JP3282045B2 - Silver halide photographic materials - Google Patents

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 layer hardened with a specific compound.

[0002]

BACKGROUND OF THE INVENTION Generally, silver halide photographic materials (hereinafter referred to as "photosensitive materials") include, for example, silver halide emulsion layers, intermediate layers, protective layers, filter layers, undercoat layers, antihalation layers, and ultraviolet absorbing layers. 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.

[0003] 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 extremely poor adhesion to the support,
There are drawbacks such as easy peeling.

[0004] For this reason, it is known that a compound called "hardener" is added to a photographic component layer to improve its mechanical strength. For example, aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732,303
No. 3,288,775; British Patent Nos. 974,723; 1,167,207
Compounds having a reactive halogen described in
Ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethyl) urea, 2-hydroxy-4,6-
Dichloro-1,3,5-triazine, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat.Nos. 3,232,763 and 3,635,718, UK patent
Compounds having a reactive olefin described in 994,809 and the like, U.S. Pat.Nos. 3,539,644 and 3,642,486, JP-B-49-1
No. 3563, No. 53-47271, No. 56-48860, JP-A-53-57257
Nos. 61-128240, 62-4275, 63-53541, 63
-264572 and the like, a vinylsulfonyl compound, N-hydroxymethylphthalimide, U.S. Pat.
N-methylol compounds described in 2,586,168, etc., U.S. Patent
Isocyanates described in 3,103,437 and the like, U.S. Pat.
Nos. 83,611, 3,107,280 and the like, aziridine compounds described in U.S. Pat.Nos. 2,725,294 and 2,725,295 and the like, acid derivatives described in 2,725,295 and the like, carbodiimide compounds described in U.S. Pat. Epoxy compounds, isoxazole compounds described in U.S. Pat. And inorganic hardeners such as zirconium sulfate and chromium trichloride.

[0005] However, these known hardeners, when used in photosensitive materials, do not have a sufficient curing action.
There is a long-term change in the hardening action called "post-hardening" caused by a slow hardening reaction to gelatin, which adversely affects the performance of the photosensitive material (especially increase in fog, decrease in sensitivity or maximum density, soft gradation) ), The curing action is lost due to other coexisting photographic additives, the effectiveness of other photographic additives (for example, couplers in internal color emulsions) is reduced, or contamination occurs. , Each had some drawbacks.

The hardening action on gelatin is relatively fast,
As a hardening agent having a low 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 JP-B No.
Acylimidazoles described in JP-38655, JP-B-53-220
No. 89, a compound having two or more N-acyloxyimino groups in the molecule, JP-A-52-93470, a compound having an N-sulfonyloxyimide group, and JP-A-58-113929.
Having a phosphorus-halogen bond described in
60-225148, 61-240236, chloroformamidinium compound described in 63-41580, JP-A-61-100743,
And the compounds described in JP-A-63-229450.

[0007] These hardeners are characterized in that they have a fast curing action and therefore have little post-hardening. However, many of these hardeners affect photographic properties, and the hardening reaction of gelatin is fast and the side reaction decomposed by water is also fast. Therefore, in a general method for producing a photographic light-sensitive material using an aqueous solution of gelatin, The effective use efficiency of the hardener was extremely low, and in order to obtain a gelatin film having a sufficient hardening degree, there was a disadvantage that a large amount of the hardener had to be used.

[0008]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is, firstly, to provide a photographic light-sensitive material which is hardened with a novel hardener which achieves a sufficient degree of hardening without any adverse effect on photographic characteristics. It is in. A second object of the present invention is to provide a photographic material hardened by a hardener having no post-hardening due to a rapid hardening action. A third object of the present invention is to provide a photographic light-sensitive material hardened by a hardening agent which reacts with high selectivity to reactive residues in gelatin and hardens gelatin efficiently.

[0009]

The object of the present invention is to provide a silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula (I): At least one of the compounds represented by
Achieved by hardening depending on the species.

[0010]

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In the formula, R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group and the like), and an alkenyl group having 2 to 20 carbon atoms (for example, vinyl group, propenyl group). An aryl group having 6 to 20 carbon atoms (e.g., phenyl, tolyl, naphthyl, etc.),
An aralkyl group having 7 to 21 carbon atoms (such as a benzyl group or a phenethyl group) and R ₄ —Y ₂ —, (R ₅ ) (R ₆ )> N— or
It represents an _{(R 7) (R 8)} > C = group represented as N-.

