JPS6016613B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material that suppresses the occurrence of fog and has improved surface properties, and more specifically, the present invention relates to a silver halide photographic material that suppresses the occurrence of fog and has improved surface properties. This invention relates to a silver halide photographic material with suppressed surface adhesion and reduced surface adhesion. In recent years, the constituent layers of silver halide photosensitive materials have been made thinner in order to improve the sharpness of images, speed up development processing, speed up drying during manufacturing, and demand for resource conservation. At the same time, high sensitivity is required, and even though the layer is thin, it has to contain a high amount of silver. On the other hand, in order to streamline the manufacturing process, there is a strong demand for rapid drying after coating a silver halide emulsion on a support or the like. Fog caused by drying has been observed in conventional silver halide photographic materials in which emulsions with low silver halide densities are dried at low speed, but this has been prevented to an extent that does not pose a practical problem. However, with the increase in silver content, thinning of the film, and rapid drying as described above, fogging due to extremely strong drying has started to occur. In order to prevent fog caused by drying, various compounds have been added to hydrophilic polymers used as binders for silver halide emulsions, such as glycerin and the like as described in U.S. Pat. Alkylene diols, or cyclohexanes as found in British Patent No. 123,933, and even US Pat. No. 365,695.
It is known to contain polyglycidol and the like described in Specification No. 6. However, even if they are included, they not only lose their antifogging effect due to high silver content and rapid drying, but even when manufactured under conventional slow drying conditions, the compounds used in this method are hygroscopic or sticky. Because of this, silver halide photographic light-sensitive materials after drying adhere to each other or to intervening paper, wrapping paper, X-ray intensifying screens, etc., resulting in peeling or transfer, etc. Various methods are known to improve such surface adhesion. For example, one of the most effective methods is to reduce the contact area by using water-insoluble fine particles called matting agents in the outermost protective layer of the silver halide photographic light-sensitive material or in the backing layer on the back of the support. There is. However, with this method, these matting agents coagulate in the coating solution, making it impossible to obtain a uniform coating film, and the photographic film loses transparency after processing, and the graininess of the image deteriorates. Has undesirable side effects. Even more fatally, even when used in combination with the drying fog improver mentioned above, it does not have the effect of suppressing the occurrence of fog caused by rapid drying. An object of the present invention is to improve the above-mentioned drawbacks and provide a silver halide photosensitive material which is excellent as a commercial product. The first object of the present invention is to provide a silver halide photographic material which suppresses the occurrence of fog even when rapidly dried during production and has excellent photographic properties. The second object of the present invention is to suppress fogging as described above, and also to prevent silver halide photographic materials from adhering to each other or to interleaved paper, wrapping paper, X-ray intensifying screen, etc. The object of the present invention is to provide a silver halide photographic material having favorable surface properties. As a result of extensive research, the present inventors found the following general formula [1
] and the following general formula [0
It has been found that the above object can be effectively achieved by incorporating in the silver halide emulsion layer a combination of at least one of the polymer compounds represented by the following. General formula [1] [In the formula, R,, R2, R3 and R4 represent the same or different hydrogen atoms or lower alkyl groups, and Z is ★C and n (where n is 0 or 1 to 5). ), (Here, R5 and R6 each represent a hydrogen atom, a methyl group, an ethyl group, or a propyl group, but both R5 and R6 are not hydrogen atoms.), -CH2-○-C& -, 1CH=CH1, 1C3C
- represents or. ] General formula [B] [In the formula, R7 and R8 each represent the same or different hydrogen atom, halogen atom (preferably a chlorine atom or bromine atom), or a lower alkyl group, M, and M
2 each represents a cation (for example a hydrogen atom, an alkali metal atom or an ammonium group). m represents the degree of polymerization and takes a value such that the molecular weight is from about 5,000 to about 300,000. General formula [1] used in the present invention
For example, the compound represented by
4 and No. 365075, it is known to be used for purposes such as adding flexibility to gelatin, and can be easily synthesized by known methods. When R,, R2, R3 and R4 in the general formula [1] are alkyl groups, if the number of carbon atoms forming the alkyl group increases, the surface adhesion will deteriorate even if the drying fog suppressing effect increases. The number of carbon atoms is selected to be 4 at most, preferably 1 or 2. Z again
Even when is an alkylene group, the number of carbon atoms forming the alkylene group is usefully 5 or less, preferably 3 or less, in order to balance the effect of suppressing drying fog with the effect of improving adhesion.
Examples of the compound represented by the general formula [1] are shown below. [
1] 1〈a〉 day○CH2-℃day 2○day [1]-(d)
HOCH2CH2CH20 days [1] - (h) HOCH2
(CH2) 8CH20th [1]-kuj> day. CH2 (CH2) 5CH20 days [1] Ikku n〉 Day〇C
H2CH2○CH2CH2○ day [1]・(r) day. C
H2CH=℃HCH20 days [1] - (S) days〇CH2G
==℃CH20 days [1]-(t)HOCH2C=℃CH
Regarding the exemplary compounds listed above, dihydroxyalkanes and hydroxyethylene oxides are advantageously used in the present invention, and among these, dihydroxyalkanes are particularly effectively used.
The compound represented by general formula [D] has a molecular weight of about 5000
The above is effective. If the molecular weight is too large, the viscosity of the silver halide emulsion containing it will be too high, making coating difficult, so it is better to keep it to about 20, more preferably about 150,000 or less. general formula

