JPH06123930A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material contg. a novel hardening agent which does not adversely affect the photographic performance. CONSTITUTION:This silver halide photographic sensitive material is hardened with at least one kind of compd. represented by the general formula (where Y is O or S and Z is a group of atoms required to form an N-contg. hetero ring).

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 In general, a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) includes, for example, a silver halide emulsion layer,
Various photographic constituent layers such as an intermediate layer, a protective layer, a filter layer, a subbing layer, an antihalation layer, an ultraviolet absorbing layer, an antistatic layer and a backing layer are provided on a support such as glass, paper and synthetic resin film. It consists of

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 they are. 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 a photographic constituent layer to improve its mechanical strength. Aldehyde compounds such as formaldehyde and glutaraldehyde, US Pat. No. 2,732,30
3, 3,288,775, British Patent 974,723, 1,167,207
Compounds having a reactive halogen as described in No.
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-diacryloylhexa Hydro-1,3,5-triazine, U.S. Patents 3,232,763, 3,635,718, British Patent 99
Compounds having a reactive olefin as described in 4,809,
U.S. Pat.Nos. 3,539,644, 3,642,486, Japanese Patent Publication No. 49-13563
No. 53-47271, 56-48860, JP-A-53-57257,
61-128240, 62-4275, 63-53541, 63-264
Vinylsulfonyl compounds described in 572, N-hydroxymethylphthalimide, U.S. Patents 2,732,316 and 2,58
N-methylol compounds described in 6,168, etc., U.S. Pat.
Isocyanates described in 3,437, US Patent 2,983,6
No. 11, No. 3,107,280 and other aziridine compounds,
U.S. Patents 2,725,294, acid derivatives described in 2,725,295 and the like, carbodiimide compounds described in U.S. Patent 3,100,704, epoxy compounds described in U.S. Patent 3,091,537, U.S. Patents 3,321,313, 3,543,292 etc. Isoxazole compounds described, halogenocarboxaldehydes such as mucochloric acid, organic hardeners such as dioxane derivatives such as dihydroxydioxane and dichlorodioxane, and inorganic hardeners such as chromium alum, zirconium sulfate and chromium trichloride. Is disclosed.

However, when these known hardeners are used in a light-sensitive material, the hardening action is not sufficient, and the hardening action referred to as "post-hardening", which is caused by a slow hardening reaction to gelatin, changes over time. There is an adverse effect on the performance of the light-sensitive material (especially, increase in fog, decrease in sensitivity or maximum density, softening of gradation, etc.), loss of hardening effect due to other coexisting photographic additives, etc. Photographic Additives (eg couplers in internal color emulsions)
Each of them had some drawbacks, such as those which reduced the efficacy of or 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 No. 55
-38655, acyl imidazoles, JP-B-53-220
Compounds containing two or more N-acyloxyimino groups in the molecule described in JP-A No. 89, compounds having an N-sulfonyloxyimide group described in JP-A-52-93470, JP-A-58-113929
Compounds having a phosphorus-halogen bond described in JP-A-6-29187
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, since many of these hardeners affect the photographic characteristics, and the hardening reaction of gelatin is fast and the side reaction which is decomposed by water is also fast, a general method for producing a photographic light-sensitive material using an aqueous solution of gelatin. However, 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 Accordingly, 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 characteristics. Especially.

Secondly, it is to provide a photographic light-sensitive material which is hardened by a hardening agent having a quick hardening action and without post-hardening.

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

[0011]

The above 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 ] A silver halide photographic light-sensitive material characterized by being hardened with at least one compound represented by the following formula.

[0012]

[Chemical 2]

The present invention will be described in detail below.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

[0016]

[Chemical 5]

[0017]

[Chemical 6]

[0018]

[Chemical 7]

Here, R ₁ is an alkyl group (eg, methyl, ethyl, n-propyl, iso-propyl, n-butyl group, etc.), an aryl group (eg, phenyl, tolyl, naphthyl group, etc.), an aralkyl group (eg, benzyl). Group, phenethyl group, etc.).

