JP2791816B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to a silver halide photographic light-sensitive material having a photographic constituent layer hardened with a specific compound.

[Background of the Invention]

Generally, silver halide photographic materials (hereinafter referred to as photosensitive materials) include, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, an undercoat layer, an antihalation layer, an ultraviolet absorbing layer, an antistatic layer, and a backing layer. Various photographic constituent layers such as layers are formed on a support such as glass, paper, or synthetic resin film.

Since these photographic constituent layers are provided with an aqueous coating solution comprising a hydrophilic polymer and / or a water-dispersible polymer, they have low mechanical strength as they are. For example, gelatin films have low melting points and are excessively water-swellable. Further, the latex film has disadvantages such as extremely poor adhesion to the support and easy peeling.

For this reason, it is known that a compound called "hardener" is added to a photographic component layer to improve its mechanical strength. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, U.S. Patent Nos. 2,732,303 and 3,28
No. 8,775, British Patent Nos. 974,723 and 1,167,207, etc., compounds having a reactive halogen, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6- Dichloro-1,3,5-triazine, divinyl sulfone, 5-
Acetyl-1,3-diacryloylhexahydro-1,3,5-
Triazines, compounds having a reactive olefin described in U.S. Pat.Nos. 3,232,763 and 3,635,718, British Patent 994,809, U.S. Pat.Nos. 3,539,644 and 3,642,486
Nos. 49-13563, 53-47271, 56-48860, JP-A-5
3-57257, 61-128240, 62-4275, 63-53
No. 54, 63-264572 and the like, vinylsulfonyl compounds, N-hydroxymethylphthalimide, U.S. Pat.
No. 2,316, N-methylol compound described in 2,586,168, etc., isocyanates described in U.S. Pat.No. 3,103,437, aziridine-based compound described in U.S. Pat.
U.S. Pat.No. 2,725,294, acid derivatives described in U.S. Pat. Organic hardeners such as isoxazole-based compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride And so on.

However, these known hardeners have insufficient curing action, have a long-term change of curing action called "post-hardening" caused by slow curing reaction to gelatin, and adversely affect the performance of photosensitive materials. (Especially increase of fog, decrease of sensitivity or maximum density, softening of gradation, etc.), loss of curing effect by other coexisting photographic additives, or other photographic additives (for example, inner color All of them have some disadvantages, such as those which reduce the effectiveness of the coupler in the emulsion or cause contamination.

Hardening agents having a relatively fast hardening action on gelatin and having a low after-hardening include compounds having a dihydroquinoline skeleton described in JP-A-50-38540 and JP-A-51-59625.
Nos. 62-262854, 62-264044, 63-84741, N-carbamoylpyridinium salts, JP-B-53
A compound having two or more N-acyloxyimino groups in the molecule described in JP-A-22089, a compound having an N-sulfonyloxyimide group described in JP-A-52-93470,
Compounds having a phosphorus-halogen bond described in JP-A-58-113929, JP-A-60-225148, JP-A-61-240236, JP-A-63-4158
The chloroformamidium compound described in No. 0 and the like are known.

These hardeners have the characteristic that they have a fast curing action and therefore have little post-hardening. However, many of these hardeners affect the photographic properties, and the hardening reaction of gelatin is fast and the side reaction decomposed by water is also fast, so that it is effective in a general method for producing a photographic light-sensitive material using an aqueous gelatin solution. In order to obtain a gelatin film having an extremely low use efficiency and a sufficient degree of hardening, a large amount of a hardening agent had to be used.

[Object of the invention]

Accordingly, an object of the present invention is, firstly, to provide a photographic light-sensitive material hardened with a novel hardener which achieves a sufficient degree of hardening without any adverse effect on photographic characteristics.

A second object of the present invention is to provide a photographic light-sensitive material hardened by a hardener having no post-hardening due to a rapid hardening action.

A third object is to provide a photographic material hardened with a hardener which reacts with high selectivity to reactive residues in gelatin and hardens gelatin efficiently.