R ₄ , R ₅ , R ₆ , R ₇ and R _{8 each} have 1 to 20 carbon atoms.
Alkyl groups (e.g., methyl, ethyl, propyl, etc.), alkenyl groups having 2-20 carbon atoms (e.g., vinyl group, propenyl group, etc.), and aryl groups having 6-20 carbon atoms (e.g., phenyl group, naphthyl group, etc.) Etc.), carbon number 7-21
(For example, benzyl group, phenethyl group, etc.). R ₅ and R ₆ , and R ₇ and R ₈ may be bonded to each other to form a ring. Examples of the ring formed by R ₅ and R ₆ include a pyrrolidine ring, a piperazine ring, a piperidine ring, and a morpholine ring. Examples of the ring formed by R ₇ and R ₈ include a cyclohexane ring and a cyclohexane ring. And a pentane ring.

R ₂ and R ₃ may be the same or different and each may be an alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), or an alkenyl group having 2 to 20 carbon atoms (eg, For example, a vinyl group, a propenyl group, etc., an aryl group having 6 to 20 carbon atoms (eg, phenyl group, tolyl group, naphthyl group, etc.) and an aralkyl group having 7 to 21 carbon atoms (eg, benzyl group, phenethyl group, etc.) are shown.

R ₂ and R ₃ may combine to form a ring. Examples of such a ring include a pyrrolidine ring, a piperazine ring, a piperidine ring, a morpholine ring and the like.

It is also preferred that R ₁ and R ₂ or R ₃ combine to form a ring. Examples of such rings are pyridine rings,
Examples include a quinoline ring, an isoquinoline ring, an imidazole ring, an oxazole ring, a thiazole ring, a benzimidazole ring, a benzoxazole ring, and a benzothiazole ring. Among these, a pyridine ring, a quinoline ring and an isoquinoline ring are particularly preferred.

R ₁ , R ₂ and R ₃ may have a substituent. Examples of preferred substituents include a halogen atom (eg, chlorine atom, fluorine atom, etc.), a hydroxyl group, an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.), an aryl group (eg, phenyl group, naphthyl group, etc.), An aryloxy group (eg, phenoxy group, tolyloxy group, naphthoxy group, etc.), a carbamoyl group (eg, N, N-dimethylcarbamoyl group, N-methylcarbamoyl group, etc.), a sulfamoyl group (eg, N, N-dimethylsulfamoyl group, N-methylsulfamoyl group), sulfo group, sulfoamino group, sulfooxy group, nitro group,
And a heterocyclic group (eg, a pyridyl group, a quinolyl group, a pyrrolidyl group, a piperidyl group, a morpholyl group, etc.).

Y ₁ represents an oxygen atom or a sulfur atom, and Z ₁ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. Y ₁
Examples of the nitrogen-containing heterocyclic group containing Z ₁ and Z ₁ include the following, but the present invention is not limited to the following.

[0018]

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[0019]

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[0020]

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In the formula, R ₁₄ represents a substituent. Examples of preferred substituents include a halogen atom (eg, chlorine atom, fluorine atom, etc.), a hydroxyl group, an alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.), an aryl group (eg, phenyl group, naphthyl group, etc.), aryl Oxy group (eg, phenoxy group, tolyloxy group, naphthoxy group, etc.), carbamoyl group (eg, N, N-dimethylcarbamoyl group, N-methylcarbamoyl group, etc.), sulfamoyl group (eg, N, N-dimethylsulfamoyl group, N -
Methylsulfamoyl group), sulfo group, sulfoamino group, sulfooxy group, nitro group, heterocyclic group (for example, pyridyl group, quinolyl group, pyrrolidyl group, piperidyl group,
Morpholyl group).

R ₁₅ is an alkyl group having 1 to 20 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, etc.);
20 aryl groups (eg phenyl, naphthyl, etc.)
Represents Preferably it is a C1-C4 alkyl group.

[0023] X ₁ ^- represents an anion to form an intramolecular salt. Preferably Cl ⁻ , Br ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , PF ₆
^-, and the like.

