JP2676536B2 - 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, a silver halide photographic light-sensitive material (hereinafter, referred to as a light-sensitive material) includes, for example, a silver halide emulsion layer, an intermediate layer, a protective layer, a filter layer, an undercoat layer, an antihalation layer, and an ultraviolet absorbing layer. And various photographic constituent layers such as an antistatic layer and a backing layer on a support such as glass, paper or synthetic resin film.

Since these photographic constituent layers are provided with an aqueous coating liquid 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. Also,
Latex membranes have disadvantages such as extremely poor adhesion to the support and easy peeling.

Therefore, 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
8,775, British Patents 974,723, 1,167,207 and the like, compounds having a reactive halogen, diacetyl, ketone compounds such as cyclopentadione, bis (2
-Chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3,5-triazine, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat.
32,763, 3,635,718, compounds having reactive olefins described in British Patent No. 994,809, N-hydroxymethylphthalimide, US Patents 2,732,316, 2,586,1
N-methylol compounds described in 68, US Pat.
Isocyanates described in 437 etc., U.S. Patent 2,983,611
No. 3,107,280, etc., aziridine compounds, U.S. Pat.Nos. 2,725,294, 2,725,295, etc., acid derivatives, carbodiimide compounds, U.S. Pat. Compounds, U.S. Pat.Nos. 3,321,313, isoxazole compounds described in 3,543,292 etc., halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxa,
Organic hardeners such as dioxane derivatives such as dichlorodioxane and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride.

However, these known hardeners have insufficient curing action when used in a light-sensitive material, and have a long-term change in the curing action called "post-hardening" which occurs because the curing reaction to gelatin is slow. Those that adversely affect the performance of the light-sensitive material (especially, increase in fog, decrease in sensitivity or maximum density, softening of gradation, etc.), the coexistence of other photographic additives causes the curing effect to be lost, or other photographs That reduce the effectiveness of additives for use (eg, couplers in internal color emulsions) or cause contamination, hardeners that are difficult to synthesize and difficult to mass-produce, and hardeners themselves are unstable and storable In many cases, there are some defects, such as poor film quality, insufficient adhesion to the support, and film peeling.

In recent years, rapid processing of light-sensitive materials has been demanded, thinning of photographic constituent layers and automatic processing machines for quick penetration of processing solutions,
A high-temperature short-time treatment is achieved by a combination of powerful treatment liquids. Therefore, there has been a demand for the development of a hardener which does not impair the photographic properties and gives sufficient film strength and adhesiveness with a support.

As such a gelatin hardener, for example, US Pat.
642,486, Japanese Patent Publication Nos. 49-13563, 50-35807, JP-A-53-66960, 53-41221, and 53-57257. It is described in these specifications that when a compound having a plurality of vinylsulfonyl groups in the same molecule is used as a gelatin hardener, a hardening action occurs rapidly.

However, when these compounds are used as gelatin hardeners, none of them have sufficient solubility in water and they are liable to cause inhomogeneous hardening in the photographic emulsion layer. In addition, a special organic solvent is often required when added to the photographic emulsion or photographic emulsion layer, and coating unevenness is likely to occur due to this organic solvent, and caution such as explosion proof is required. There was such a problem.

As a means for solving this problem, JP-A-61-128240 proposes vinyl sulfonyl compounds having a sulfonic acid group in the molecule, but since these compounds have properties as an anionic surfactant, Addition to the coating solution causes thickening, and it is difficult to add a large amount.

[Object of the Invention] Accordingly, an object of the present invention is to provide a halogen using a gelatin hardener which has a rapid hardening action, high water solubility, and does not cause thickening when added to a coating solution. It is to provide a silver halide photographic light-sensitive material.

[Structure of the Invention] The above object is to provide a silver halide photographic light-sensitive material characterized in that at least one of the photographic constituent layers formed on a support is cured with a compound represented by the general formula [I]. Achieved by the material.