[Configuration of the invention]

An object of the present invention is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers is a compound represented by the following general formula [I]: At least one of the following.

In the formula, R ₁ and R ₂ may be the same or different from each other, and may be an alkyl group, an aryl group, an aralkyl group, an acyl group, a substituted or unsubstituted carbamoyl group, an O-substituted oxycarbonyl group, a substituted sulfonyl group or Represents a substituted, unsubstituted sulfamoyl group, at least one of R ₁ , R ₂ is an acyl group, a substituted, unsubstituted carbamoyl group, an O-substituted oxycarbonyl group, a substituted sulfonyl group or a substituted, unsubstituted sulfamoyl group Represents These groups may be further substituted, or R ₁ and R ₂ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring.

R ₃ represents a hydrogen atom or a substituent.

A represents a divalent organic group or a single bond, and L represents -O-,-.
Represents NR ₄ — or a single bond. R ₄ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.

 Hereinafter, the present invention will be described more specifically.

In the general formula [I], the alkyl group represented by R ₁ and R ₂ may be a linear alkyl group such as a methyl group, an ethyl group, or a propyl group, or a branched alkyl group such as an i-propyl group or a sec-butyl group. It may be an alkyl group.

The aryl group represented by R ₁ and R ₂ includes a phenyl group and a naphthyl group.

Examples of the aralkyl group include a benzyl group and a phenethyl group.

The acyl group may be a saturated aliphatic group such as an acetyl group, a propionyl group or a butyryl group, an unsaturated aliphatic group such as an acryloyl group, a propioloyl group or a crotonoyl group, or an aromatic group such as a benzoyl group or a toluoyl group. Preferably, it is a saturated aliphatic acyl group having 1 to 4 carbon atoms.

Examples of the substituted carbamoyl group, O-substituted oxylcarbonyl group, substituted sulfonyl group or substituted sulfamoyl group include a methyl group, an ethyl group, an alkyl group such as a propyl group, a phenyl group, an aryl group such as a naphthyl group,
And aralkyl groups such as benzyl group and phenethyl group. Preferably it is a C1-C4 alkyl group.

These groups may be further substituted, as a substituent, methyl group, ethyl group, alkyl group such as propyl group, vinyl group, alkenyl group such as allyl group, phenyl group, aryl group such as naphthyl group, Aralkyl groups such as benzyl group and phenethyl group, halogen atoms such as fluorine atom and chlorine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and naphthoxy group, acetyl group, propionyl group and benzoyl group Acyl group, sulfo group, sulfooxy group, sulfoamino group and the like. When a sulfo group, a sulfooxy group or a sulfoamino group is substituted, a counter salt that cancels the charge is formed. Preferred as the substituent are an alkyl group, an alkoxy group and a sulfo group.

Preferred examples of the heterocycle in the case where R ₁ and R ₂ are bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle are shown below.

Here, R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , and R ₁₂ are a substituted or unsubstituted alkyl group, an aralkyl group, an alkylaryl group, an aryl group or a hydrogen atom, or- COO−, −CON
H -, - OCO -, - NHCO -, - SO 2 -, - SO 2 NH -, - NHSO
_{2 -, - SO 3 -,} - represents a straight-chain comprising at least one linking group selected from branched or cyclic hydrocarbon group - OSO _2.

Examples of the substituent include a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, a carbamoyl group, a sulfamoyl group, a sulfo group, a sulfoamino group, a sulfooxy group, and the like.

R ₃ represents a hydrogen atom or a substituent, examples of the substituent include a methyl group, an ethyl group, an alkyl group such as a propyl group, a vinyl group, an alkenyl group such as an allyl group, a phenyl group, an aryl group such as a naphthyl group, Aralkyl groups such as benzyl group and phenethyl group, halogen atoms such as fluorine atom and chlorine atom, alkoxy groups such as methoxy group and ethoxy group, aryloxy groups such as phenoxy group and naphthoxy group, acetyl group, propionyl group and benzoyl group Acyl group and the like. R ₃ is preferably a hydrogen atom.