Specific examples of the compound represented by [0] are shown below. The terminal end of the compound is a hydrogen atom. General formula used in the invention

The compound represented by [0] is disclosed in French Patent No. 764394 and German Patent No. 64.
As described in the specification of No. 5625, it is known as a hydrophilic polymer and has been used in silver halide photographic materials as a substitute for gelatin. It can be easily obtained by radical polymerizing a monomer and maleic anhydride, hydrolyzing the resulting polymer, and then neutralizing it. General formula [1] used in the present invention and

The initial objective can be achieved by incorporating one or more of the compounds represented by [0] into the element layer constituting the silver halide photographic light-sensitive material. Among these constituent layers, it is most effective to include it in the silver halide emulsion layer, but
It may also be included in a protective layer or other component layer adjacent to the silver halide emulsion layer. In order to incorporate the compound, it is added to the coating solution for forming the component layer by dissolving it in water or a solvent compatible with water (for example, lower alcohols, ester ketones), or a mixed solvent thereof. 'Mayoi. The addition time may be at the time of coating or any time before coating, but if the layer to be contained is a silver halide emulsion layer, it is preferably added after chemical ripening and during coating. The addition amount of the compound represented by the general formula [1] is preferably in the range of 10M to 500M per night of gelatin contained in the layer, whether the compound represented by the general formula [1] is used alone or in combination of two or more. More preferable results are obtained in the range of 1 to 300 nails 9. general formula

The compound represented by [0] varies depending on the amount of the compound represented by the general formula [1] used together, but in general, the total amount of gelatin contained in the layer to be contained is 10 to 200 o per night. Preferably, the weight ratio of the compound 10 of the general formula [1] to the compound 10 of the general formula [1] is

