JPH0527358A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the silver halide photographic sensitive material capable of forming a sufficient hard film without exerting any adverse effect on photographic characteristics by hardening a photographic constituent layer by a specified compound. CONSTITUTION:The silver halide photographic sensitive material has on a support at least one of hydrophilic colloidal layers hardened by at least one of compounds represented by formula I in which A is a group of formula II; X is -CO-, -CS-, or -SO2-; Y is a simple bond or -O-, -S-, or the like: L is a group of formula III; R3 is H or a substituent; J is a divalent organic or simple bond; Q is -O-, -N(R4)-, or a simple bond; R4 is alkyl, aryl, or the like; and M<+> is an alkali metal or ammonium ion, thus permitting the efficient hardening action to be achieved without impairing the photographic characteristics even in an small amount of hardener to be used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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.

[0002]

BACKGROUND OF THE INVENTION Generally, silver halide photographic light-sensitive materials (hereinafter referred to as light-sensitive materials) include, for example, silver halide emulsion layers, intermediate layers, protective layers, filter layers, subbing layers, antihalation layers and ultraviolet absorbing layers. , An antistatic layer, a backing layer, and other various photographic constituent layers are formed on a support such as glass, paper, and synthetic resin film.

Since these photographic constituent layers are formed by coating an aqueous coating solution composed of a hydrophilic polymer and / or a water-dispersible polymer, the mechanical strength is weak as it is. For example, gelatin films have low melting points and are overly water-swellable.
Further, the latex film has a drawback that the adhesion to the support is extremely poor and the latex film is easily peeled off.

Therefore, it is known that a compound called "hardener" is added to the photographic constituent layers to improve the mechanical strength thereof. Aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732,303
No. 3,288,775, British Patent 974,723, No. 1,167,207
Compounds having a reactive halogen atom, diacetyl, ketone compounds such as cyclopentadione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-dichloro-1,3,5-triazine , Divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Patents 3,232,763, 3,635,718, British Patent 99
A compound having a reactive olefin as described in 4,809,
U.S. Pat.Nos. 3,539,644 and 3,642,486, Japanese Patent Publication No. 49-13563
No. 53-47271, 56-48860, JP-A-53-57257,
61-128240, 62-4275, 63-53541, 63-26457
No. 2, etc., vinylsulfonyl compounds, N-hydroxymethylphthalimide, U.S. Patents 2,732,316, 2,586,1
N-methylol compounds described in No. 68, U.S. Patent 3,103,43
Isocyanates described in No. 7, 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, U.S. Pat.No. 3,100,704, etc., carbodiimide compounds, U.S. Pat. Compounds, U.S. Pat. It is an inorganic hardener such as zirconium sulfate and chromium trichloride.

However, these known hardeners, when used in a light-sensitive material, have insufficient curing action,
There is a long-term change in the hardening action called "post-hardening" that occurs due to the slow hardening reaction to gelatin, and it adversely affects the performance of the light-sensitive material (especially increased fog, decreased sensitivity or maximum density, and soft gradation). And the like, or the coexistence of other photographic additives causes the curing effect to be lost, and other photographic additives (eg couplers in internal color emulsions)
Each of them had some drawbacks, such as the ones that reduced the efficacy of and caused pollution.

The hardening action on gelatin is relatively fast,
As a hardener with less post-hardening, compounds having a dihydroquinoline skeleton described in JP-A-50-38540, JP-A-51-5
9625, 62-262854, 62-264044, 63-184741
N-carbamoylpyridinium salts described in Japanese Patent Publication No. Sho 55
-38655 acylimidazoles, Japanese Patent Publication No. 53-220
Compounds containing two or more N-acyloxyimino groups in the molecule described in 89, compounds having N-sulfonyloxyimide groups described in JP-A-52-93470, JP-A-58-113929
Compounds having a phosphorus-halogen bond described in Japanese Patent
The chloroformamidinium compounds described in 0-225148, 61-240236 and 63-41580 are known.

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

[0008]

OBJECTS OF THE INVENTION Therefore, firstly, the object of the present invention is to provide a photographic light-sensitive material hardened by a novel hardener which achieves sufficient hardness without any adverse effect on photographic properties. Especially.

