic colloid solution such as a gelatin solution using a dispersant. As the dispersant, a surfactant commonly used for photography can be used, for example, saponin (steroid), alkylene oxide derivative (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivative (alkenyl succinate) Acid polyglyceride),
Non-ionic surfactants such as fatty acid esters of polyhydric alcohols and alkyl esters of sugars, carboxyl groups, sulfo groups, and phospho groups such as alkyl carboxylate, alkyl sulfates and alkyl phosphates Surfactants containing an acidic group such as a sulfonic acid group or a phosphoric acid ester group; amphoteric surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphate esters; fatty acids or aromatic quaternary An O / W type emulsion is prepared using an ultrasonic homogenizer or a valve homogenizer, using an appropriate one selected from cationic surfactants such as ammonium salts, pyridinium, heterocyclic quaternary ammonium hydrochloride such as imidazolium, and then This dispersion is added to the gelatin solution and halogenated. Emulsion layers constituting photographic light-sensitive material, and is contained in the outermost layer to the support, such as a protective layer or a back layer.

The compound of the formula (2) is used after being dispersed in a fine emulsion state as described above. At this time, the particle diameter of the dispersion is preferably 1 μm or less, and more preferably 1 μm or less. It is preferably 0.5 μm or less. In particular, it can be used most preferably when there is at most 1% or less of components in a range of 0.05 to 0.4 μm and a particle size of 1 μm or more in the particle size distribution. Even if the compound of the formula (2) having such a particle size range is introduced into any layer constituting the photographic light-sensitive material, the film is homogeneous, excellent in transparency or gloss, and adversely affected by light scattering during exposure. And can be used very preferably. If the volume average particle diameter is less than 0.05 μm, the effects of the present invention are hardly exhibited, which may be undesirable. Conventionally, in the emulsification dispersion of the compound of the formula 2,
Although only emulsions having a particle size of about several microns were obtained, in recent years, the development of emulsification and dispersion technology has made it possible to reduce the particle size. For example, Chukyo Yushi Co., Ltd. has supplied emulsions of 0.5 microns or less. The present inventors have found that dry fog and scratch resistance are greatly improved by using a finely divided emulsion, and have reached the present invention. Furthermore, it was confirmed that haze and image quality did not deteriorate even when a relatively large amount was used for the surface layer of the film photosensitive material.

Even if the compound represented by the formula (2) is not in the above-mentioned particle size range, it can be used in the emulsion layer as a measure to prevent the above-mentioned dry fog, and can exhibit the effect, and is contained in the outermost layer. This improves the surface properties. Further, when the particle diameter is within the above range, it can be most preferably used in terms of image quality and production process.

The desired object can be attained by incorporating the above compound into a photographic constituting layer, that is, a silver halide emulsion layer, a protective layer, an intermediate layer, an undercoat layer, an antihalation layer, a backcoat layer, and the like. . In particular, by including the silver halide emulsion layer in a silver halide emulsion layer, it is possible to prevent dry fog under severe conditions such as high-speed high-temperature drying. The dry fogging prevention effect is most preferably contained in the silver halide emulsion layer,
There is also an effect when it is contained in a layer adjacent to the silver halide emulsion layer.

The above compound is added to a silver halide emulsion layer and / or
Or, by introducing it into the layer adjacent to it, even if photographic materials are manufactured under the conditions of high-speed and high-temperature drying, the stress due to the shrinkage of the emulsion layer coating is reduced, and the effect of the stress on the silver halide crystal is reduced. It has been found in the present invention that dry fogging can be effectively prevented. The addition of the above compound to the emulsion layer causes the production of a photographic light-sensitive material which has been conventionally coated and dried at a drying temperature of at most about 40 to 50 ° C., but produces a dry fog even under high-temperature drying conditions of, for example, about 50 to 80 ° C. One of the effects of the present invention is that it is possible to perform drying at a high speed without any problem, and that the contribution to the efficiency in the manufacturing process is extremely large.

Further, when the above compound is contained in a layer farthest from the support (surface layer such as a protective layer), the slip property and scratch resistance are remarkably improved. In the present invention, the outermost layer is composed of a gelatin binder and usually serves as a protective layer for the silver halide emulsion layer. When there is no protective layer, the silver halide emulsion layer may be the outermost layer. In such a case, the compound of the present invention is contained in the silver halide emulsion layer. One or more backing layers may be provided on the opposite side of the emulsion layer. The same effect can be obtained by including the above compound in the outermost layer of the backing layer.