A represents a divalent organic group or a single bond, and examples of the divalent organic group include an alkylene group, an arylene group, and -O
-, -NH-, -COO-, -CONH-, -OCO-, -NHCO-,
_{-SO 2 -, - SO 2 NH} -, - NHSO 2 - and linking groups such as divalent organic group formed by combining them. Preferably, it is a single bond and an alkylene group having 1 to 4 carbon atoms.

L is -NR ₄ - if it is, R ₄ is an alkyl group, an aryl group, and an aralkyl group or a hydrogen atom, preferably a hydrogen atom.

Examples of the alkyl group, aryl group and aralkyl group represented by R ₄ include the same groups as those described for R ₁ and R ₂ .

Although the compound represented by the general formula [I] forms an intramolecular counter salt, another compound represented by MX may be added.

M represents a cation, and examples thereof include a hydrogen atom, an alkali metal atom such as lithium, sodium and potassium, an alkaline earth metal atom such as magnesium and calcium, and an ammonium group such as ammonium, triethylammonium and tetramethylammonium. X represents an anion, for example, an anion such as a halogen ion such as chloro, bromo and iodo, a sulfate ion, a p-toluenesulfonic acid ion and a nitrate ion.

Hereinafter, examples of the compound used in the present invention will be described.
The present invention is not limited to this.

The compound of the present invention can be easily synthesized by a known method,
As one method, a compound represented by the following general formula [II] is reacted with phosgene or trichloromethyl chloroformate, N-chloroformylated, and then reacted with a pyridine compound represented by the general formula [III]. By doing so, it can be synthesized with a high yield.

Formula [II] R ₁ —NH—R _{2 In the} formula, R ₁ and R ₂ each have the same meaning as in Formula [I].

In the formula, R ₃ , A, and L each represent the same as those in the general formula [I].

Next, the synthesis method will be described in detail using the exemplified compound (1) as an example.

<Synthesis of Exemplified Compound (1)> Synthesis of N-chloroformyl-N-methylacetamide A solution of 50 g of phosgene in 300 ml of toluene was prepared, and a solution of 29.5 g of N-methylacetamide and 51 g of triethylamine in 200 ml of toluene was added dropwise at room temperature. did. After completion of the dropwise addition, heating was started and the mixture was stirred at 90 ° C. for 1 hour. After cooling, the precipitate was filtered and the filtrate was concentrated under reduced pressure to obtain 60.6 g of crude crystals. This was recrystallized from acetonitrile to obtain 45.5 g of white crystals.

Synthesis of Compound (1) 54.9 g of 4- (2-sulfoethyl) pyridine was suspended in 100 ml of dimethylformamide and 200 ml of methanol. Next, 35.6 g of triethylamine is added to completely dissolve 4- (2-sulfoethyl) pyridine.

At room temperature, a solution of 36.4 g of N-chloroformyl-N-methylacetamide in 200 ml of dimethylformamide was added dropwise to the resulting clear solution. The precipitated crystals were collected by filtration, washed with methanol, and dried to obtain Compound (1). (Yield 6
2.0 g) It was confirmed by NMR and IR that this was Exemplified Compound (1).

Other compounds of the present invention can be synthesized in good yield by the same method.

The amount of the hardener used in practicing the present invention varies depending on the type of the light-sensitive material to be applied and the type of the hydrophilic binder, but is preferably 0.01 to 100% by weight, more preferably 0.1 to 100% by weight of the dry weight of the binder. It is in the range of ~ 30% by weight.

The hydrophilic binder used in the practice of the present invention is arbitrary, such as generally used gelatin, a gelatin derivative, and a graft polymer of gelatin and another polymer.

As the water-dispersible polymer contained in the photographic constituent layer, an aqueous dispersion of a hydrophobic polymer or copolymer obtained from a vinyl compound, or an aqueous dispersion of a condensation polymerization type polymer such as polyester can be used.