[0024] -SO ₃ ^- anionic groups in the molecule, such as is also preferred.

Among the compounds represented by the general formula [I], a compound represented by the general formula [II] is particularly preferable.

[0026]

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In the formula, R ₉ is an alkyl group having 1 to 20 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group and the like), and an alkenyl group having 2 to 20 carbon atoms (for example, vinyl group,
A C6-C20 aryl group (e.g., phenyl, tolyl, naphthyl, etc.);
To 21 aralkyl groups (for example, benzyl group, phenethyl group, etc.). R ₉ may further have a substituent. Preferred substituents include a halogen atom (eg, a chlorine atom, a fluorine atom, a bromine atom, etc.), a hydroxy group,
Alkoxy group (eg, methoxy group, ethoxy group, propoxy group, etc.), carbamoyl group (eg, N, N-dimethylcarbamoyl group, N-methylcarbamoyl group, etc.), sulfamoyl group (eg, N, N-dimethylsulfamoyl group, N -
Methylsulfamoyl group), a sulfo group, a sulfoamino group, a sulfooxy group, and the like. Particularly preferred substituents include an alkoxy group and a sulfo group.

R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ represent a hydrogen atom or a substituent. Preferred substituents include a halogen atom (eg, a chlorine atom, a fluorine atom, a bromine atom, etc.), a hydroxy group, an alkoxy group (eg, a methoxy group, an ethoxy group, a propoxy group, etc.), and a carbamoyl group (eg, N, N-
Dimethylcarbamoyl group, N-methylcarbamoyl group, etc.), sulfamoyl group (eg, N, N-dimethylsulfamoyl group, N-methylsulfamoyl group, etc.), sulfo group, sulfoamino group, sulfooxy group, nitro group and the like. Can be Adjacent substituents may combine to form a condensed ring (for example, a quinoline ring, an isoquinoline ring, etc.).

[0029] _{Y 3, Z 2, X 2} - is the Y ₁ in the general formula (I), Z _1, X ₁ ^- represents the same as.

Examples of the compounds represented by formulas [I] and [II] are shown below. The present invention is not limited to this.

[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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The compound of the present invention can be easily synthesized by a known method. One method is to react a compound represented by the general formula [IV] with a compound represented by the following general formula [III]. The compound synthesized by this method can also change the anion in the molecule by an anion exchange reaction.

[0040]

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Wherein R _{1 to} R ₃ are the same as those in the general formula [I]. X ₃ represents a leaving group such as a halogen atom and a sulfonyloxy group. X ₄ ^- represents the release of anions to form an intramolecular salt. Y ₄ represents a sulfur atom or an oxygen atom, and Z ₃ represents an atom group necessary for forming a nitrogen-containing heterocyclic ring. Here, the compound represented by the general formula [III] is converted into a quaternary salt by a reaction such as halogenation or sulfonation of the compound represented by the following general formula [V], or represented by the general formula [VI]. To a quaternary ammonium compound with the compound represented by the general formula [VII].

[0042]

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Wherein R _{1 to} R ₃ are the same as those in the general formula [I]. X ₅ and X ₆ represent a leaving group such as a halogen atom or a sulfonyloxy group. Next, the synthesis method will be specifically described using the exemplified compound (1) of the present invention as an example.

2-Chloropyridine (11.35 g, 0.10 mol) and dimethyl sulfate (13.5 g, 0.10 mol) were refluxed in acetonitrile for 3 hours and then cooled. 2-Hydroxypyridine (9.51 g, 0.10 mol) was added, and then a solution of triethylamine (10.20 g, 0.10 mol) in acetonitrile (30 m
l) was added. The reaction mixture was refluxed for 2 hours and then cooled. The triethylamine hydrochloride was removed, and the mouth liquid was concentrated to dryness. Sodium fluoroborate (23 g) was dissolved in water (40 ml) and this solution was added to the above residue,
Stir vigorously. Since the product precipitated, it was taken out, washed with isopropyl alcohol, and dried at 40 ° C. Yield is
The amount was 21.19 g (81.5% yield).

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

Other compounds of the present invention can be synthesized in good yield by the same method. The amount of the hardener used in the practice of the present invention varies depending on the type of the light-sensitive material to be applied, but is preferably in the range of 0.01 to 100% by weight, more preferably 0.1 to 30% by weight of the dry weight of the binder. It is.