Secondly, it is to provide a photographic light-sensitive material which is hardened by a hardening agent having no rapid hardening by a quick hardening action.

A third object is to provide a photographic light-sensitive material which is hardened with a hardener which reacts with high reactivity to a reactive residue in gelatin and hardens gelatin efficiently.

[0011]

The object of the present invention is to provide a silver halide photographic light-sensitive 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]: At least one of the compounds represented by
This is achieved by a silver halide photographic light-sensitive material characterized by being hardened with a seed.

General formula [I]

[0013]

[Chemical 5]

[In the formula, A represents a group selected from the groups represented by the following general formula [II].

General formula [II]

[0016]

[Chemical 6]

R ₁ represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

Z represents an atomic group necessary for forming a 5- or 6-membered heterocycle. ) Further, L represents a group selected from the groups represented by the general formula [III] or the general formula [IV].

General formula [III]

[0021]

[Chemical 7]

(In the above general formula [III], R ₃ represents a hydrogen atom or a substituent.

J represents a divalent organic group or a single bond.

Q represents --O--, --N (R ₄ )-or a single bond.

R ₄ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom.

M ⁺ represents an alkali metal ion or an ammonium ion. ) General formula [IV]

[0027]

[Chemical 8]

(In the above general formula [IV], R ₅ and R ₆ may be the same or different from each other,
It represents an aryl group, an acyl group or a substituted sulfonyl group. These groups may be further substituted. Further, R ₅ and R ₆ may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. )] Further, the present invention will be described in detail.

Preferred examples of the group represented by the general formula [II] are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 9]

[0031]

[Chemical 10]

[0032]

[Chemical 11]

[0033]

[Chemical 12]

[0034]

[Chemical 13]

[0035]

[Chemical 14]

[0036]

[Chemical 15]

[0037]

[Chemical 16]

[0038]

[Chemical 17]

[0039]

[Chemical 18]

[0040]

[Chemical 19]

[0041]

[Chemical 20]

[0042]

[Chemical 21]

[0043]

[Chemical formula 22]

[0044]

[Chemical formula 23]

[0045]

[Chemical formula 24]

[0046]

[Chemical 25]

[0047]

[Chemical formula 26]

[0048]

[Chemical 27]

Here, R ₁ represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

In addition, R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ and R ₁₂ are
Hydrogen atom, or a substituted or unsubstituted alkyl group, an aralkyl group, an aryl group, or, -CO ₂ -, - CONH
-, - OCO -, - NHCO -, - SO 2 -, - SO 2 NH -, - NHSO 2
It represents a linear, branched or cyclic organic group containing at least one linking group selected from —, —SO ₃ — and —OSO ₂ —.

As the substituent, 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 etc. are mentioned.

More specifically, R ₁ , R ₂ , R ₇ , R ₈ , R ₉ ,
In R ₁₀ , R ₁₁ and R ₁₂ , the substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl, butyl, pentyl, cyclohexyl, 2-ethylhexyl, Dodecyl, etc., aryl groups having 6 to 20 carbon atoms such as phenyl, tolyl, naphthyl, and aralkyl groups having 7 to 20 carbon atoms such as benzyl and phenethyl. Can be mentioned.

In the substituents, examples of the halogen atom include bromine atom, chlorine atom and fluorine atom, examples of the alkoxy group include methoxy and ethoxy, and examples of the aryloxy group include phenoxy and naphthoxy.

R ₃ represents a hydrogen atom or a substituent.

As the substituent, an alkyl group (eg methyl, ethyl, propyl etc.), an alkenyl group (eg vinyl, allyl etc.), an aryl group (eg phenyl, naphthyl etc.), an aralkyl group (eg benzyl, phenethyl etc.), Halogen atom (eg fluorine atom, chlorine atom etc.), alkoxy group (eg methoxy, ethoxy etc.), aryloxy group (eg phenoxy, naphthoxy etc.), acyl group (eg acetyl, propionyl,
Benzoyl etc.) and the like. R ₃ is preferably
It is a hydrogen atom.