In the general formula _{[I] (CH 2 = CH} -SO 2 n A ( wherein, A is a straight-chain alkyl group with a terminal hydroxyl group of valence n which at least one useful as substituent attached directly to the carbon atom Organic group, n is 2, 3 or 4
Represents Next, specific examples of the compound represented by the general formula [I] will be illustrated, but the present invention is not limited thereto.

Illustrative compounds Although the compounds of the present invention are all novel compounds, they can be synthesized in good yield by known general reactions.

The synthetic method of the compound represented by the general formula [I] is described below.
It will be specifically described with the exemplified compound (1) as an example.

-Synthesis of Exemplified Compound (1) -1) Synthesis of 2,3-bis (β-hydroxyethylsulfonyl) propanol 70% of 2-mercaptoethanol sodium salt (13.9 g) was added to 70 ml of methanol, and the mixture was stirred at 20 ° C or lower to give 2 Add 9.0 g of 3,3-dichloropropanol and reflux for 5 hours. The inorganic salt is filtered and then concentrated to obtain a waxy solid. This is dissolved in 40 ml of water, 1 g of sodium tungstate is added, 0 ml of 35% hydrogen peroxide 2 water is added dropwise with stirring, and the reaction is further carried out at 80 ° C. for 3 hours. The reaction liquid is concentrated and then cooled to precipitate crystals. The crude crystals were recrystallized from methanol-water to obtain 11.8 g of crystals.

2) Synthesis of 2,3-bis (β-chloroethylsulfonyl) propanol 40 ml of dimethylformamide (DMF) was added with 2,3-bis (β
-Hydroxyethyl sulfonyl) propanol 11.8 g is dissolved, thionyl chloride 9.0 ml is dripped in this, and it recirculate | refluxes at 80 degreeC for 1 hour. After distilling off excess thionyl chloride, concentration,
Crystals precipitate on cooling. After washing with acetone and drying, 7.8 g of white crystals were obtained.

3) Synthesis of 2,3-bis (vinylsulfonyl) propanol Dissolve 7.8 g of 2,3-bis (β-chloroethylsulfonyl) -propanol in 50 ml of DMF and add 5.6 ml of triethylamine with stirring at room temperature. After standing overnight, salt is filtered and concentrated under reduced pressure to obtain 4.8 g of white crystal.

This was confirmed to be Exemplified Compound (1) by NMR, IR and elemental analysis.

Elemental analysis results H C actual measurement 4.99 35.01 calculation 5.03 35.00 Compounds other than the above can also be easily synthesized by the above method or a method similar thereto.

The amount of the hardener used in carrying out the present invention varies depending on the type of the photosensitive material applied and the type of the hydrophilic binder, but is preferably 0.01 to 100 wt% of the dry weight of the binder, more preferably 0.1. In the range of up to 10% by weight.

The hydrophilic binder used in carrying out the present invention may be any of commonly used gelatin, gelatin derivatives, and graft polymers of gelatin and other polymers.

Further, 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.

Hydrophilicity such as silver halide, chemical sensitizer, silver halide solvent, spectral sensitizing dye, antifoggant, gelatin and the like used in the silver halide emulsion layer or other layers of the light-sensitive material in carrying out the present invention. The protective colloid, ultraviolet absorber, polymer latex, whitening agent, color coupler, anti-fading agent, dye, matting agent, surfactant and the like are not particularly limited. For example, Research Disclosure, Vol. December 1978), 22
The materials described on page 31 can be used.

Further, the description in the above-mentioned Research Disclosure Magazine can be referred to for the support of the photosensitive material, the development processing method, the constituent layers of the photosensitive material, and the like.

[Examples] The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Reference Example Exemplified Compound (1) according to the present invention, Exemplified Compound (11), and Comparative Compound (I) disclosed in JP-A No. 53-41221 as a comparison and U.S. Pat. No. 3,642,486 are disclosed. The comparative compound (II) and the comparative compound (III) disclosed in JP-A No. 61-128240 are each added in an amount of 10 g per 100 m.
It was added to 1 l of water and then stirred at 25 ° C. for 5 hours. The insoluble matter was collected by filtration, dried, and then its weight was determined. In 100 ml of 6% gelatin aqueous solution at 30 ℃,
The presence or absence of thickening was investigated when 2 g of each was added.

