JPH0553235A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a sufficiently high degree of hardening without adversely affecting photographic characteristics by hardening at least one of hydrophilic colloidal layers with at least one kind of specified compd. CONSTITUTION:At least one of hydrophilic colloidal layers is hardened with at least one kind of compd. represented by formula I (where A is a group represented by formula II and L is a group represented by formula III, IV or V). In the formula II, Y1 is a single bond, -O-, -S-, -N(R1)-, -(R2)C=N- or -N=C(R2)-, R1 is optionally substd. alkyl, aryl or aralkyl, R2 is H, optionally substd. alkyl, aryl or aralkyl and Z1 is a group of atoms required to form a 5- or 6-membered hetero ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. 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]

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 comprising 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 to add a compound called "hardener" 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, 1,167,207
Compounds having 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 68, U.S. Patent 3,103,43
Isocyanates described in No. 7, U.S. Patent 2,983,611
No. 3, aziridine compounds described in 3,107,280, etc., U.S. Pat.Nos. 2,725,294, acid derivatives described in 2,725,295, etc., carbodiimide compounds described in U.S. Pat. No. 3,100,704, epoxies described in U.S. Pat. Compounds, U.S. Pat.Nos. 3,321,313, isoxazole compounds described in 3,543,292 and the like, halogenocarboxaldehydes such as mucochloric acid, dihydroxydioxane, organic hardeners such as dioxane derivatives such as dichlorodioxane and chromium alum, It is an inorganic hardener such as zirconium sulfate and chromium trichloride.

However, these known hardeners, when used in light-sensitive materials, have insufficient curing action,
There is a long-term change in the hardening action called "post-hardening" that occurs because the hardening reaction to gelatin is slow, and it adversely affects the performance of the light-sensitive material (especially increased fog, decreased sensitivity or maximum density, soft gradation). And other coexisting photographic additives may cause the curing effect to be lost, or other photographic additives (eg couplers in internal color emulsions)
Each of them had some drawbacks, such as those 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 characteristics, and the curing reaction of gelatin is fast and the side reaction that is decomposed by water is also fast, so 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
It is achieved by a silver halide photographic light-sensitive material characterized by being hardened with a seed.

General formula [I]

[0013]

[Chemical 6]

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

General formula [II]

[0016]

[Chemical 7]

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 ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. ) Further, L is a general formula [III], a general formula [IV] or a general formula [V]
Represents a group selected from the groups represented by.

General formula [III]

[0020]

[Chemical 8]

(In the above general formula [III], Y ₂ is a single bond, -O-, -S-, -N (R ₃ )-, -N = C (R ₄ )-or-
(R ₄₎ represents a C = N-.

R ₃ represents the same as R ₁ .

R ₄ represents the same as R ₂ .

Z ₂ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. ) General formula [IV]

[0025]

[Chemical 9]

(In the above general formula [IV], R ₅ represents a hydrogen atom or a substituent.

J represents a divalent organic group or a single bond.

Q represents --O--, --N (R ₆ )-or a single bond.

R ₆ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. ) General formula [V]

[0030]

[Chemical 10]

(In the above general formula [V], R ₇ and R ₈ may be the same or different from each other,
It represents an aryl group, an aralkyl group, an acyl group or a substituted sulfonyl group. These groups may be further substituted. Further, R ₇ and R ₈ may be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

X ⁻ represents an anion for canceling the charge in the molecule, and n represents the number of anions necessary in the molecule for canceling the charge. )] Further, the present invention will be described in detail.

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

[0034]

[Chemical 11]

[0035]

[Chemical formula 12]

[0036]

[Chemical 13]

[0037]

[Chemical 14]

[0038]

[Chemical 15]

[0039]

[Chemical 16]

[0040]

[Chemical 17]

[0041]

[Chemical 18]

[0042]

[Chemical 19]

[0043]

[Chemical 20]

[0044]

[Chemical 21]

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.

Further, R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅
And R ₁₆ is a hydrogen atom, or a substituted or unsubstituted alkyl group, aralkyl group, aryl group, or —CO ₂
-, - CONH -, - 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 organic group - OSO _2.

More specifically, R ₁ or R ₂ is preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, cyclohexyl, 2-ethylhexyl, dodecyl, etc.), aryl groups having 6 to 20 carbon atoms (eg phenyl, tolyl, naphthyl, etc.) and aralkyl groups having 7 to 7 carbon atoms.
21 aralkyl groups (eg benzyl, phenethyl etc.)
And so on.

The alkyl group, aryl group or aralkyl group represented by R ₁ and R ₂ may have a substituent, and the substituent may be a halogen atom (eg, bromine atom, chlorine atom, fluorine atom, etc.). , An alkoxy group (eg, methoxy, ethoxy, 1-propyloxy, 2-propyloxy, etc.), an aryloxy group (eg, phenoxy, tolyloxy, naphthoxy, etc.), an acyl group (eg, acetyl, propionyl, benzoyl, etc.), a carbamoyl group, Examples thereof include a sulfamoyl group, a sulfo group, a sulfoxy group, and a sulfamino group. The number and position of these substituents can be arbitrarily selected.