When the present invention is carried out, the silver halide emulsion layer of the light-sensitive material or a silver halide used in the other layers, a chemical sensitizer, a silver halide solvent, a spectral sensitizing dye, an antifoggant, a hydrophilic agent such as gelatin, etc. The protective protective colloid, ultraviolet absorber, polymer latex, brightener, color coupler, anti-fading agent, dye, matting agent, surfactant and the like are not particularly limited. For example, Research Disclosure, Vol. 176, 22 ~ 31 pages (12 December 1978
) Can be used.

Further, for the support of the light-sensitive material, the developing method, the constituent layers of the light-sensitive material, etc., the description in the above-mentioned Research Disclosure Magazine can be referred to.

〔Example〕

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto.

In Example 1 the following examples, the amount of silver halide photographic light-sensitive material is particularly shows the g per 1 m ² unless otherwise noted. Further, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye was represented by the number of moles per mole of silver.

Each layer having the following composition was formed on the triacetyl cellulose film support in this order from the support side to form a multilayer color photographic light-sensitive material. First layer: Antihalation layer (HC) Black colloidal silver 0.15 Ultraviolet absorption Agent (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling solvent (Oil-1) 0.20 High boiling solvent (Oil-2) 0.20 Gelatin 1.6 Second layer: Intermediate layer (IL-1) Gelatin 1.3 3 layers: low-sensitivity red-sensitive emulsion layer (RL) silver iodobromide emulsion (Em-1) 0.4 silver iodobromide emulsion (Em-2) 0.3 sensitizing dye (S-1) 3.2 × 10 ^-4 sensitizing dye (S-2) 3.2 × 10 ^-4 sensitizing dye (S-3) 0.2 × 10 ^-4 cyan coupler (C-1) 0.50 cyan coupler (C-2) 0.13 colored cyan coupler (CC-1) 0.07 DIRization Plate (D-1) 0.006 DIRized plate (D-2) 0.01 High boiling point solvent (Oil-1) 0.55 Additive (SC-1) 0.003 Gelatin 1.0 Fourth layer: High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-1) 1.7 × 10 ^-4 Sensitizing dye (S-2) 1.6 × 10 ^-4 sensitizing dye (S-3) 0.1 x 10 ^-4 cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIRized substrate (D-2) 0.02 High boiling solvent (Oil-1) 0.25 Additive (SC-1) 0.003 Gelatin 1.0 Fifth layer: Intermediate layer (IL-2) Gelatin 0.8 Sixth layer: Low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6 Iodine Silver bromide emulsion (Em-2) 0.2 sensitizing dye (S-4) 6.7 × 10 ^-4 sensitizing dye (S-5) 0.8 × 10 ^-4 magenta coupler (M-1) 0.17 magenta coupler (M-2) 0.43 Colored Magenta Coupler (CM-1) 0.10 DIRized Base (D-3) 0.02 High Boiling Solvent (Oil-2) 0.70 Additive (SC-1) 0.003 Gelatin 1.0 7th Layer: High Sensitive Edge Sensitive Emulsion Layer (GH) Halide emulsion (Em-3) 0.9 Sensitizing dye (S-6) 1.1 × 10 -4 Sensitizing dye (S-7) 2.0 × 10 -4 Sensitizing dye (S-8) 0.3 × 10 -4 Magenta coupler (M-1) 0.03 Magenta coupler (M-2) 0.13 Colored magenta coupler (CM-1) 0.04 DIR compound (D-3) 0.004 High boiling solvent (Oil-2) 0.35 Additive (SC-1) 0.003 Gelatin 1.0 Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-2) 0.12 High boiling solvent (Oil-2) 0.15 Gelatin 1.0 9 layers: low-sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion (Em-1) 0.25 silver iodobromide emulsion (Em-2) 2.25 sensitizing dye (S-9) 5.8 × 10 ^-4 yellow coupler ( Y-1) 0.60 Yellow coupler (Y-2) 0.32 DIR compound (D-1) 0.003 DIR compound (D-2) 0.006 High boiling solvent (Oil-2) 0.18 Additive (SC- ) 0.004 Gelatin 1.3 10th layer: high sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.5 Sensitizing dye (S-10) 3.0 × 10 -4 Sensitizing dye (S-11) 1.2 × 10 ^-4 Yellow coupler (Y-1) 0.18 Yellow coupler (Y-2) 0.10 High boiling solvent (Oil-2) 0.05 Additive (SC-1) 0.002 Gelatin 1.0 11th layer: 1st protective layer (PRO- 1) Silver iodobromide emulsion (Em-5) 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) 0.1 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 0.8 12th layer: 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethyl methacrylate (average particle size) 0.02 Sliding agent (WAX-1) 0.04 Charge control agent (SU-1) 0.004 Charge control agent (SU-2) 0.02 Gelatin 0.5 Sample Nos. 1 to 8 were prepared by adding the hardener of the present invention or a comparative hardener as shown in FIG.

