JPH10177232A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the stability of a latent image by hardening a silver halide emulsion layer with a vinylsulfone hardening agent having a hydroxyl group and specifying the electric potential of silver in the layer. SOLUTION: This silver halide photographic sensitive material has at least one silver halide photographic emulsion layer on the substrate. The emulsion layer has been hardened with a vinylsulfone hardening agent having at least one hydroxyl group and the electric potential of silver in the layer is 50-125mV. Hydrophilic colloid used is gelatin freed of calcium. The thickness of the hydrophilic colloidal layer on the substrate is 10-25μm. The electric potential of the silver is measured by cutting 500cm<2> of the silver halide photographic sensitive material in a strip shape in a darkroom, immersing it in 100cc pure water for 6hr and disposing a silver ion electrode and a satd. silver-silver chloride electrode as a reference electrode in the water. The electric potential of the silver is regulated by adding a water-soluble silver salt and a water-soluble halide to a coating soln. for the photographic sensitive material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material, and more particularly, to a silver halide photographic material having improved latent image stability.

[0002]

2. Description of the Related Art In recent years, with the widespread use of films with lenses and the like, the number of photo opportunities at, for example, summer tourist spots has been rapidly increasing. Frequently, the user is exposed to a high-temperature and high-humidity environment such as a car or a bag between the start of shooting and the end of shooting, and it has become important to improve the stability of the latent image under such circumstances.

As a technique for improving the stability of a latent image, reduction sensitization has long been known. JP-A-3-19613
Nos. 6 and 4-32832 disclose a technique for improving the stability of a latent image by reduction sensitization with ascorbic acid or a derivative thereof in the presence of an oxidizing agent such as thiosulfonic acid. It was not enough to accompany.

Also, a method using a benzothiazolium described in Japanese Patent Application Laid-Open No. 50-94918 and a method using a Schiff base described in Japanese Patent Application Laid-Open No. 57-100425 are known. Did not.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having high sensitivity and excellent latent image stability.

[0006]

The above objects of the present invention have been attained by the following constitutions.

(1) A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the silver halide emulsion layer has a vinyl sulfone hardened film having at least one hydroxyl group. A silver halide photographic light-sensitive material characterized by being hardened by an agent and having a coating silver potential of 50 mv or more and 125 mv or less.

(2) The silver halide photographic material as described in (1) above, wherein the silver halide photographic material is a silver halide color photographic material.

(3) The silver halide photographic material as described in (1) or (2) above, wherein the hydrophilic colloid used in the silver halide photographic material is decalcified gelatin.

(4) The thickness of the hydrophilic colloid layer on the support is from 10 to 25 μm.
Or the silver halide photographic light-sensitive material according to 3.

The silver potential of the coating film in the present invention is defined as the silver halide photographic material 500 cm ² coated on a support, cut into strips in a dark room, immersed in 100 cc of pure water for 6 hours, Is measured using a silver ion electrode using a commercially available saturated silver-silver chloride electrode as a reference electrode.

The coating silver potential is adjusted by adding a water-soluble silver salt (eg, AgNO ₃ ) and a water-soluble halide (eg, KBr, NaBr) to a coating solution of a photographic light-sensitive material. When the silver halide photographic material is composed of a plurality of layers, the layer to which the compound for adjusting the silver potential of the coating film is not limited to a layer containing silver halide.

The silver potential of the coating film for obtaining the latent image stability improving effect of the present invention is 125 mv or less, preferably 70 mv or less.
mv or more. On the other hand, if it is less than 50 mv, the sensitivity is remarkably lowered, which is not preferable.

The vinyl sulfone hardener having a hydroxyl group of the present invention is preferably represented by the following general formula (1).

Formula (1) (CH ₂ ＣＨCHSO ₂ ) _n A In the formula, A is an n-valent group having at least one hydroxyl group, and n is 2, 3 or 4.