Comparative Compound _{(I) CH 2 = CHSO 2} CH 2 CONHCH 2 CH 2 NHCOCH 2 SO 2 CH = CH 2 (II) CH 2 = CHSO 2 CH 2 OCH 2 SO 2 CH = CH 2 Compounds recovered in Table-1 and calculated from them 25
The amount soluble in 100 ml of water at ℃ and the viscosity increase of gelatin aqueous solution are shown.

As is clear from Table-1, the compounds (1) and (11) of the present invention both have significantly improved solubility as compared with known comparative compounds, and also cause thickening when added to an aqueous gelatin solution. There is no such thing.

In Example 1 the following examples, showing what per 1 m ² unless the added amount is specifically described in the silver halide photographic light-sensitive material.
Further, silver halide and colloidal silver are shown in terms of silver.

On the triacetyl cellulose film support, layers having the following compositions were sequentially formed from the support side to prepare multilayer color photographic light-sensitive material samples Nos. 1 to 8.

First layer: Antihalation layer (HC) Gelatin layer containing black colloidal silver.

Gelatin 2.2 g / m ² Second layer; Intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.2 g / m ² 3rd layer; low-sensitivity red-sensitive silver halide emulsion layer (RL) Monodisperse emulsion consisting of AgBrI containing average grain size () 0.30 μm, AgI 6 mol% (Emulsion I) Silver coating amount 1.8 g / m ² Sensitizing dye I 6 × 10 ^-5 mol per mol of silver Sensitizing dye II 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1) 0.06 mol per mol of silver Colored cyan coupler (CC-1) 0.003 mol per mol of silver DIR compound (D-1) 0.0015 mol per mol of silver DIR compound (D-2) 0.002 mol per mol of silver gelatin 1.4 g / m ² 4th layer: High-sensitivity red-sensitive silver halide emulsion layer (RH) Monodisperse emulsion consisting of AgBrI containing 0.5 μm average grain size () and 7.0 mol% AgI (emulsion II) Silver coating amount 1.3 g / m ² Sensitizing dye I 3 × 10 ⁻⁵ mol per mol of silver Sensitizing dye II 1.0 × 10 ⁻⁵ mol per mol of silver Cyan coupler (C-1) 0 per mol of silver .02 mol Colored cyan coupler (CC-1) 0.0015 mol per mol of silver DIR compound (D-2) 0.001 mol per mol of silver Gelatin 1.0 g / m ² Fifth layer; Intermediate layer (IL) The same gelatin layer as the two layers.

Gelatin 1.0g / m ² 6th layer; low-sensitivity green-sensitive silver halide emulsion layer (GL) Emulsion I Silver coating amount 1.5g / m ² Sensitizing dye III 2.5 × 10 ^-5 mol sensitized to 1 mol silver Dye IV: 1.2 × 10 ^-5 mol per mol of silver Magenta coupler (M-1) 0.05 mol per mol of silver Colored magenta coupler (CM-1) 0.009 mol per mol of silver DIR compound (D- 1) 0.0010 mol per mol of silver DIR compound (D-3) 0.0030 mol per mol of silver Gelatin 2.0 g / m ² 7th layer; high-sensitivity green-sensitive silver halide emulsion layer (GH) emulsion II silver Coating amount 1.4 g / m ² Sensitizing dye III 1.5 × 10 ^-5 mol to 1 mol silver Ag Sensitizing dye IV 1.0 × 10 ^-5 mol to 1 mol silver Magenta coupler (M-1) To 1 mol silver On the other hand 0.020 mol Colored magenta coupler (CM-1) 0.002 mol per mol silver DIR compound (D-3) 0.0010 mol per mol silver Zera Chin 1.8 g / m ² Eighth layer; Yellow filter layer (YC) A gelatin layer containing yellow colloidal silver and an emulsion dispersion of 2,5-di-t-octylhydroquinone.