J represents a divalent organic group or a single bond. As the divalent organic group, an alkylene group having 1 to 10 carbon atoms (eg methylene, ethylene, propylene, etc.), an arylene group having 6 to 12 carbon atoms (eg 1,4-phenylene,
1,3-phenylene, 1,2-phenylene, 1,4-naphthalene-diyl, etc.), or -O -, - NH -, - CO 2 -, - CONH -, -
OCO -, - NHCO -, - SO 2 -, - SO 2 NH -, - NHSO 2 - linking group and the alkylene group such as a divalent organic formed by combining two or more groups selected from arylene groups Groups. Preferred are an alkylene group having 1 to 4 carbon atoms and a single bond.

Q represents --O--, --N (R ₄ )-or a single bond,
R ₄ represents an alkyl group (eg methyl, ethyl, propyl, butyl etc.), an aryl group (eg phenyl, tolyl etc.), an aralkyl group (eg benzyl, phenethyl etc.) or a hydrogen atom. R ₄ is preferably a hydrogen atom.

M ⁺ is an alkali metal ion (for example, sodium ion, potassium ion, lithium ion, etc.),
Or represents an ammonium ion (eg, trimethylammonium ion, triethylammonium ion, tetramethylammonium ion, etc.). Preferred is sodium ion or potassium ion.

R ₅ or R ₆ is preferably an alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, 2-ethylhexyl, dodecyl, etc.), aryl having 6 to 20 carbon atoms. A group (eg phenyl, tolyl, naphthyl etc.), an acyl group having 2 to 20 carbon atoms (eg acetyl, propionyl, benzoyl etc.) or a substituted sulfonyl group (eg methanesulfonyl,
Benzenesulfonyl, paratoluenesulfonyl, etc.), which may be the same as or different from each other. Further, it may further have a substituent.

As the substituent, an alkyl group (eg methyl, ethyl, propyl etc.), an alkenyl group (eg vinyl, allyl etc.), an aryl group (eg phenyl, naphthyl etc.), an aralkyl group (eg benzyl, phenethyl etc.), Halogen atom (eg chlorine atom, fluorine atom etc.), alkoxy group (eg methoxy, ethoxy etc.), aryloxy group (eg phenoxy, naphthoxy etc.), acyl group (eg acetyl, propionyl,
Benzoyl), a sulfo group, a sulfooxy group, a sulfoamino group, and the like. Preferred as the substituent is an alkoxy group or a sulfo group.

R ₅ and R ₆ are bonded to each other to form a 5-membered or 6-membered group.
It is also preferable to form a membered nitrogen-containing heterocycle. Examples of the heterocycle in that case are shown below, but the present invention is not limited thereto.

[0063]

[Chemical 28]

In the formula, R ₁₃ represents a substituent. Examples of the substituent include the same substituents as R ₅ and R ₆ . m represents 0, 1 or 2.

Examples of the compound represented by the general formula [I] are shown below, but the invention is not limited thereto.

[0066]

[Chemical 29]

[0067]

[Chemical 30]

[0068]

[Chemical 31]

[0069]

[Chemical 32]

[0070]

[Chemical 33]

The compound of the present invention can be easily synthesized by a known method. For example, it can be easily synthesized by reacting a compound represented by the following general formula [V] with a compound represented by the general formula [VI] or general formula [VII].

[0072]

[Chemical 34]

(In the above general formula [V], A represents the same as A in the general formula [I], R represents a lower alkyl group, and X represents a halogen atom.
In the formula, R ₃ , J, Q and M ⁺ in the general formula [III] are
Represents the same as R ₃ , J, Q and M ⁺ . In formula [VII], R _5, R ₆ represent the same meanings as R _5, R ₆ in the general formula [IV]. ) Here, the compound represented by the general formula [V] can be easily prepared by reacting the monoalkyl phosphate dihalogen compound represented by the general formula [VIII] with the compound represented by the general formula [IX]. Can be obtained.

General formula [VIII]

[0075]

[Chemical 35]

General formula [IX] AH In the above general formula [VIII], X and R are represented by the general formula [V]
Represents the same as X and R in. Also, the general formula [IX]
In the formula, A represents the same as A in formula [I].

Next, the synthesis method will be specifically described by taking Exemplified Compound 1 as an example.