Good results can be obtained with the compound represented by [0] at a ratio of 1 to 5. However, it goes without saying that the above-mentioned amount to be added is appropriately selected depending on the type of silver halide, the layer to be added or the type of compound used. General formula according to the present invention [
Compounds 1] and [B] may be mixed in advance and then added to the coating solution, or they may be added separately without any difference in effect, and in some cases they may be added to different layers. It's okay. Silver halide photographic materials to which the present invention can be applied include various types of silver halide photographic materials. For example, general black and white photographic materials, X-ray photographic materials, color photographic materials, photographic materials for printing, photographic materials for copying, diffusion transfer photographic materials, silver dye bleaching photographic materials, direct positive photographic materials. Although the present invention can be effectively applied to any materials, particularly good results can be obtained when applied to X-ray photographic materials. The silver halide used in these silver halide photographic light-sensitive materials includes silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloride, silver chlorobromide, silver halide of various crystal habit and grain size depending on the purpose.
Various materials such as silver iodochlorobromide are used. - These photosensitive silver halide emulsions are obtained by suspending them in a hydrophilic colloid by a known method. In that case, it may be adjusted by any of the ammonia method, neutral method, or acid method, and any mixing method such as single jet method or double jet method may be used. Hydrophilic colloids to which the present invention is applied include proteins such as gelatin, albumin, and casein as binder components, hydroxyethyl cellulose, carboxymethyl cellulose,
Examples of cellulose derivatives, starch, sugar derivatives such as agar, sodium alginate, dextran sulfate, polyvinyl alcohol, polyN-vinylpyrrolidone, polyacrylic acid derivatives, etc. may be used. In particular, hydrophilic colloids made of gelatin are commonly used. The silver halide emulsion of the present invention includes noble metal sensitization, sulfur sensitization,
Chemical sensitization methods such as reduction sensitization can be applied. In order to improve the storage stability of the silver halide emulsion according to the present invention, known stabilizers such as azaindenes, thiazolium salts, mercaptotetrazoles, etc., and fog inhibitors can be used. The silver halide emulsion according to the present invention includes cyanine, merocyanine, hemicyanine, rhodacyanine,
Spectral sensitization can be performed using methine dyes such as oxonol, styryl dyes, and the like. The silver halide photographic light-sensitive materials to which the present invention can be applied include aldehyde-based, aziridine-based, isoxazole-based, epoxy-based, vinyl sulfone-based, acryloyl-based, carposimide-based, and maleimide-based photographic hardeners in the coating solution. , acetylene-based, methanesulfonic acid ester-based, and triazine-based compounds can be used as appropriate. When the silver halide photographic light-sensitive material of the present invention is an X-ray photographic light-sensitive material, preferable effects can be obtained by using an aldehyde-based hardening agent. In the component layer of the silver halide photographic light-sensitive material to which the present invention is applied, coating aids such as /ionic activators such as saponin or sulfosuccinic acid type anionic activators are used to facilitate the coating of the layer. can contain. When the present invention is applied to a color photosensitive material, various couplers can be used. For example, a closed ketomethylene type coupler is used as a yellow coupler, and a pyrazolone type, pyrazolotriazole type, or pyrazolino type coupler is used as a magenta coupler. Examples include benzimidazole-based, imidazolone-based, and other compounds. As cyan couplers, phenolic couplers, naphthol type couplers, color magenta couplers, colored cyan couplers, development inhibitor-releasing couplers, development inhibitor-releasing substances, Wiskapfuu-competing couplers, etc. may be used. The silver halide photographic material of the present invention does not prevent the inclusion of ultraviolet absorbers, image stabilizers, antifouling agents, metal ion sequestering agents, etc. in the silver halide emulsion layer or its adjacent layer. As mentioned above, in the silver halide photographic light-sensitive material according to the present invention, layers other than the silver halide emulsion layer include a protective layer, an intermediate layer, a filter layer, an antihalation layer, an undercoat layer, an auxiliary layer,
These layers may have a backing layer, etc. as a support, such as baryta paper, polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate, polyvinyl acetal, polypropylene, such as polyethylene terephthalate, etc. There are polyester films, polycarbonate films, styrene films, etc., and these supports may be subbed-treated if necessary, or may contain optical brighteners, etc., depending on the intended use of the silver halide photographic light-sensitive material. be selected accordingly. Next, the developer used in the present invention may be of a commonly used type, for example, hydroquinone,
N.methyl-p-aminophenol, 1-phenyl-3-pyrazolidone, paraphenylene diamines, etc. are used alone or in combination. In addition, the developer contains alkaline agents such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metaborate, alkanolamine, etc., and preservatives include sodium sulfite, potassium sulfite, sodium bisulfite, potassium pyrosulfite, etc. Development fog inhibitors such as formaldehyde and sodium bisulfite adducts include, for example, 5-nitrobenzimidazole, 5-methylbenzotriazole, 6-nitrobenzotriazole,
Azoles such as 1-phenyl-5-captotetrazole can be used as appropriate. A hardening agent may be included in the developer. For example, among aldehydes, dialdihyde compounds such as glutaraldehyde, maleic dialdehyde, and their bisulfites are effectively used. The present invention is particularly effective when processing with a developer containing a glutaraldehyde salt as a high-temperature rapid developer for X-rays. In addition, the developer may contain an antioxidant, a chelating agent, a development accelerator, a pH adjuster, and the like. The development time may be appropriately selected depending on the silver halide photographic material, developer, processing temperature, etc. The development process can be carried out using a rapid automatic device using a hat type or roller transfer type, and a temperature of 50° C. without 17q0 is selected depending on the purpose. Rapid drying as used in the present invention means rapid evaporation of moisture from the constituent layers of the coated silver halide emulsion, etc. Specifically, the air conditions during the lapse rate drying period in the drying process are as follows. It refers to something. That is, the dry bulb temperature is about 28°C to about 45°C (preferably 3000° to 40°C), and the wet bulb temperature is about 2°C to 27°C (preferably 23°C to 25°C) (with the relative humidity not exceeding 50%). ) and has a boundary heat transfer coefficient of 50 and 10 cal/hrqC. Example 1 A highly sensitive silver iodobromide emulsion containing 2.0 mol% of silver iodide was chemically ripened and then halogenated using 4-hydroxy-6-methyl-1.3.$.7-tetrazaindene as a stabilizer. A ratio of 2.0 per mole of silver was added, and predetermined amounts of saponin as a coating aid and formalin as a hardening agent were added, respectively. This emulsion contains 60 gelatin per mole of silver halide.
#Contains. The emulsion thus obtained was divided into 9 parts, each of the compounds according to the present invention was added singly or in fine combination as shown in Table 1 below, and then 9/1 of gelatin 25 was added onto a polyethylene terephthalate film base.
It was applied evenly to give a coating of 0.00. After coating and solidifying, the film is divided into two parts, one of which is used as a normal dry sample, and it takes about 1 hour under the conditions of a dry bulb temperature of 24qo, a green bulb temperature of 18°C, and a film heat transfer coefficient of 1 plate cal'〆hr°C. and dried. The remaining sample was used as a quick drying sample according to the present invention and was rapidly dried in about 5 minutes under the conditions of hrqC with a dry bulb temperature of 30q0, a wet bulb temperature of 24qo, and a film heat transfer coefficient of 7 female cal/. did. The normal dry film and quick dry film thus obtained were each subjected to wedge exposure with white light using a KS-1 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) according to the JIS method, and then the following formulation was applied. 2 with developer [A]
After developing for 4 minutes at ◯, fixing, washing with water, and drying were carried out in the usual manner to obtain a sample. The sensitometric results of these samples are shown in Table 1, and the sensitivities in the table are based on a sample that does not contain any compound according to the present invention, and the film was dried under rapid drying conditions. Shown as relative values. Developer (A) Table 1 As shown in Table 1 above, general formula [1] according to the present invention and