R ₅ 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 ₅ 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 ₆ )-or a single bond,
R ₆ 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.

R ₇ or R ₈ 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 aralkyl group having 7 to 21 carbon atoms (eg benzyl, phenethyl etc.), an acyl group having 2 to 20 carbon atoms (eg acetyl, propionyl, benzoyl etc.) or a substituted sulfonyl group ( For example, 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 ₇ and R ₈ 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.

[0057]

[Chemical formula 22]

In the formula, R ₁₇ represents a substituent. Examples of the substituent include the same substituents as R ₇ and R ₈ . m represents 0, 1 or 2.

X ⁻ represents an anion for canceling charges in the molecule, and n represents the number of anions necessary for canceling in the molecule. Examples include halide ions, sulfonate ions, sulfate ions, phosphonate ions,
Phosphate _{^{ion, BF 4 -, ClO 4 -}} , PF 6 - , but like,
Preferred are Cl ⁻ , BF ₄ ⁻ , PF ₆ ⁻ and sulfonate ions.

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

[0061]

[Chemical formula 23]

[0062]

[Chemical formula 24]

[0063]

[Chemical 25]

[0064]

[Chemical formula 26]

[0065]

[Chemical 27]

[0066]

[Chemical 28]

The compound of the present invention can be easily synthesized by a known method. One of the methods is as follows.
The compound represented by the general formula [VII] is reacted with phosgene or trichloromethylchloroformate to form a compound represented by the general formula [VII].
The compound can be easily synthesized by reacting with the compound represented by the general formula [IX] in the presence of a base or the compound represented by the general formula [X].

[0068]

[Chemical 29]

[The above general formula [VI] and general formula [VII]
In, Y ₁ and Z ₁ are the same as those in the general formula [II]. In the general formula [VIII], Y ₂ and Z ₂ are the same as those in the general formula [III]. General formula (I
X], R ₅ , J and Q are the same as those in formula [IV]. In the general formula [X], R ₇ and R ₈ are the same as those in the general formula [V]. 〕next,
The synthesis method will be specifically described by taking the exemplified compounds 18, 23 and 31 of the present invention as examples.

<Synthesis of Exemplified Compound 18> (1) 2-Methyl-1,3,4-oxadiazoline-5-thione-4-
Synthesis of Carbonyl Chloride A solution of phosgene (50 g) in toluene (300 ml) is prepared, and a solution of 2-methyl-1,3,4-oxadiazoline-5-thione (58 g) and triethylamine (51 g) in toluene (200 ml) is added dropwise thereto at room temperature. After completion of dropping, heating is started and the mixture is stirred at 90 ° C for 1 hour. After cooling
The precipitate is filtered and the filtrate is concentrated under reduced pressure to obtain 87 g of crude crystals. This was recrystallized from acetonitrile to obtain 65.8 g (yield 74%) of white crystals.

(2) Synthesis of Compound 18 62.4 g of 4- (2-sulfoethyl) -pyridine was suspended in 100 ml of dimethylformamide and 200 ml of methanol, and then 34.0 g of triethylamine was added to complete the solution.

The resulting clear solution was added with 2-methyl at room temperature.
A solution of 57.1 g of -1,3,4-oxadiazoline-5-thione-4-carbonyl chloride in 200 ml of dimethylformamide was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 24 hours. The precipitated crystals were collected by filtration, washed with methanol, and dried to obtain 68.5 g (yield 65%) of white crystals of compound 18.

The structure of this product was confirmed by NMR and IR.

<Synthesis of Exemplified Compound 23> A solution of 50 g of phosgene in 300 ml of toluene was prepared, and 3-methyl-1,2,
116 g of 4-oxadiazole-5-thione and triethylamine 1
A solution of 01 g of toluene in 400 ml is added dropwise. After completion of dropping, heating is started and the mixture is stirred at 90 ° C for 1 hour. After cooling, the precipitate is filtered,
The filtrate is concentrated under reduced pressure to obtain 150 g of crude crystals. This was recrystallized from acetonitrile to give a white crystal of Exemplified Compound 23 9
2.0 g (yield 73%) was obtained. The structure of this product was confirmed by NMR and IR.

<Synthesis of Exemplified Compound 31> (1) Synthesis of 3-methyl-1,2,4-thiadiazole-5-thione-4-carbonyl chloride A solution of 50 g of phosgene in 300 ml of toluene was prepared, and this was mixed at room temperature for 3 hours. A solution of 66 g of -methyl-1,2,4-thiadiazole-5-thione and 51 g of triethylamine in 200 ml of toluene is added dropwise. After completion of dropping, heating is started and the mixture is stirred at 90 ° C for 1 hour. After cooling, the precipitate is filtered and the filtrate is concentrated under reduced pressure to obtain 96.3 g of crude crystals. This was recrystallized from acetonitrile to obtain 75.9 g (yield 78%) of white crystals.