Synthesis of Exemplified Compound 1 (1) Synthesis of methyl 3,5-dioxo-4-methyl-1,2,4-oxadiazolidinylphosphonate monochloride 3,5-dioxo-4-methyl-1 1,2,4-oxadiazolidine 11.6
g (0.1 mol) and triethylamine 10.1 g (0.1 mol) in 50 ml of methylene chloride were added to methyl dichloride 14.9 g (0.1 mol).
(Mol) in a 50 ml solution of methylene chloride in 10 minutes. After completion of the dropping, the mixture was heated under reflux for 2 hours. After cooling, the precipitate is filtered and the filtrate is concentrated under reduced pressure to obtain 22 g of crude crystals. This was recrystallized from acetonitrile to obtain 17.2 g (78%) of white crystals.

(2) Preparation of Exemplified Compound 1 Sodium 2- (4-pyridyl) -ethanesulfonate 10.5 g (0.0
A solution of 5 mol of dimethylformamide in 20 ml of methanol in 40 ml is prepared and cooled to 0 ° C. Then 3,5-dioxo-4-
Methyl-1,2,4-oxadiazolidinylphosphonic acid methyl monochloride 11.4 g (0.05 mol) dimethylformamide 30 m
1 solution was added and stirred until uniform. The resulting solution was allowed to stand overnight, then 300 ml of ether was added to precipitate crystals. The precipitated crystals were filtered, washed with ether and dried to obtain 20 g of crude crystals. This was recrystallized from methanol-acetonitrile to obtain 16.1 g (76%) of white crystals.
The structure of this product was confirmed by NMR and IR.

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

The amount of the hardener used in carrying out the present invention is
It depends on the type of the light-sensitive material applied and the type of hydrophilic binder, but is preferably 0.
It is in the range of 01 to 100% by weight, more preferably 0.1 to 10% by weight.

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

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

Silver halides, chemical sensitizers, silver halide solvents, spectral sensitizing dyes, antifoggants, gelatin, etc. used in the silver halide emulsion layer or other layers of the light-sensitive material in carrying out the present invention. Hydrophilic colloid,
There is no particular limitation on the ultraviolet absorber, the polymer latex, the whitening agent, the color coupler, the anti-fading agent, the dye, the matting agent, the surfactant, etc., for example, Research Disclosure Volume 176 (1978 12
Mon.), pages 22 to 31 can be used.

Regarding the support of the light-sensitive material, the development processing method, the constituent layers of the light-sensitive material, etc., the description in Research Disclosure can be referred to.

[0086]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

Example 1 In the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver. The sensitizing dye is shown by the number of moles per mole of silver.

On the triacetyl cellulose film support, each layer having the following composition was sequentially formed from the support side to prepare a multilayer color photographic light-sensitive material sample.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (Oil-1) 0.20 High boiling point solvent (Oil-) 2) 0.20 gelatin 1.6 Second layer: intermediate layer (IL-1) gelatin 1.3 Third layer: 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 DIR compound (D-1) 0.006 DIR compound (D-2) 0.01 High boiling 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) 9 Sensitizing dye (S-1) 1.7 × 10 ^-4 Sensitizing dye (S-2) 1.6 × 10 ^-4 Sensitizing dye (S-3) 0.1 × 10 ^-4 Cyan coupler (C-2) 0.23 Colored cyan Coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling point 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 Silver iodobromide 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 DIR compound (D-3) 0.02 High boiling solvent (Oil-2 ) 0.70 Additive (SC-1) 0.003 Gelatin 1.0 Seventh layer: High sensitivity green sensitive emulsion layer (GH) Silver iodobromide 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 point solvent (Oil-2) 0.35 Additive (SC-1) 0.003 Gelatin 1.0 Eighth layer: Yellow filter layer (YC) Add yellow colloidal silver 0.1 Agent (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-2) 0.12 High boiling point solvent (Oil-2) 0.15 Gelatin 1.0 9th layer: Low sensitivity blue-sensitive emulsion layer (BL) Iodine Silver bromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-9) 5.8 x 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 point solvent (Oil-2) 0.18 Additive ( SC-1) 0.004 gelatin 1.3 10th layer: high-sensitivity blue-sensitive emulsion layer (B-H) 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 point solvent (Oil-2) 0.05 Additive (SC-1) 0.002 Gelatin 1.0 11th layer: 1st layer Protective layer (PRO-1) Silver iodobromide emulsion (Em-5) 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) 0.10 Additive (HS-1) 0.2 Additive (HS-2) ) 0.1 High boiling point 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 Polymethylmethacrylate (Average particle size-3 μm) 0.02 Sliding agent (WAX-1) 0.04 Charge control agent (SU-1) 0.004 Charge control agent ( U-2) 0.02 gelatin 0.5 The hardener of the present invention or the comparative hardener is added to the 12th layer (second protective layer) so that the amount shown in Table 1 is obtained with respect to the gelatin of all layers. Samples 1 to 8 were prepared.