Gelatin 1.5g / m ² 9th layer; low-sensitivity blue-sensitive silver halide emulsion layer (BL) Monodisperse emulsion consisting of AgBrI with average grain size () 0.48μm, AgI 6mol% (Emulsion III) Silver coating amount 0.9g / m ² Sensitizing dye V 1.3 × 10 ⁻⁵ mol per 1 mol of silver Yellow coupler (Y-1) 0.29 mol per 1 mol of silver Gelatin 1.9 g / m ² 10th layer; high-sensitivity blue-sensitive halogenation Silver emulsion layer (BH) Monodispersed emulsion consisting of AgBrI containing average grain size () 0.8 μm and AgI 15 mol% (Emulsion IV) Silver coating amount 0.5 g / m ² Sensitizing dye V 1.0 × 10 to 1 mol silver ^-5 mol Yellow coupler (Y-1) 0.08 mol per mol of silver DIR compound (D-2) 0.0015 mol per mol of silver Gelatin 1.6 g / m ² 11th layer; 1st protective layer (Pro- 1) Silver iodobromide [AgI 1 mol%, average particle size () 0.07 μm] Silver coating amount 0.5 g / m ² A gelatin layer containing ultraviolet absorbers (UV-1) and (UV-2).

Gelatin 1.2g / m ² 12th layer; 2nd protective layer (Pro-2) Polymethylmethacrylate particles (average particle size 1.5μm) 50mg / m ² Polydimethylsilicone 5mg / m ² Ethylmethacrylate methylmethacrylate-methacrylic acid co- Polymer particles (average particle size 2.5 μm) 50 mg / m ² And a gelatin layer containing formalin scavenger (HS-1).

Gelatin 1.2 g / m ^{2 In} addition to the above, each layer contains the hardener of the present invention or a comparative hardener, and surfactants (1), (2), (3 ) And (4) were added respectively.

The compounds contained in each layer of the sample are as follows.

Sensitizing dye I; anhydro-5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; anhydro-9-ethyl-3,3 '-Di- (3
-Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide sensitizing dye III; anhydro-5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl Propyl) oxacarbocyanine hydroxide Sensitizing dye IV; anhydro-9-ethyl-3,3'-di- (3
-Sulfopropyl) -5,6,5 ', 6'-dibenzoxacarbocyanine hydroxide sensitizing dye V; anhydro-3,3'-di- (3-sulfopropyl) -4,5-benzo-5' -Methoxythiocyanine hydroxide Surfactant Each of the prepared samples was used as a fresh sample, and a sample left at room temperature for 7 days and a sample forcibly deteriorated by leaving it 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.

The sensitivity was represented by the reciprocal of the exposure amount that gives a density of fog + 0.5, and was shown as a relative sensitivity with the sensitivity of the sample (1) 7 days after coating as 100.

The sample kept at room temperature for 7 days was immersed in water at 30 ° C for 5 minutes, a sapphire needle with a radius of 0.3 mm was pressed against the sample surface, and the sample was moved in parallel on 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 also shown in Table 2 below.

Processing 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-hydroxyethyl) aniline sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1

(Bleaching solution) Iron ammonium salt of ethylenediaminetetraacetate 100 g Diammonium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Add water to make 1 and adjust to pH = 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 KONIDAX (manufactured by Konica Corporation) 7.5 ml Add water to make 1.

As is clear from the results in Table 2 above, Sample Nos. 1 to 6 using the hardener according to the present invention are all comparative samples N
There is only a slight decrease in relative sensitivity as compared with o.7 to 8, and no deterioration of fog is observed.

Even if it is forcibly deteriorated, comparative sample No. 7 ~
Compared with No. 8, the samples No. 1 to 6 of the present invention showed 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.

Further, as is clear from the results of the scratch resistance indicating the film strength, it is found that the sample of the present invention is good.

Example 2 X-ray photosensitive material samples Nos. 9 to 13 were obtained by sequentially forming layers having the compositions shown below on both sides of an undercoated polyethylene terephthalate support from the support side.