Each layer has a coating aid (SU-4) and a dispersion aid (SU-
3), stabilizer (ST-1), preservative (DI-1), antifoggant (AF-1), (AF-2), dye (AI-1), (AI-
2) was added as appropriate.

The emulsions used in the above samples are as follows.
Each is an internal high iodine type monodisperse emulsion.

Em-1: Average silver iodide content 7.5 mol% Average grain size 0.55 μm Grain shape Octahedron Em-2: Average silver iodide content 2.5 mol% Average grain size 0.36 μm Grain shape Octahedron Em-3: Average iodine Silver halide content 8.0 mol% Average grain size 0.84 μm Grain shape Octahedral Em-4: Average silver iodide content 8.5 mol% Average grain size 1.02 μm Grain shape Octahedral Em-5: Average silver iodide content 2.0 mol % Average particle size 0.08μm Each of the prepared samples was used as a fresh sample, and a sample in which the sample was allowed to stand at room temperature for 7 days and a sample in which the sample was forcibly deteriorated by allowing it to stand at 50 ° C. and 50% RH for 2 days were prepared.

After exposing these samples to wedges with white light, the following treatments were performed, and the sensitivity and fog were measured.

Sensitivity is represented by the reciprocal of the exposure amount that gives a density of fog +0.5.
The relative sensitivity was set to 0.

The sample left at room temperature for 7 days was immersed in water at 30 ° C. for 5 minutes, a sapphire needle having a radius of 0.3 mm was pressed against the sample surface, and moved parallel to the film surface at a speed of 2 mm per second. While the pressure contact load of the sapphire needle was continuously changed in the range of 0 to 200 g, the load when the film surface of the sample was damaged was determined as the scratch resistance.

 The results are shown in Table 1 below.

(Processing process) Color development 38 ° C 3 minutes 15 seconds Bleaching 38 ° C 6 minutes 30 seconds Rinse 38 ° C 3 minutes 15 seconds Fixed 38 ° C 6 minutes 30 seconds Rinse 38 ° C 3 minutes 15 seconds Stabilize 25 ° C 1 minute 30 seconds drying 45 ° C The composition of the processing solution used in each processing step is as follows.

(Color developing solution) 4-amino-3-methyl-N-ethyl-N-β-hydroxyethylaniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g odor Sodium chloride 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1.

(Bleaching solution) Ammonium salt of iron (III) ethylenediaminetetraacetate 100.0 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to 1 and adjust the pH to 6.0 using aqueous ammonia.
Adjust to

(Fixing solution) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Add water to 1 and adjust the pH to 6.0 using acetic acid.

(Stabilizing solution) Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konia) 7.5 ml Add water to make 1.

As is clear from the results of Table 1 above, Sample Nos. 1 to 5 using the hardener according to the present invention were all Comparative Samples N
There is only a slight decrease in relative sensitivity as compared with o.6 to 8, and no fog deterioration is observed.

In addition, even if it is forcibly deteriorated, the comparative sample No. 6 ~
Compared with Sample No. 8, Samples Nos. 1 to 5 of the present invention show a slight decrease in sensitivity and a slight increase in fog.

Accordingly, it can be seen that the hardener according to the present invention hardly inhibits the photographic properties.