R ₂ represents a hydrogen atom or a lower alkyl group (eg, methyl, ethyl, n-propyl group, etc.). or,
The above-exemplified groups may be further substituted, and preferred substituents are halogen atom (eg chlorine, fluorine atom etc.), alkoxy group (eg methoxy, ethoxy group etc.), sulfo group, sulfoamino group, sulfooxy group etc. Is mentioned.

Hereinafter, examples of the compound represented by the general formula [I] according to the present invention will be given, but the present invention is not limited thereto.

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

[0025]

[Chemical 11]

[0026]

[Chemical 12]

The above compounds of the present invention can be easily synthesized by known methods. For example, it can be easily obtained by reacting a compound represented by the following general formula [II] with phosgene or diphosgene in the presence of a base at a low temperature.

[0028]

[Chemical 13]

In the formula, Y and Z have the same meanings as those represented by the general formula [I].

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

(Synthesis of Exemplified Compound 1) To a methylene chloride solution containing 9.9 g of trichloromethyl chloroformate, a methylene chloride solution containing 19 g of 2-hydroxypyridine and 21 g of triethylamine was added dropwise at an internal temperature of 0 ° C., and then at 0 ° C. for 2 hours. It was stirred. The precipitated triethylammonium chloride was removed by filtration, and then concentrated under reduced pressure at 30 ° C or lower to obtain crude crystals. The crude crystals were recrystallized from toluene to obtain 18 g of Compound 1. (Mp 86 ° C). 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 the practice of the present invention is
The dry weight of the binder is preferably 0.01, although it varies depending on the type of the photosensitive material applied and the type of the hydrophilic binder.
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), 22-31 ( 19
The one described in December 1978) can be used.

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

[0037]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example 1 In all the following examples, the addition amount in the silver halide photographic light-sensitive material is the weight (g) per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms 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.

First layer: antihalation layer (HC) Black colloidal silver 0.15 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.02 High boiling point solvent (O-1) 0.20 High boiling point solvent (O-2) 0.20 Gelatin 1.6 Second layer: Intermediate layer (IL-1) Gelatin 1.6 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 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) 0.5 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 point solvent (O-1) 0.55 Additive (SC-1) 0.003 Gelatin 1.0 4th layer: High sensitivity red feeling Emulsion layer (RH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-1) 1.7 × 10 -4 ( mol / mole of silver) Sensitizing dye (S-2) 1.6 × 10 -4 ( Mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D-2) 0.02 High boiling point 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 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 (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^{− 4} (mol / silver 1 mol) 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 point solvent (O-2) 0.70 Additive (SC-1) 0.003 Gelatin 1.0 7th layer: High-sensitivity red-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S- 6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / 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 (O-2) 0.35 Additive (SC) -1) 0.003 Gelatin 1.0 Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 Additive (HS-1) 0.07 Additive (HS-2) 0.07 Additive (SC-2) 0.12 High boiling point solvent (O- 2) 0.15 gelatin 1.0 9th layer: low-sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion (Em-1) 0.25 iodobromide Emulsion (Em-2) 0.25 Sensitizing dye (S-9) 5.8 × 10 -4 ( mol / mole of silver) 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 (SC-1) 0.002 Gelatin 1.3 10th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodide emulsion (Em-4) 0.50 Sensitizing dye (S-10) 3.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) 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: 1st protective layer (PRO-1) Fine grain silver iodobromide emulsion (Em-5) 0.3 UV absorber (UV-1) 0.07 UV absorber (UV-2) 0.10 High boiling point solvent (O-1) 0.07 High boiling point solvent (O-3) 0. 07 Additive (HS-1) 0.2 Additive (HS-2) 0.1 Gelatin 0.8 12th layer: Second protective layer (PRO-2) Charge series control agent (Su-1) 0.004 Charge series control agent (Su-2) ) 0.02 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 Gelatin 0.5 In addition to the above, each layer contains Samples 1 to 8 were prepared by adding the hardener of the invention or the comparative hardener.