In general, when a compound which improves the slipperiness is added to the outermost layer of the support and used, the adhesion to the binder constituting the outermost layer is particularly important. That is, in the production of silver halide photographic light-sensitive materials, water-soluble polymers such as gelatin are preferably used from the viewpoints of ease of multilayer coating and film properties, and various slip agents are used with such water-soluble polymers as binders. When a layer is formed in a state of being dispersed in a binder, when the surface comes into contact with a carrier such as a roll at the time of manufacture and use, the slip agent peels off from the binder, and the surface is scratched by the dropped lubricant. There are many. This is particularly noticeable when a sliding agent other than a metal salt of a higher fatty acid such as calcium stearate or zinc stearate is used as the sliding agent. In such a case, a problem that is easily damaged occurs.

In the case where a transparent support such as a film is used as the support, there is a problem that the surface should not be scratched. In addition, when the use of a lubricant greatly impairs the transparency, However, such lubricants cannot be used. In the case of the metal salt of a higher fatty acid represented by Chemical formula 2 according to the present invention, by adding the metal salt to the layer forming the outermost layer with respect to the support and using it, the adhesiveness to the binder forming the layer is obtained. Because it does not desorb from the outermost layer even when an excessive load is applied to the surface, such as during high-speed transport, and it is possible to significantly improve slipperiness even with a small amount of addition. Even when transparency is required as in the case of a film support, the effect is that the transparency is not impaired.

The amount of the compound of the formula (2) in one constituent layer is in the range of 0.01 to 10 grams per square meter, and more preferably in the range of 0.01 to 1 gram. If the amount is less than the above range and the amount is less than 0.01 g, the improvement effect is hardly exhibited, and if the amount exceeds the above range, transparency may be remarkably reduced, which is not preferable. Even when the compound of formula 2 is contained in a plurality of constituent layers, the total content is preferably 10 g or less.

The silver halide used in the photosensitive silver halide emulsion of the photographic light-sensitive material of the present invention is not particularly limited, but a surface latent image type silver halide emulsion is preferred. Silver chlorobromide, silver chloroiodobromide, silver bromoiodide,
Silver bromide or the like can be used. When silver chloroiodobromide or silver bromoiodide is used, the content of silver iodide is preferably within a range of 5 mol% or less. Morphology of silver halide grains,
The crystal habit and size distribution are not particularly limited, but those having a particle diameter of 0.7 μm or less are preferred. Silver halide emulsions include a gold compound such as chloroaurate and gold trichloride, a sulfur compound which forms silver sulfide by reacting with a salt or a silver salt of a noble metal such as rhodium and iridium, a stannous salt, Sensitivity can be increased without reducing particles with a reducing substance such as an amine. Further, iron compounds such as salts of noble metals such as rhodium and iridium, and red blood salts can be present during physical ripening or nucleation of silver halide grains.

In the present invention, the surface latent image type halide is an emulsion comprising silver halide grains having a surface sensitivity higher than the internal sensitivity. This emulsion is preferably US Pat. No. 4,224,401. It has a difference between the surface sensitivity and the internal sensitivity specified in the specification. The silver halide emulsion is desirably monodispersed, particularly in the above-mentioned U.S. Pat.
Emulsions having the monodispersity specified in JP-A-224,401 are preferred. The silver halide emulsion used in the present invention preferably contains a water-soluble rhodium salt (for example, rhodium dichloride, rhodium trichloride, potassium rhodium (III) hexachloride, ammonium rhodium (III) hexachloride, etc.). . The addition amount of the rhodium salt is preferably from 1 × 10 ⁻⁷ mol to 1 × 10 ⁻⁴ mol per mol of silver halide. The average grain size of the silver halide used in the present invention is preferably 0.7 microns or less, particularly preferably in the range of 0.1 to 0.4 microns. The shape of silver halide grains is cubic,
It may be a regular one such as an octahedron or a mixed crystal, but it is preferably a so-called monodisperse emulsion having a relatively narrow particle size distribution. The term "monodisperse emulsion" as used herein means an emulsion in which 90%, more preferably 95%, of the total number of grains falls within a grain size range of ± 40% of the average grain size. The form of reacting a soluble silver salt with a soluble halide salt for preparing a silver halide emulsion in the present invention may be any one of a single jet method, a double jet method, and a reverse mixing method formed in excess of silver ions. Although a means may be used, for the purpose of the present invention, a double jet method in which a soluble silver salt and a soluble halogen salt are simultaneously added in an acidic solution to form grains is particularly preferable. The silver halide emulsion prepared in this manner may or may not be chemically sensitized, and when chemically sensitized, ordinary silver sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, etc. Is used.