It can be seen that by containing the compounds represented by [0] in combination, the occurrence of fogging can be significantly suppressed even in the case of rapid drying. It is also a feature of the present invention that normal drying does not show any effect. Example 2 A highly sensitive silver iodobromide emulsion for X-rays containing 1.5 mol% of silver iodide was chemically ripened with gold sensitization and a sulfur sensitizer, and then 4-hydroxy-6-methyl-1 was added as a stabilizer.・3・3
・2.7-tetrazaindene per mole of silver halide.
Further, predetermined amounts of saponin as a coating aid and formalin as a hardening agent were added. This emulsion contains 70 gelatin per mole of halogenated radiation.
Contains ta. One portion of the silver halide emulsion thus obtained was divided into 15 parts, uniformly coated on a polyethylene terephthalate film base so that the amount of gelatin was 25 o/100, and then solidified. A comparison sample was prepared by drying for 5 minutes under the same rapid drying conditions as in Example 1. Separately, exemplified compounds included in the general formulas [1) and [B] according to the present invention were added to the remaining portion of the emulsion separated above, either alone or in combination, as shown in Table 1 below. It was quickly dried and used as a sample. All of these samples were subjected to wedge exposure with white light using a KS-1 type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.) according to the JIS method, and then developed and fixed with a developer according to the following development method [B]. The film was processed using a continuous roller conveyance type developing machine that allows washing and drying to be done in one step. Developer formulation [B] (Development time: 3:0, 3: developer sand) Hydroquinone, 10% polyanhydrous sodium sulfite, 70%, boric anhydride
1 night Sodium carbonate (monohydrate)
2091-phenyl-113-pyrazolidone 0.35 Sodium hydroxide
5-5-methylbenzotriazole
0.05 Potassium bromide
5 evening Glutaraldehyde bisulfite 15
Add 8 ounces of glacial acetic acid and make 1 cup.The sensitivities shown in the table are relative sensitivity values, with the sensitivity of a comparative sample that does not contain the compound according to the present invention set as 100. Table 2 Compounds of general formula [1] and general formula according to the present invention from Table 2 above