The hydrophilic binder used in practicing the present invention is arbitrary, such as generally used gelatin, gelatin derivatives, and graft polymers of gelatin and other polymers.

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

In practicing the present invention, silver halide, a chemical sensitizer, a silver halide solvent, a spectral sensitizing dye, a silver halide used in a silver halide emulsion layer or other layers of a light-sensitive material.
There are no particular restrictions on antifoggants, hydrophilic protective colloids such as gelatin, ultraviolet absorbers, polymer latex, brighteners, color couplers, antifading agents, dyes, matting agents, surfactants, etc., for example, research.・ Disclosure (Research Disclosure) Volume 176, pages 22-31 (19
(December 1978) can be used.

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

[0051]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples.

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

On a 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.

First layer; Antihalation layer (HC) Black colloidal silver 0.15 Ultraviolet absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling solvent (O-1) 0.20 High boiling solvent (O- 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 (O-1) 0.55 Additive (SC-1) 0.003 gelatin 1.0 fourth layer; high-sensitivity red-sensitive emulsion layer (R-H) silver iodobromide emulsion (Em-3) increased by 0.9 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 solvent (O-1) 0.25 Additive (SC-1) 0.003 Gelatin 1.0 Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 Sixth layer; Low Sensitive 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 (O-2) 0.70 Additive (SC-1) 0.003 Gelatin 1.0 Layer 7; High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S- ) 1.1 × 10 ^-4 Sensitizing dye (S-7) 2.0 × 10 -4 Sensitizing dye (S-8) 0.3 × 10 -4 Magenta coupler (M-1) 0.03 Magenta coupler (M-2) 0.13 Colored magenta Coupler (CM-1) 0.04 DIR compound (D-3) 0.004 High boiling solvent (O-2) 0.35 Additive (SC-1) 0.003 Gelatin 1.0 8th layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-2) 0.12 High boiling point solvent (O-2) 0.15 Gelatin 1.0 Ninth layer; Low-sensitivity blue-sensitive emulsion layer (BL) Silver halide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em-2) 0.25 Sensitizing dye (S-9) 5.8 × 10 ^-4 Yellow coupler (Y-1) 0.60 Yellow coupler (Y-2) 0.32 DIR Compound (D-1) 0.003 DIR compound (D-2) 0.006 High boiling point solvent (O-2) 0.18 Additive (S C-1) 0.004 gelatin 1.3 10th layer; high-sensitivity blue-sensitive emulsion layer (BH) silver iodobromide emulsion (Em-4) 0.5 sensitizing dye (S-10) 3.0 × 10 ^-4 sensitizing dye ( S-11) 1.2 × 10 ^-4 yellow coupler (Y-1) 0.18 yellow coupler (Y-2) 0.10 high boiling point solvent (O-2) 0.05 additive (SC-1) 0.002 gelatin 1.0 11th layer; Protective layer (PRO-1) Silver iodobromide emulsion (Em-5) 0.3 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.1 Additive (HS-1) 0.2 Additive (HS-2) 0.1 High boiling solvent (O-1) 0.07 High boiling solvent (O-3) 0.07 Gelatin 0.8 12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Poly Methyl methacrylate (average particle size 3 μm) 0.02 Sliding agent (WAX-1) 0.04 Charge control agent (SU-1) 0.004 band The modifier (SU-2) 0.02 Gelatin 0.5 layers was as shown in Table 1 in addition to the above by adding a hardener or a comparison of the hardening agent of the present invention to create a sample 1-16.

Each layer has a coating aid (SU-4),
Dispersing aid (SU-3), stabilizer (ST-1), preservative (DI-1), antifoggant (AF-1), (AF-
2) and dyes (AI-1) and (AI-2) were appropriately added.

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

Em-1: average silver iodide content of 7.5 mol%
Average particle size 0.55 μm Grain shape Octahedron Em-2: Average silver iodide content 2.5 mol% Average particle 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 particle size
1.02 μm Grain shape Octahedron Em-5: Average silver iodide content 2.0 mol% Average grain size
0.08μm

[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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Each of the prepared samples was used as a fresh sample,
The sample was allowed to stand at room temperature for 7 days,
The samples were left at 2% RH for 2 days to prepare forcibly deteriorated samples.