In the light-sensitive material of the present invention, a hydrazine compound may be contained in the silver halide emulsion layer.
Further, it may contain a new aqueous colloid layer adjacent to the surface latent image type silver halide emulsion layer. Such a layer is a layer having any function, such as an undercoat layer, an intermediate layer, a filter layer, a protective layer, and an antihalation layer, as long as it does not prevent the hydrazine compound from diffusing into the silver halide grains. There may be. Since the content of the hydrazine compound in the layer depends on the characteristics of the silver halide emulsion used, the chemical structure of the compound, and the development conditions, the appropriate content can vary over a wide range. A range of about 1.times.10.sup.- ⁶ to 1.times.10.sup.- ² mole per mole of silver in the latent image type silver halide emulsion is practically useful.

The photographic emulsion used in the present invention may be spectrally sensitized with a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. These sensitizing dyes
They may be used alone or in combination. Combinations of sensitizing dyes are often used, especially for supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that does not itself have spectral sensitization or a substance that does not substantially absorb visible light and that exhibits supersensitization.

Gelatin is advantageously used as a binder or protective colloid which can be used in the emulsion layer, surface protective layer (including backing layer) and intermediate layer of the light-sensitive material of the present invention. Can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol It is possible to use various kinds of synthetic hydrophilic high-molecular substances such as a single or copolymer such as a partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, and polyvinylimidazole. I can do it. Examples of gelatin include lime-processed gelatin, acid-processed gelatin, Bull. Soc. Sci. Photo. Japan, N
o. 16, p. Enzyme-treated gelatin as described in No. 30 (1966) may be used, and hydrolysates or enzymatic degradation products of gelatin can also be used.

When a hydrazine compound is contained in the emulsion layer, a conventional safelight dye may be added to the emulsion layer or another hydrophilic colloid layer. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts,
Nitroimidazoles, nitrobenzimidazoles,
Chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, mercaptotetrazole, mercaptopyrimidines, mercaptotriazines, thioketo compounds, azeindenes, etc. Many compounds, known as stabilizers, can be added. Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazoles) and nitroindazoles (eg, 5-nitroindazole).

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in a hydrophilic colloid layer such as an emulsion layer and a surface protective layer. For example, chromium salts (such as chrome alum), aldehydes (such as formaldehyde and glyoxal), N-methylol compounds, dioxane derivatives (such as 2,3-dihydroxydioxane), active vinyl compounds, and active halogen compounds (such as 2,4-dichloro-6) −
Such as hydroxy-s-triazine) can be used alone or in combination. In the photosensitive silver halide emulsion layer or a layer adjacent thereto, Research Disclosure (Research Disclosure) 17 is used for the purpose of increasing sensitivity, increasing contrast, or promoting development.
No. 465, Sections XX} BD. Particularly, it is preferable to add polyethylene glycol or a derivative thereof.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or hardly soluble synthetic polymer decomposition product in the photographic emulsion layer or other hydrophilic colloid layers for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl acetate, acrylonitrile, olefin, styrene or the like alone or in combination, or acrylic acid, methacrylic acid, α , Β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrenesulfonic acid and the like can be used as a monomer component.

[0034]

The present invention will be described more specifically with reference to the following examples, but the embodiments of the present invention are not limited thereto. Example 1 In the formulation of the emulsion layer, the average particle size of iridium-containing particles adjusted by a control double jet was 0.2.
A 5 micron monodispersed silver chlorobromide emulsion was prepared. After desalting, washing and re-dissolving by flow curation method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added to a concentration of 0.2 g / m ² to give a sensitizing dye. Anhydro-5,5-dichloro-9-ethyl-3,3 '
- di - (3-sulfopropyl) oxacarbocyanine hydroxide pyridinium was added to a 0.2 g / m ^2. The emulsion thus obtained was adjusted so that the dispersion of polyethylene acrylate was 2 g / m ² , the gelatin was 2.5 g / m ² , and the polyethylene glycol was 0.1 g / m ² . As a hardening agent, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium is used in 1% of gelatin.
Was added.

Emulsion (silver chlorobromide) 640 g gelatin 50 g amphitro-5,5-dichloro-9-ethyl-3,3'-di- (3-sulfofluoropropyl) oxacarboxycyanine Dispersion 40 g Polyethylene glycol 2 g 6-Methyl-4-humanperoxy-1,3,3a, 7-tetrasaindene 4 g Finished with water to 1000 g.

The emulsion layer having the above formulation was coated on a polyethylene terephthalate film, and a protective layer was further coated thereon. The protective layer of gelatin 1 g / m ² and a polyethylene glycol 0.2 g / m ^2, silica matting agent 0.03 g / m ²
And hydrin F-115 (zinc stearate emulsion, volume average particle diameter 0.13 μm) obtained from Chukyo Yushi Co., Ltd. as a compound of the present invention.
Protective layer to which hydrin F-115 was added in a solid content of 0.25 g / m ² (Αsample), protective layer to which 0.50 g / m ² was similarly added (sample B), and 1.00 g / m ^{2 to} likewise A protective layer (C sample) was formed. Further, as the present invention, a protective layer (sample D) to which 1.00 g / m ^{2 of a} zinc stearate emulsion having a volume average particle diameter of 1 μm was added, and 1.00 g / m ^{2 of a} zinc stearate emulsion having a volume average particle diameter of 5 μm were added. A protective layer (E sample) was prepared.