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

First layer: Crossover layer Dye (I) 3 mg / m ² Gelatin 0.2 g / m ² Second layer: Emulsion layer Emulsion composed of AgBrI containing average grain size 1.2 μm and AgI 1.5 mol% Silver coating amount 4 g / m ² Sensitizing dye (A) 450 mg Sensitizing dye (B) 20 mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.2 g Diethylene glycol 11.0 g p-Nitrophenyltriphenylphosphonium chloride 0.2 g Gelatin 2.0 g / m ² Polyethyl acrylate latex 1.0 g / m ² Third layer: protective layer Diethylhexyl succinate sodium sulfonate 0.015 g / m ² Polymethylmethacrylate (average particle size 3 to 4 μm) 50 mg / m ² Polyoxy Sodium ethylene-di-nonylphenyl ether sulfate 50 mg / m ² Polyoxyethylene nonylphenyl ether 5 mg / m ² Gelatin 1.0 g / m ² Polyethyl acrylate latex 0.5 g / m ² CaF ₁₇ SO ₃ K 3 mg / m ² Hardener (Table- (Described in 3) Each sample was subjected to a storage test in the same manner as in Example 1, exposed to light and subjected to the following processing, and the same photographic characteristics and film strength as in Example 1 were measured.

The sensitivity was shown as a relative sensitivity with the sensitivity of the sample (9) 7 days after application as 100.

 The results are shown in Table-3.

(Processing process) Image 30 ° C 45 seconds Settling 25 ° C 35 seconds Water wash 15 ° C 35 seconds Dry 45 ° C 20 seconds (Developer) Phenidone 0.4g Metol 5g Hydroquinone 1g Anhydrous sodium sulfite 60g Sodium carbonate (monohydrate) 54g 5-Nitroimidazole 100mg Potassium bromide 2.5g Add water to make pH 1 and adjust to pH 10.20.

(Fixing solution) (Part A) Ammonium thiosulfate 170 g Sodium sulfite 15 g Boric acid 6.5 g Glacial acetic acid 12 ml Sodium citrate (dihydrate) 2.5 g Add water to make 275 ml.

(Part B) Aluminum sulfate 15g 98% sulfuric acid 2.5g Add water to make 40ml.

When using, add water to Part A: 275 ml and Part B: 40 ml to make 1

Also, while keeping the sample at 25 ° C. and 50% RH, 2 hours, 1 day and 7 days after application, a part of each sample was taken out.
Swell in water at 30 ℃ for 5 hours, measure the film thickness of each sample,
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 3 below.

Comparative compound (V) HCHO As is clear from the results shown in Table 3, in the X-ray photosensitive material samples Nos. 9 to 11 in which the hardener of the present invention was added to the protective layer, there were almost no fluctuations in photographic characteristics such as decrease in sensitivity and increase in fog. Further, after 1 day or more after application and drying, the change in swelling degree was small and stable, and the post-hardening property was remarkably improved as compared with Comparative Sample Nos. 12 to 13.

Example 3 Layers having the compositions shown below were sequentially formed on both sides of a polyethylene terephthalate support which had been subjected to subbing, from the support side to obtain photosensitive material samples Nos. 14 to 18 for plate making.

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

First layer: Emulsion layer Emulsion composed of AgBrCl containing 0.2 μm of average particle size and 24 mol% of AgBr Coating amount 4.0 g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.6 g Polyoxyethylene nonylphenyl ether 50 mg / m ² Styrene-butyl acrylate copolymer latex 1.5 mg / m ² Gelatin 5.5 g / m ² Second layer: protective layer Gelatin 1.0 g / m ² Styrene-butyl acrylate copolymer latex 0.8 g / m ² polymethylmethacrylate (average particle diameter 3 to 4 μm) 50 mg / m ² hardener (listed in Table 4) Each sample was stored in the same manner as in each of the above Examples, then exposed to wedges, and subjected to the following treatments. Then, the post-hardening property and the film strength were measured.

 Table 4 shows the results.