After subjecting these samples to wedge exposure with white light, the following treatments were performed to measure the sensitivity and fog.

The sensitivity is represented by the reciprocal of the exposure amount giving a density of fog + 0.5, and is expressed as a relative sensitivity with the sensitivity of Sample 1 left at room temperature for 7 days after coating as 100.

The sample left for 7 days at room temperature was
Immersed 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 a range of 0 to 200 g while moving in parallel on the membrane surface at a speed of 2 mm per second. The load when the film surface of the sample was damaged by continuous change was determined as the scratch resistance.

The results are shown in Table 1 below.

Processing Step Color development 38 ° C 3 minutes 15 seconds Bleaching 38 ° C 6 minutes 30 seconds Rinse 38 ° C 3 minutes 15 seconds Fix 38 ° C 6 minutes 30 seconds Rinse 38 ° C 3 minutes 15 seconds Stabilize 25 ° C 1 Min. 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 liter.

(Bleaching solution) 100 g of ammonium ammonium salt of ethylenediaminetetraacetic acid 100 g of diammonium salt of ethylenediaminetetraacetic acid 150 g of ammonium bromide 10 g of glacial acetic acid 10 ml of water was added to make 1 liter, and the pH was adjusted to 6.0 with aqueous ammonia.

(Fixing solution) Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water was added to 1 liter, and the pH was adjusted to 6.0 with acetic acid.

(Stabilizing Solution) Formalin (37% aqueous solution) 1.5 ml KONIDAX (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

[0078]

[Table 1]

[0079]

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As is clear from the results in Table 1 above, Samples 1 to 12 using the hardener according to the present invention showed only a slight decrease in relative sensitivity as compared with Comparative Samples 13 to 16, No fog deterioration is observed.

Even in the case of forced deterioration, Samples 1 to 12 of the present invention show a slight decrease in sensitivity and a slight increase in fog compared to Comparative Samples 13 to 16.

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

Further, from the results of the scratch resistance indicating the film strength, each of the samples of the present invention 1 to 12 shows a higher film strength as compared with the comparative samples 13 to 16; Indicates that the film is hardened more efficiently than the comparative compound.

Example 2 Layers having the following compositions were sequentially formed on both sides of a subbed polyethylene terephthalate support from the support side to obtain photosensitive material samples 17 to 32 for X-rays.

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

First layer: Crossover cut layer Dye (I) 3 mg / m ² Mordant (II) 0.12 g / m ² Gelatin 0.20 g / m ² Second layer: Emulsion layer Average particle size 0.57 μm, AgI 2 mol% Emulsion consisting of AgBrI containing silver coating amount 4.5 mg / m ² sensitizing dye (A) 450 mg sensitizing dye (B) 20 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3.0 g t- Butyl-catechol 400mg Polyvinylpyrrolidone (Molecular weight 10,000) 1.0g Styrene-maleic anhydride copolymer 2.5g Trimethylolpropane 10.0g Diethylene glycol 5.0g p-nitrophenyl-triphenylphosphonium chloride 50mg 1,3-dihydroxybenzene-4-sulfone Ammonium citrate 4.0g 2-Mercaptobenzimidazole-5-sodium sulfonic acid 15mg Additive A 70mg Additive B 1.0g 1,1-dimethylol-1-bromo-1-nitromethane 10mg Gelatin 2g / m ² Third layer: protective layer Polymeth Methacrylate (average particle diameter 5μm) 7mg / m ² Colloidal silica (average particle diameter 0.013μm) 70mg / m ² Additives C 10 mg / m ² Additives D 2 mg / m ² Additives E 7 mg / m ² Additives F 15 mg / m ² gelatin 1 g / m ² hardener (described in Table 2) Preservative DI-1 was added to each sample.

[0087]

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[0088]

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[0089]

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After a storage test was performed on each sample in the same manner as in Example 1, the sample was exposed to light and subjected to the following treatment, and the photographic characteristics were measured in the same manner as in Example 1.

The sensitivity of the sample 17 on the 7th day after application was 100
The relative sensitivity was expressed as

Table 2 shows the results.