In each layer, coating aid (SU-4), dispersion aid (SU-3), stabilizer (ST-1), preservative (D).
I-1), antifoggants (AF-1), (AF-2),
Dyes (AI-1) and (AI-2) were added appropriately.

The emulsions used in the above samples are as follows. All are internal high iodine type monodisperse emulsions.

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 silver iodide content 8.0 mol% Average grain size 0.84
μm grain shape octahedron Em-4: average silver iodide content 8.5 mol% average grain size 1.02
μm Grain shape Octahedron Em-5: Average silver iodide content 2.0 mol% Average grain size 0.88
μm

[0093]

[Chemical 36]

[0094]

[Chemical 37]

[0095]

[Chemical 38]

[0096]

[Chemical Formula 39]

[0097]

[Chemical 40]

[0098]

[Chemical 41]

[0099]

[Chemical 42]

[0100]

[Chemical 43]

[0101]

[Chemical 44]

[0102]

[Chemical 45]

Each of the prepared samples was used as a fresh sample,
This sample was left at room temperature for 7 days, and at 50 ° C,
Samples that were forcibly deteriorated by leaving them for 2 days under the condition of relative humidity of 50% RH were prepared.

After these samples were wedge-exposed with white light, the following processing was carried out to measure sensitivity and fog.

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 Sample 1 which was left at room temperature for 7 days after coating as 100.

Also, the sample left for 7 days at room temperature was used for 30 days.
Immerse in ℃ water for 5 minutes, press a sapphire needle with a radius of 0.3 mm against the sample surface, and move the sapphire needle in the range of 0 to 200 g while moving parallel on the film surface at a speed of 2 mm per second. The load when the film surface of the sample was continuously changed and damaged was obtained as the scratch resistance.

The results are also shown in Table 1.

[0108] The composition of the processing liquid used in each processing step is as follows.

(Color developer) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75g anhydrous sodium sulfite 4.25g hydroxylamine / 1/2 sulfate 2.0g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1000 ml.

(Bleach) Ethylenediaminetetraacetic acid ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10 ml Water is added to 1000 ml, and pH is adjusted to 6.0 using ammonia water.

(Fixer) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1000 ml, and pH is adjusted to 6.0 using acetic acid.

(Stabilizing Solution) Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1000 ml.

[0113]

[Chemical 46]

[0114]

[Table 1]

As is clear from the results shown in Table 1, all of the samples 1 to 5 using the hardener according to the present invention showed a slight decrease in relative sensitivity as compared with the comparative samples 6 to 8. ,
No deterioration (increase) in fog was observed.

Further, even in the case of forced deterioration, Samples 1 to 5 of the present invention showed a slight decrease in sensitivity and a slight increase in fog as compared with Comparative Samples 6 to 8.

Therefore, it is understood that the hardener according to the present invention hardly impairs photographic characteristics.

Further, from the results of the scratch resistance indicating the film strength, all of Samples 1 to 5 of the present invention showed higher film strength than Comparative Samples 6 to 8, and therefore, the hardener of the present invention. It can be seen that is hardened more efficiently than the comparative compound.

Example 2 X-ray photosensitive materials 9 to 14 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 in amounts per mol of silver halide unless otherwise specified.