(Processing process) Current image 29 ℃ 30 seconds Settlement 28 ℃ 20 seconds Water wash 20 ℃ 20 seconds Dry 45 ℃ 30 seconds [Developer (stock solution)] Potassium bromide 2.5g Ethylenediaminetetraacetic acid disodium 1g Potassium sulfite (55 % Aqueous solution) 90 ml potassium carbonate 25 g hydroquinone 10 g 5-methylbenzotriazole 100 mg 5-nitrobenzotriazole 100 mg 1-phenyl-5-mercaptotetrazole 30 mg 5-nitroimidazole 50 mg 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 0.5 g Diethylene glycol 60 g Add water to bring the total volume to 500 ml, and adjust the pH to 1 using sodium hydroxide.
Adjust to 0.6.

At the time of use, the above-mentioned stock solution is diluted with water to a double volume before use.

(Fixer) (Part A) Ammonium thiosulfate 170g Sodium sulfite 15g Boric acid 6.5g Glacial acetic acid 12ml Sodium citrate (dihydrate) 2.5g Add water to make 275ml.

(Part B) Amminium sulfate (18-hydrate) 15 g 98% sulfuric acid 2.5 g Add water to make 40 ml.

About 600 ml of water was added to 275 ml of Part A above, 40 ml of Part B was added, and water was further added to 1000 ml to adjust the working solution.

As is clear from the results of Table 4 above, Sample Nos. 14 to 16 according to the present invention have a post-hardening property as compared with Comparative Samples No. 17 to 18,
Both the film strength and the film strength are improved as in the above examples.

Example 4 A 175 μm-thick polyethylene terephthalate film biaxially stretched and heat-treated was subjected to a corona discharge treatment of 30 W / m ² min, and 10 ml of the resin below cited and 2 of a surfactant having the following structure were used.
% Aqueous solution (1 ml) and a hardener (shown in Table 5) for coating a layer having a thickness of 20 μm, and dried at 100 ° C. for 1 minute.

Next, 1 g of gelatin and 0.2 ml of a 10% saponin aqueous solution were adjusted to 100 ml with pure water to apply an upper layer coating solution to a film thickness of 20 μm, and dried at 100 ° C. for 1 minute.

The undercoated polyester film obtained by the above operation was sequentially coated with each layer having the composition shown below from the support side to prepare X-ray photosensitive material samples Nos. 19 to 27.

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

First layer: Crossover layer Compound (I) 10 mg / m ² Dye (II) 3 mg / m ² Gelatin 0.2 g / m ² Second layer: Emulsion layer Average grain size 1.2 μm, AgI 1.5 mol% included Emulsion composed of AgBrI Coating amount of silver 4g / m ² 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1.2g Diethylglycol 11.0g p-Nitrophenyltriphenylphosphonium chloride 0.2g Gelatin 2.0g / m ² polyethyl acrylate latex 1.0 g / m ² 3rd layer: protective layer sodium diethylhexyl succinate sulfonate 0.015 g / m ² polymethylmethacrylate (average particle size 3 to 4 μm) 50 mg / m ² polyoxyethylene-di -Sodium nonylphenyl ether sulfate 50 mg / m ² Gelatin 1.0 g / m ² Polyethyl acrylate latex 0.5 g / m ² CaF ₁₇ SO ₃ K 3 mg / m ² Hardener (listed in Table-5) Dye (II) The following adhesive strength test was performed on each of the prepared samples.

 The results are shown in Table-5.

Adhesion test Sample with dry film Make a shallow scratch on the emulsion surface of the sample with a razor,
After the cellophane adhesive tape was pressure-bonded thereon, and when the tape was rapidly peeled off, the residual ratio of the emulsion film to the adhesive area of the cellophane tape is shown in percentage.

Sample with treatment film In the treatment bath, the emulsion surface of the sample was scratched in the shape of a checkerboard with sharp conical tips, and the surface was rubbed, and the residual rate of the emulsion film was shown as a percentage.

 In practice, if this percentage is 80% or more, there is no problem.

The following were used as the comparative hardener and the resin cited below in Table 5 above.