By combining the compound [0] with silk, fogging will occur significantly even when a silver halide emulsion for X-rays is coated using a rapid drying method and then subjected to high-temperature rapid development processing containing a dialdehyde type hardener. It can be seen that a high-sensitivity silver halide photographic material with a small amount of gamma reduction and no gamma reduction can be obtained. Example 3 In exactly the same manner as in Example 2, the compounds according to the present invention were added singly or in combination as shown in Table 3 below. In addition, for comparison, a blank sample containing nothing and the following compounds which are reported to improve anti-fogging properties and adhesion properties similar to the compound represented by the general formula [1] were also used, as shown in Table 2 below. A comparative sample was prepared by adding the compound in combination with the compound of general formula [B] according to the present invention. Drying was carried out in the same manner as the rapid drying in Example 1. Comparison of Comparative Compounds [Compounds described in BP1239337] Comparison [B-[Compounds described in USP 3042524] The obtained film samples were cut into two pieces each with a size of 35 sides x 7 sides, and then heated at a temperature of 23 oo and a relative humidity of 55%. After being left in the air-conditioned room for 2 hours, these films were brought into contact with each other with the silver halide emulsion surfaces facing each other, and then heated in the air-conditioned room for another 24 hours with a load of about lk9 applied from above. I left it for a while. After standing, the film was peeled off, and the adhesiveness of the film was calculated from the ratio of the total area to the area where the emulsion surface adhered.
On the other hand, the photographic properties of these films were separately determined by using fresh samples, exposing them to white wedge light in the same manner as in Example 2, and then developing them with developer [B]. The results obtained are shown in Table 3 below. However, the sensitivity in the table is shown with a blank sample containing nothing as 100. Third
Table 3 shows that the silver halide photographic material of the present invention not only suppresses the occurrence of fogging even when it is rapidly dried during production, but also exhibits extremely effective interaction even when left and stored at high temperatures. It is clear that the adhesion of ■ and Tsukuda, which are similar to the compound of general formula [1] according to the present invention used as a comparison, do not show any effect when used in combination with the compound of general formula [0], and even though the rapid drying fog suppressing effect is obtained, the adhesion is not improved. It is shown that. Example 4 In the same manner as in Example 2, the compounds according to the present invention were added singly or in bulk as shown in Table 4 below. In addition, for comparison, a blank sample containing nothing and a comparative sample prepared by adding a compound similar to the compound represented by the general formula [B] of the present invention, either singly or in combination with the compound of the general formula [1] according to the present invention. And so. It was dried in the same manner as in Example 1. Comparison Compound Comparison 'c' Molecular weight 100,000 Comparison [d' Molecular weight 100,000 The obtained film samples were examined for inter-film adhesion and photographic properties in the same manner as in Example 3 above. It is a table. Table 4 The above Table 4 shows general formulas similar to the present invention.

When [0] is used in combination with comparative sample 'c or [d], the effect of suppressing rapid drying capri is obtained, but the adhesion is not improved, and the silver halide photographic light-sensitive material of the present invention does not suppress fog for the first time. This shows that improvements in adhesion can also be obtained. Example 5 This example shows that the method of the present invention does not cause fogging or decrease in sensitivity even when subjected to mechanical force due to film bending.
kmmark) test results. A highly sensitive silver iodobromide emulsion containing 3 mol % of silver iodide (this emulsion contains 60 ta of gelatin per mol of silver halide) is added with 4-hydroxy-6 as a stabilizer after chemical ripening.
-Methyl-1,3,$,7-tetrazaindene was added at 2.0# per mole of silver halide, and anhydro-5,6-cyclo-1,3-diethyl-5'-methoxy (3 -sulfopropyl) penzimidazolooxacarbocyanine hydroxide was added as a methanol solution at 9:150/mole of silver halide to prepare an emulsion. This emulsion was divided into 10 parts, 1 part (as is) was used for comparison, and to the remaining 9 parts of the emulsion, compounds according to the present invention were added singly or in bulk as shown in Table 4 below. Also, for comparison purposes, a sample was prepared in which the comparative compound style [B} and [C} were used simultaneously. A coating solution was prepared by adding saponin as a coating agent and a predetermined amount of mucochloric acid as a hardening agent to each emulsion. The resulting coating solution was uniformly coated on a polyethylene terephthalate film base so that the amount of gelatin was 9/100 of 23, and then rapidly dried in 5 minutes by the method of Example 1 to prepare a sample. After drying, all film samples were heated in 35 mL each.
After the film was cut into pieces, the film was bent tightly onto a metal cylinder having a major axis of about 5 cm with the emulsion layer facing outward, and both ends of the film were fixed to prepare a test sample. This sample was placed in an air-conditioned room at a temperature of 23:00 and a relative humidity of 55%.
After being left in the field for a period of time, the curved portion was exposed to white wedge light and its photographic characteristics were investigated. The developer used was [B] in Example 2, and the sensitivity in the table was obtained by subtracting Capri from the blackening density when a constant exposure amount was given.
It is a relative value with the comparative sample as 100. Table 5 As is clear from Table 5 above, the silver halide photographic light-sensitive material of the present invention shows that the knick fog or knick desensitization caused by bending due to mechanical force is also improved. . Example 6 A color red-sensitive silver iodobromide emulsion containing a cyan coloring agent was coated as a first layer on a triacetate film base having an antihalation layer, and an intermediate layer made of gelatin was formed as a second layer on top of this layer. has been established. Next, a color green-sensitive silver iodobromide emulsion containing a magenta coupler was coated as a third layer, and a yellow filter layer was provided thereon as a fourth layer. Next, a color tone-sensitive silver iodobromide emulsion containing a yellow coupler was coated as a fifth layer. Furthermore, a protective layer made of gelatin was provided as a sixth layer to prepare a multilayer color negative film. The respective sensitizing dyes and coloring agents used in the above emulsion are as described below, and are used in a conventional manner. The first, third and fifth layers have general formula [1] according to the present invention and