(Processing step) Insertion 1.2 seconds Development + migration 35 ° C 14.6 seconds Fixing + migration 33 ° C 8.2 seconds Rinse + migration 25 ° C 7.2 seconds Squeeze 40 ° C 5.7 seconds Drying 45 ° C 8.1 seconds (Developer) Hydroquinone 25.0 g phenidone 1.2 g Potassium sulfite 55.0 g Boric acid 10.0 g Sodium hydroxide 21.0 g Triethylene glycol 17.5 g 5-Nitroimidazole 0.10 g 5-Nitrobenzimidazole 0.10 g Glutaraldehyde bisulfite 15.0 g Glacial acetic acid 16.0 g Potassium bromide 4.0 g Triethylene Add 2.5g of tetramine hexaacetic acid to make up to 1 liter.

(Fixing solution) Ammonium thiosulfate 130.9 g Anhydrous sodium sulfite 7.3 g Boric acid 7.0 g Acetic acid (90 wt%) 5.5 g Sodium acetate (trihydrate) 25.8 g Aluminum sulfate (18 hydrate) 14.6 g Sulfuric acid (50 wt%) 6.77g Add water to make up to 1 liter.

Further, while keeping the sample at 25 ° C. and 50% RH, 2 hours, 8 hours, 1 day and 7 days after application, a part of each sample was taken out and swollen in 30 ° C. water for 5 minutes. Then, the film thickness of each sample was measured, and the degree of swelling V represented by the following equation was calculated.
The change over time (post-hardening property) of the curing action was observed.

The results are shown in Table 2 below.

[0097]

(Equation 1)

[0098]

[Table 2]

As is clear from the results shown in Table 2, in the X-ray photosensitive materials 17 to 28 in which the hardener of the present invention was added to the protective layer, almost no change in photographic characteristics such as a decrease in sensitivity and an increase in fog was observed. is not, moreover coating, if built one day or more after drying also small and stable change in the degree of swelling after the same manner as in Comparative sample 29 to 32
Hardness has been improved. Also, when the final degree of swelling is compared, it can be seen that the hardening is efficiently performed.

[0100]

As described above, according to the present invention, a hardening action can be efficiently performed even with a small amount of a hardening agent without impairing photographic performance.
A silver halide photographic light-sensitive material containing a novel hardener having no post-hardening action can be provided.

Continuation of the front page (56) References JP-A-63-229450 (JP, A) JP-A-61-100743 (JP, A) JP-A-60-225148 (JP, A) JP-A-1-155334 (JP) JP-A-2-37339 (JP, A) JP-A-3-501033 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03C 1/30 CAPLUS (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A silver halide photographic material having at least one hydrophilic colloid layer on a support, wherein at least one of the hydrophilic colloid layers has the following general formula [I]:
A silver halide photographic light-sensitive material, which is hardened with at least one compound represented by the formula: Embedded image [Wherein, R ₁ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, and R ₄ —Y ₂ —,
It represents a _{(R 5) (R 6)} > N- or _{(R 7) (R 8)} > C = group represented as N-. (However, R ₄ , R ₅ , R ₆ , R ₇ , and R ₈ each represent an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ₇ and R ₈ may be hydrogen atoms. R ₅ and R ₆ ,
R ₇ and R ₈ may be bonded to each other to form a ring. Y ₂ represents an oxygen atom or a sulfur atom. ) R ₂ , R
₃ is an alkyl group which may be the same or different,
Represents an alkenyl group, an aryl group, or an aralkyl group.
Any _{two of} R ₁ , R ₂ and R ₃ may be bonded to form a ring. Y ₁ represents an oxygen atom or a sulfur atom. Z ₁
Represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring. X
₁ ^- represents an anion portion of the free anion or molecules to form an intramolecular salt. ] 2. The silver halide photographic material according to claim 1, wherein the general formula [I] is represented by the following general formula [II]. Embedded image [R ₉ represents an alkyl group, an alkenyl group, an aryl group, or an aralkyl group. R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ represent a hydrogen atom or a substituent. R ₁₀ and R _11, R ₁₁ and R _12, or substituents attached adjacent to the R ₁₂ and R _13, may form a condensed ring. Y ₃ represents an oxygen atom or a sulfur atom. Z ₂ represents an atomic group necessary for forming a nitrogen-containing heterocyclic ring. X ₂
^- represents an anion portion of the free anion or molecules to form an intramolecular salt. ]