Comparative compound (VII) Comparative compound (VIII) Comparative compound (IX) (Compounds described in JP-A-53-57257) Resin cited below: Copolymerized latex having a dry solid content of 30% by weight obtained by polymerizing monomers having the following composition From Table-5 above, Sample No. 19 using the hardener of the present invention
It can be seen that in Nos. 24 to 24, the adhesive force between the support and the emulsion layer is significantly improved as compared with Comparative Sample Nos. 25 to 27 using the comparative hardener. In particular, when the hardener of the present invention is used for the undercoat layer, the adhesive strength is improved as is clear from Sample Nos. 19-23.

Further, as is clear from Sample No. 24, the adhesive strength is improved if the hardener of the present invention is used in the protective / emulsion layer without using the hardener of the present invention in the undercoat layer. Therefore, it can be seen that the adhesive strength is improved when the hardener of the present invention is used in at least one of the photographic constituent layers.

Example 5 X-ray photosensitive material samples Nos. 28 to 32 were obtained by sequentially forming layers having the compositions shown below on both sides of a polyethylene terephthalate support which had been subjected to undercoating, from the support side.

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

First layer: Crossover layer Dye (I) 3 mg / m ² Mordant (II) 0.12 g / m ² Gelatin 0.2 g / m ² Second layer: Emulsion layer Average grain size 0.57 μm, consisting of AgBrI containing 2% by mole AgI Emulsion Coating amount of silver 4.5g / m ² Sensitizing dye (A) 450mg Sensitizing dye (B) 20mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3.0g t-butyl-catechol 400mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane 10 g Diethylene glycol 5 g p-Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 4 g 2-Mercapto Benzimidazole-5-sodium sulfonate 15mg 1,1-dimethylol-1-bromo-1-nitromethane 10m
g Gelatin 2g / m ² 3rd layer: protective layer Polymethylmethacrylate (average particle size 5μm) 7mg / m ² Colloidal silica (average particle size 0.013μm) 70mg / m ² Gelatin 1 g / m ² hardener (described in Table 6) Each sample was subjected to a storage test in the same manner as in Example 2, exposed to light, and subjected to the following processing, and photographic characteristics were measured in the same manner as in Example 2.

The sensitivity was shown as relative sensitivity with the sensitivity of Sample No. 28 7 days after application as 100.

 The results are shown in Table-6.

(Processing step) Insertion −-1.2 seconds Development + Transition 35 ° C 14.6 seconds Fixing + Transition 33 ° C 8.2 seconds Washing + Transition 25 ° C 7.2 seconds Squeeze 40 ° C 5.7 seconds Dry 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 0.10 g 5-Nitrobenzimidazole 0.10 g Glutaraldehyde bisulfite 15.0 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylenetetramine Hexaacetic acid 2.5 g Add water to finish to 1.

(Fixer) 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 Add to finish 1.

Also, while keeping the sample at 25 ° C. and 50% RH, 2 hours, 1 day and 7 days after application, a part of each sample was taken out.
Swell in water at 30 ° C for 5 minutes, measure the thickness of each sample,
The swelling degree V represented by the following formula was calculated, and changes over time in the curing action (post-hardening property) were observed.

 The results are shown in Table 6 below.

As is clear from the results of Table-6, in the X-ray photosensitive material sample Nos. 28 to 30 in which the hardener of the present invention was added to the protective layer,
Almost no change in photographic characteristics such as decrease in sensitivity or increase in fog was observed, and the change in swelling was small after 1 day of coating and drying, which was stable and stable compared to Comparative Sample Nos. 31 and 32. The post-dural property is remarkably improved.

[Effects of the Invention] According to the present invention as described above, the film strength is sufficiently secured without impairing the photographic characteristics, and there is no post-hardening effect.
It is possible to provide a silver halide photographic light-sensitive material containing a hardener having excellent adhesiveness to a support and having sufficient water solubility without increasing viscosity even when added to an emulsion.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material characterized in that at least one of the photographic constituent layers formed on a support is cured with a compound represented by the general formula [I]. In the general formula _{[I] (CH 2 = CH} -SO 2 n A ( wherein, A is a straight-chain alkyl group with a terminal hydroxyl group of valence n which at least one useful as substituent attached directly to the carbon atom Organic group, n is 2, 3 or 4
Represents )