(2) Synthesis of Exemplified Compound 31 4- (2-Sulfoethyl) -pyridine (62.4 g) is suspended in dimethylformamide (100 ml) and methanol (200 ml), and triethylamine (34.0 g) is added to complete the solution. At room temperature, the resulting clear solution was treated with 3-methyl-1,2,4-thiadiazole-5-thione-4-carbonyl chloride 63.4 g of dimethylformamide.
The 200 ml solution was added dropwise. After completion of dropping, the mixture was stirred at room temperature for 24 hours. The precipitated crystals were filtered and washed with methanol,
The crystals were dried to obtain 85.5 g (yield 76%) of white crystals of Exemplified Compound 31. 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 preferably 0.
It is in the range of 01 to 100% by weight, more preferably 0.1 to 30% 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 developing treatment method, the constituent layers of the light-sensitive material, etc., the description in Research Disclosure can be referred to.

[0083]

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, layers having the following compositions were 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. Then, samples 1 to 9 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

[0090]

[Chemical 30]

[0091]

[Chemical 31]

[0092]

[Chemical 32]

[0093]

[Chemical 33]

[0094]

[Chemical 34]

[0095]

[Chemical 35]

[0096]

[Chemical 36]

[0097]

[Chemical 37]

[0098]

[Chemical 38]

[0099]

[Chemical Formula 39]

Each of the prepared samples was used as a fresh sample,
This sample was left for 7 days at room temperature, and left for 2 days under the conditions of 50 ° C. and relative humidity of 50% RH to forcibly deteriorate the sample.

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 after coating for 7 days as 100.

Further, the sample left at room temperature for 7 days 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.

Processing step Color development 38 ° C. 3 minutes 15 seconds Bleach 38 ° C. 6 minutes 30 seconds Water washing 38 ° C. 3 minutes 15 seconds Settling 38 ° C. 6 minutes 30 seconds Water washing 38 ° C. 3 minutes 15 seconds Stabilization 25 ° C. 1 min 30 sec Dry 45 ° C. The composition of the treatment liquid used in each treatment step is as follows.

(Color developer) 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 Water is added to make 1000 ml.

(Bleach) Ethylenediaminetetraacetic acid iron 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 the 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.

[0110]

[Chemical 40]

[0111]

[Table 1]

As is clear from the results shown in Table 1, all of the samples 1 to 6 using the hardener according to the present invention showed a slight decrease in relative sensitivity as compared with the comparative samples 7 to 9. ,
No deterioration (increase) in fog was observed.

Further, even in the case of forced deterioration, Samples 1 to 6 of the present invention showed a slight decrease in sensitivity and a slight increase in fog as compared with Comparative Samples 7 to 9.

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

Further, from the results of scratch resistance indicating the film strength, Samples 1 to 6 of the present invention show higher film strength than Comparative Samples 7 to 9, 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 10 to 18 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) 0.
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.

[0119]

[Chemical 41]

[0120]

[Chemical 42]

[0121]

[Chemical 43]

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 10 7 days after application as 100.

The results are shown in Table 2.

(Processing step) Insertion 1.2 seconds Development + Crossover 35 ° C 14.6 seconds Fixing + Crossover 33 ° C 8.2 seconds Wash + Crossover 25 ° C 7.2 seconds Squeeze 40 ° C 5.7 seconds Dry 45 ° C 8.1 seconds (Developer) Hydroquinone 25.0g Phenidone 1.2 g 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 Triethylene Tetramine 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.
Add 77g water to make 1000ml.

Also, while keeping the samples at 25 ° C. and 50% RH for 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

[0129]

[Table 2]

As is clear from the results shown in Table 2, in the X-ray photosensitive material samples 10 to 14 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 moreover, one 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 Samples 15-18. Further, it can be seen that even a small amount of hardener is effective for hardening.

[0131]

As described above, according to the present invention, the hardening effect can be efficiently achieved even with a small amount of hardener without impairing the 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 comprises a compound represented by the following general formula [I]: A silver halide photographic light-sensitive material characterized by being hardened with at least one kind. 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 ₁ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. ) Further, L is a general formula [III], a general formula [IV] or a general formula [V]
Represents a group selected from the groups represented by. General formula [III] (In the general formula [III], Y ₂ is a single bond, —O—, —
_{S -, - N (R 3} ) -, - N = C (R 4) - or - (R ₄₎ represents a C = N-. R ₃ represents the same as R ₁ . R ₄ represents the same as R ₂ . Z ₂ represents an atomic group necessary for forming a 5- or 6-membered heterocycle. ) General formula [IV] (In the above general formula [IV], R ₅ represents a hydrogen atom or a substituent, J represents a divalent organic group or a single bond, and Q represents —O.
_{-, - N (R 6)} - or a single bond. R ₆ represents an alkyl group, an aryl group, an aralkyl group or a hydrogen atom. ) General formula [V] (In the general formula [V], R ₇ and R ₈ may be the same as or different from each other, an alkyl group, an aryl group,
It represents an aralkyl group, an acyl group or a substituted sulfonyl group.
These groups may be further substituted. Also, R ₇ , R ₈
May be bonded to each other to form a 5- or 6-membered nitrogen-containing heterocycle. X ⁻ represents an anion for canceling the charge in the molecule, and n represents the number of anions necessary in the molecule for canceling the charge. )]