In addition, from the results of the scratch resistance indicating the film strength, the sample of the present invention N
o.1 to 5 all show higher film strength compared to Comparative Samples Nos. 6 to 7, indicating that the hardener of the present invention hardens more efficiently than the comparative compound. I understand.

Example 2 Layers having the following composition were sequentially formed on both sides of a polyethylene terephthalate support having been subjected to undercoating from the support side to obtain photosensitive material samples for X-ray Nos. 9 to 14.

Additives other than silver halide were shown per mole of silver halide unless otherwise specified.

First layer: Crossover cut layer Dye (I) 3.0 mg / m ² Mordant (II) 0.12 g / m ² Gelatin 0.2 g / m ² For each sample, after a storage test in the same manner as in Example 1, exposure was performed and the following treatment was performed, and photographic characteristics were measured in the same manner as in Example 2.

The sensitivity was shown as a relative sensitivity when the sensitivity of Sample No. 9 on the 7th day after application was set to 100.

 Table 2 shows the results.

(Processing process) Insertion 1.2 seconds Developing + migrating 35 ° C 14.6 seconds Fixing + migrating 33 ° C 8.2 seconds Rinse + migrating 25 ° C 7.2 seconds Squeeze 40 ° C 5.7 seconds Drying 45 ° C 8.1 seconds (Developer) Hydroquinone 25.0 g Phenidone 1.2 g Potassium sulfite 55.0 g Boric acid 10.0 g Sodium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Nitroimidazole 0.1 g 5-Nitrobenzimidazole 0.1 g Glutaraldehyde bisulfite 15.0 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylenetetramine 6 Acetic acid 2.5g Add water to finish.

(Fixing solution) Ammonium thiosulfate 130.9 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Sodium acetate (trihydrate) 25.8 g Aluminum sulfate (18 hydrate) 14.6 g Sulfuric acid (50 wt%) 6.77 g Water In addition, finish to 1.

Also, keep the sample at 25 ° C and 50% RH before application.
Time, 1 day, 7 days later, remove part of each sample, 30 ℃
Was swelled in water for 5 minutes, the thickness of each sample was measured, the degree of swelling V represented by the following equation was calculated, and the change over time (post-hardening property) of the curing action was observed.

 The results are shown in Table 2 below.

As is evident from the results in Table 2, in the photosensitive material samples for X-rays Nos. 9 to 11 in which the hardener of the present invention was added to the protective layer, fluctuations in photographic characteristics such as a decrease in sensitivity and an increase in fog were almost nonexistent. No change was observed, and the change in the degree of swelling was small and stable one day or more after application and drying, and the post-hardening property was remarkably improved as compared with Comparative Sample Nos. 13 and 14. In addition, it can be seen from the comparison with Sample 12 that the hardened film is efficiently formed.

〔The invention's effect〕

As described above, according to the present invention, there is provided a silver halide photographic light-sensitive material containing a novel hardening agent which efficiently performs a hardening action even with a small amount of a hardening agent and has no post-hardening action without impairing photographic performance. can do.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/30

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula [I]:
A silver halide photographic light-sensitive material, which is hardened with at least one compound represented by the formula: (In the formula, R ₁ and R ₂ may be the same or different from each other, and may be an alkyl group, an aryl group, an aralkyl group, an acyl group, a substituted or unsubstituted carbamoyl group, an O-substituted oxycarbonyl group, or a substituted sulfonyl group. Or represents a substituted or unsubstituted sulfamoyl group, and at least one of R ₁ and R ₂ is an acyl group, a substituted or unsubstituted carbamoyl group, an O-substituted oxycarbonyl group, a substituted sulfonyl group or a substituted or unsubstituted sulfamoyl group. Represents a group. These groups may be further substituted, or R ₁ and R ₂ may combine with each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring. R ₃ represents a hydrogen atom or a substituent. A represents a divalent organic group or a single bond, and L represents -O-, -NR
₄ - or represents a single bond. R ₄ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. ]