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

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

Em-1: Average silver iodide content 7.5 mol% Average particle 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 Rate 2.0 mol% Average particle size 0.08 μm

[0044]

[Chemical 14]

[0045]

[Chemical 15]

[0046]

[Chemical 16]

[0047]

[Chemical 17]

[0048]

[Chemical 18]

[0049]

[Chemical 19]

[0050]

[Chemical 20]

[0051]

[Chemical 21]

[0052]

[Chemical formula 22]

[0053]

[Chemical formula 23]

[0054]

[Chemical formula 24]

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,
The samples were left for 2 days at 50% RH and forcedly deteriorated to prepare samples.

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

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

A sample left at room temperature for 7 days was
Immerse in 30 ° C water for 5 minutes, press a sapphire needle with a radius of 0.3 mm against the surface of the sample, move the film surface in parallel at a speed of 2 mm per second, and press the sapphire needle in the range of 0 to 200 g. Was continuously changed and the load when the film surface of the sample was damaged was determined as the scratch resistance.

The results are also shown in Table 1 below.

Processing step A (38 ° C.) Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry Drying The composition of the treatment liquid used in each sample process 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 (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter.

[Bleach] Ethylenediaminetetraacetic acid iron ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 ml Water is added to make 1 liter, and pH is adjusted to 6.0 using ammonia water. .

[Fixing solution] Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

[0065]

[Table 1]

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

Even when the samples were forcibly deteriorated, the samples 1 to 5 of the present invention showed a slight decrease in sensitivity and a slight increase in fog as compared with the comparative samples 6 to 8.

Therefore, it can be seen that the hardener according to the present invention hardly impairs photographic characteristics.

Further, from the result of the scratch resistance indicating the film strength,
Inventive Samples 1 to 5 all exhibit higher film strength than Comparative Samples 6 to 8, indicating that the hardener of the present invention hardens more efficiently than the comparative compound. .

Example 2 X-ray photosensitive material samples 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) 0.12 g / m ² gelatin 0.2 g / m ² Second layer: emulsion layer Average particle size 0.57 μm, AgI 2 mol% AgBrI containing emulsion coating silver amount 4.5mg / m ² Sensitizing dye (A) 450mg Sensitizing dye (B) 20mg 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 3.0g t- Butyl-catechol 400 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.5 g Trimethylolpropane 10 g Diethylene glycol 5 g p-Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 4g 2-Mercaptobenzimidazole-5-sodium sulfonate 15mg Additive A 70mg Additive B 1g 1,1-Dimethylol-1-bromo-1-nitromethane 10mg Gelatin 2g / m ² Third layer: Protective layer Polymethylmethacrylate (Average particle size 5 μm) 7 mg / m ² colloidal silica (average particle size 0.013 μm) 70 mg / m ² additive C 10 mg / m ² additive D 2 mg / m ² additive E 7 mg / m ² additive F 15 mg / m ² Gelatin 1 g / m ² Hardener (listed in Table 2) Preservative DI-1 was added to each sample.

[0073]

[Chemical 25]

[0074]

[Chemical formula 26]

[0075]

[Chemical 27]

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.

[0079] (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 16.0g Potassium bromide 4.0g Triethylenetetramine hexaacetic acid 2.5g Add water to make 1 liter.

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

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.

Swelling degree V = thickness increased by swelling / thickness after drying The obtained results are shown in Table 2 below.

[0083]

[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, variations in photographic characteristics such as decrease in sensitivity and increase in fog were hardly observed. It can be seen that no change is observed, and that the change in swelling degree is small and stable after 1 day or more after coating and drying, and the post-hardening property is remarkably improved. Further, it can be seen that the dura mater is made more efficient as compared with Samples 12 to 14.

[0085]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide containing a novel hardener which exhibits a hardener effect efficiently even with a small amount of hardener without impairing photographic performance and has no post-hardener effect. A photographic light-sensitive material can be provided.

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 [Chemical 1]