The hydrin F- of the C sample of the present invention described above.
In the same manner as above except that a lubricant emulsion (volume average particle diameter 5 μm) composed of a higher fatty acid ester (glycerol tripalmitate) was used instead of 115,
A sample (X) for comparison was prepared.

A comparative sample (Y) was prepared in the same manner except that the higher fatty acid ester was not used when preparing the coating composition of the comparative sample (X).

Evaluation of the surface layer of the photographic light-sensitive material The scratch resistance was evaluated using a HEDON-18 stylometer.
The sample was scratched with a continuous load of 0 to 100 g with a sapphire needle of 05 mmR, and the sample was subjected to MRA-CD401 and CF.
901 (manufactured by Mitsubishi Paper Mills) with a developer and fixer at 38 ° C
After the treatment for 20 seconds, the load (g) at which the scratch starts to be seen was visually evaluated. The turbidity was evaluated using a POIC haze meter by stacking 10 samples after the development processing and measuring the haze value of the sample. Table 1 shows the above results.

[0040]

[Table 1]

As is clear from the table, the samples A to E comprising the protective layer containing the compound according to the present invention have higher scratch resistance than the samples X and Y. In particular, by using a zinc stearate emulsion having a volume average particle diameter of 0.5 μm or less, scratch resistance is improved and an increase in haze value can be suppressed.

Example 2 In the formulation of the emulsion layer, the average particle size of iridium-containing particles adjusted by a control double jet was 0.2.
A 5 micron monodispersed silver chlorobromide emulsion was prepared. After desalting, washing and re-dissolving by flow curation method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added to a concentration of 2 g / m ² and anhydro-sensitizing dye was added. 5,5-dichloro-9-ethyl-3,3'-di - (3-sulfopropyl) oxacarbocyanine hydroxide pyridinium was added to a 0.2 g / m ^2. To the emulsion thus obtained, the compound of the present invention and the comparative compound were respectively added so as to have a solid content of 0.5 g / m ² , and the gelatin was further adjusted to be 2.5 g / m ² . As a hardening agent, 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium is used in 1% of gelatin.
Was added.

An emulsion coating solution having the above formulation was applied to a polyethylene terephthalate film which had been subjected to an aqueous subbing treatment using a rod bar.
It dried in the blast dryer set to 60 degreeC or 60 degreeC. The obtained photographic light-sensitive material sample was image-exposed using a xenon sensitometer, subjected to normal development processing, and then subjected to image density (Dm
ax) and the background density (Dmin) were determined by measuring the transmission density. The results are shown in Table 2.

[0044]

[Table 2]

As can be seen from the results in Table 2, the increase in Dmin was not observed for the sample to which the compound of the present invention was added even under the high-temperature drying conditions at 60 ° C., whereas the comparative sample 1 significantly increased. Also, the conventionally known dry antifoggants could not provide a sufficient effect. In this example, there was no effect on the photosensitive properties (sensitivity, tone, etc.) of the photosensitive material due to the presence or absence of the compound of the present invention, and the effect on the photosensitive properties was observed even after long-term storage. Did not.

[0046]

According to the present invention, the compound of the present invention has higher scratch resistance than the conventional one by being contained in the surface protective layer, and
The haze value also does not increase significantly. Dry fog can be greatly reduced by including it in the silver halide emulsion layer.

Claims (6)

[Claims] 1. A silver halide photographic material having at least a photosensitive silver halide emulsion layer on a support,
A silver halide photographic light-sensitive material characterized in that at least one layer constituting the photographic light-sensitive material contains a compound represented by the following general formula. Embedded image M represents a divalent metal. R ₁ and R ₂ represent an alkyl group;
The total number of carbon atoms is 25 or more and 100 or less. 2. The silver halide photograph according to claim 1, wherein the compound of the general formula is added in the form of a dispersion having a volume average particle diameter of 0.5 μm or less. Photosensitive material. 3. The silver halide photographic material according to claim 1, wherein the layer containing the compound of the general formula is an outermost layer with respect to the support. 4. The silver halide photographic material according to claim 1, wherein the layer containing the compound of the general formula is a silver halide emulsion layer. 5. The silver halide photographic material according to claim 1, wherein the compound of the general formula is zinc stearate. 6. The silver halide photographic material according to claim 3, wherein the compound of the general formula is contained in the outermost layer with respect to the support in a range of 0.01 g / m ² to 10.0 g / m ² .