First layer: crossover cut layer Dye (I) 3 mg / m ² mordant (II)
12g / m ² Gelatin 0.2 g / m ² Second layer: emulsion layer Emulsion composed of AgBrI containing 0.57 μm average grain size and AgI 2 mol% Silver coating amount 4.5 g / m ² Sensitizing dye (A) 450 mg Sensitizing dye (B) 20 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3.0 mg t-butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000)
1.0g Styrene-maleic anhydride copolymer 2.5g Trimethylolpropane 10g Diethylene glycol 5g p-Nitrophenyl-triphenylphosphonium chloride 50mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 4g 2-Mercaptobenzimidazole-5-sulfone Acid soda 15mg Additive A
70mg additive B
1g 1,1-Dimethylol-1-bromo-1-nitromethane 10mg 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 additive C 10mg / m ² additive D
2mg / m ² additive E
7mg / m ² additive F 1
5 mg / m ² gelatin 1 g / m ² hardener (listed in Table 2) Preservative DI-1 was added to each sample.

[0122]

[Chemical 47]

[0123]

[Chemical 48]

[0124]

[Chemical 49]

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 photographic characteristics were measured in the same manner as in Example 1.

The sensitivity was shown as a relative sensitivity with the sensitivity of Sample 9 7 days after coating as 100.

The results are shown in Table 2.

[0128] (Developer) Hydroquinone 25.0g Phenidone 1.2g Potassium sulfite 55.0g Boric acid 10.0g Sodium hydroxide 21.0g Triethylene glycol 17.5g 5-Nitroimidazole 0.10g 5-Nitrobenzimidazole 0.10g Glutaraldehyde bisulfite 15.0g Glacial acetic acid 16.0g Potassium bromide 4.0g Triethylenetetramine hexaacetic acid 2.5g Add water to make 1000ml. (Fixer) Ammonium thiosulfate 130.9g Anhydrous sodium sulfite 7.3g Boric acid 7.0g Acetic acid (90wt%) 5.5g Sodium acetate (trihydrate) 25.8g Aluminum sulfate (18hydrate) 14.6g Sulfuric acid (50wt%) 6.77g Water Add to make 1000 ml.

While the samples were kept at 25 ° C. and 50% RH, 2 hours, 1 day, and 7 days after application, a part of each sample was taken out and swollen in water at 30 ° C. for 5 minutes. The film thickness of the sample was measured, the swelling degree V represented by the following equation was calculated, and the change with time of the curing action (post-hardening property) was observed.

The results are shown in Table 2 below.

V = increased film thickness due to swelling / film thickness after drying Comparative compound (IV) HCHO (V) OCH-CHO

[0132]

[Table 2]

As is clear from the results shown in Table 2, in the X-ray photosensitive material samples 9 to 11 in which the hardener of the present invention was added to the protective layer, fluctuations in photographic characteristics such as decrease in sensitivity and increase in fog occurred. Almost no change was observed, and after 1 day or more after coating and drying, the change in swelling degree was small and stable, and the post-hardening property was remarkably improved as compared with Comparative Samples 13-14. Further, it can be seen that the dura mater is efficiently made as compared with Sample 12.

[0134]

As described above, according to the present invention, a hardener can be efficiently used even with a small amount of hardener without impairing photographic performance.
It is possible to provide a silver halide photographic light-sensitive material containing a novel hardener having no post-hardening effect.

Claims (1)

Claims: 1. A silver halide photographic light-sensitive 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 characterized by being hardened with at least one compound represented by General formula [I] [In the formula, A represents a group selected from the groups represented by the following general formula [II]. General formula [II] R ₁ represents a substituted or unsubstituted alkyl group, aryl group or aralkyl group. R ₂ represents a hydrogen atom or a substituted or unsubstituted alkyl group, aryl group or aralkyl group. Z represents an atomic group necessary for forming a 5- or 6-membered heterocycle. ) Further, L is represented by the general formula [III] or the general formula [I
V] represents a group selected from the groups represented by the following. General formula [III] (In the above general formula [III], R ₃ represents a hydrogen atom or a substituent, J represents a divalent organic group or a single bond, and Q represents −.
_{O -, - N (R 4} ) - or a single bond. R ₄ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. M ⁺ represents an alkali metal ion or an ammonium ion. ) General formula [IV] (In the general formula [IV], R ₅ and R ₆ may be the same as or different from each other, an alkyl group, an aryl group,
It represents an acyl group or a substituted sulfonyl group. These groups may be further substituted. Further, R ₅ and R ₆ may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. )]