As shown in Table 6 below, samples were prepared in which the compound represented by [0] was contained in a common amount in each layer, either singly or in combination, and samples in which the compound was not contained in any layer for comparison. When included, it was added immediately before coating the silver halide emulsion forming each layer. After each layer was applied, it was dried under the same conditions as the rapid drying in Example 1. The sensitizing dye and coupler used in this example have the following structure. After exposure, the obtained sample of the red-sensitive sensitizing dye was subjected to the usual color processing of color development, bleaching, fixing, and water washing according to the following recipe. 1 Color developer (370) Sodium metachloride 25 Sodium sulfite 2 Hydroxyl sulfate 2 Potassium bromide
0.5 ta sodium hydroxide
34 Tajethylparaphenylenediamine sulfate 3 Add water and finish overnight 2 Bleach solution (370) Ethylenediaminetetraacetic acid ammonium salt 20 ethylenediaminetetraacetic acid iron (m) ammonium salt
10M ammonium bromide salt
65 Yusui acetic acid
6 [Sodium nitrate
Adjust the pH to 6.0 with 50 t ammonium hydroxide Add water and finish 3 Fixer (370) Ammonium thiosulfate 120 t Sodium sulfite Add 20 t water and finish Finish Processing process Color development (3 minutes 19 sand) → Water washing (3 minutes) → Bleaching (6 minutes) → Water washing (5 minutes) → Fixing (8 minutes) → Water washing (5 minutes) → Drying The results obtained are shown in Table 6. However, the sensitivity values in the table are expressed as relative sensitivity values when the respective sensitivities of cyan, magenta, and yellow of a Planck sample containing no compound of the present invention are taken as 100. Table G The above Table 6 shows that the silver halide photographic material of the present invention is useful as a multilayer color photographic material. Each of the multilayer color films obtained in Example 5 was cut into a size of 6 x 50 cm, and one side of the film was fixed in an air-conditioned room at a temperature of 25 qo and a relative humidity of 30% and 40% for 2 hours. The film was left to stand and the curling state of the film was tested. The results obtained are shown in Table 7, and show that the combined samples according to the present invention provide color light-sensitive materials with extremely little curling under low humidity conditions. The curling values in the table are the radius of curvature of the curl (in units)
It is expressed as the reciprocal of , and the smaller the number, the less curl there is. Table 7

Claims (1)

[Scope of Claims] 1. In a silver halide photographic material having a support and at least one light-sensitive silver halide emulsion layer on the support, at least one of the light-sensitive silver halide emulsion layers contains the following general formula [I] ] A silver halide photographic light-sensitive material characterized by containing a combination of at least one compound represented by the formula [II] below and at least one polymer compound having a molecular weight of 50,000 to 300,000. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, and R_4 each represent the same or different hydrogen atoms or lower alkyl groups, and Z is -(CH) - (where n is 0 or 1
Represents an integer from 5 to 5. ), ▲Mathematical formulas, chemical formulas, tables, etc.▼ (Here, R_5 and R_6 each represent a hydrogen atom, methyl group, ethyl group, or propyl group. However, R_5 and R_6 cannot both be hydrogen atoms.) -CH_2OCH_2-, -CH=CH,
Represents -C≡C- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. ) General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. Represents a cation. m represents the degree of polymerization. ]