In the general formula (1) of the present invention, A represents an n-valent acyclic hydrocarbon group having 1 to 10 carbon atoms, a 5- or 6-membered heterocyclic ring containing nitrogen, oxygen or sulfur atom, 5 or 6 Membered cycloaliphatic radical or at least one aralkylene radical having 7 to 10 carbon atoms. The acyclic hydrocarbon group is preferably an alkylene group having 1 to 8 carbon atoms. Each group represented by A may have a substituent or may be linked to one another via a heteroatom such as a nitrogen, oxygen and / or sulfur atom, or a carbonyl or carbamide group. A may be substituted with, for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group and an ethoxy group, a halogen atom such as a chlorine atom and a bromine atom, and an acetoxy group.

The hardener of the general formula (1) of the present invention can be obtained, for example, by the same method as described in US Pat. No. 4,173,481.

The hardener represented by the general formula (1) of the present invention is used in an amount of 1 to 25 mg per 1 g of the hydrophilic colloid,
Preferably it is 2 to 20 mg.

Gelatin is particularly preferred as the hydrophilic colloid of the present invention. As the gelatin, any of alkali-treated gelatin and acid-treated gelatin can be preferably used. Gelatin is preferably one from which salts such as calcium are removed, and the concentration of calcium is 100 ppm or less,
Preferably it is 50 ppm or less. Examples of other hydrophilic colloids include water-soluble polymers such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and dextran sulfate.

When gelatin is used for the hydrophilic colloid layer, the amount of the gelatin is ² to 25 g / m ² , preferably 3 to 20 g / m ² .

Specific examples of the hardener represented by the general formula (1) will be given.

[0022]

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[0023]

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As the hardener of the present invention, in addition to the hardener represented by the general formula (1), other hardeners may be added as long as the stability of the latent image is not impaired. For example, other vinyl sulfone hardeners, carboxy active hardeners, etc. may be mentioned, but hardeners represented by the following general formula (2) are preferred.

[0025]

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In the general formula (2), M is Na
Is preferred.

The composition of the silver halide photographic emulsion according to the present invention has an arbitrary halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chloroiodobromide, silver chloroiodide and the like. It may be something.

The silver halide used in the present invention is preferably a tabular silver halide. These tabular silver halides have an average aspect ratio of 5 to 20, preferably 8 to 20. The diameter is preferably 0.3 to 10 microns, more preferably 0.5 to 5 microns. The thickness is preferably 0.05 to 1.5 microns.

As the silver halide grains according to the present invention, grains having a single shape are preferably used, but it is also preferable to add two or more monodispersed silver halide emulsions to the same layer.

As the apparatus and method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion according to the present invention may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form in which the soluble silver salt and the soluble halide salt are reacted may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one type of the double jet method, a pAg controlled double jet method described in JP-A-54-48521 can be used.

Further, JP-A-57-92523, JP-A-57-92523.
No.-92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device disposed in a reaction mother liquor, and a water-soluble silver described in DE-A-2,921,164. A device for continuously adding a salt and an aqueous solution of a water-soluble halide salt while changing the concentration,
No. 501776, etc., a reaction mother liquor may be taken out of a reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

In the present invention, it is preferable to use a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization. As the chemical sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used. Photographic additives that can be used in the present invention include RD308119 and R
D17643, RD18716 and the like.

Various couplers can be used in the present invention, and specific examples are also described in the above RD.

The additive used in the present invention is RD3081
RD17643, p. 28, RD187.
The supports described on pages 16647-8 and XIX of RD308119 can be used.

The light-sensitive material of the present invention includes the aforementioned RD3081
Auxiliary layers such as a filter layer and an intermediate layer described in 19VII-K can be provided, and various layer configurations such as a normal layer, a reverse layer, and a unit configuration can be adopted.

The present invention can be applied to various color photosensitive materials represented by color negative films for general use or movies, color reversal films for slides or televisions, and color positive films.

In these color photosensitive materials, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 25 μm or less, more preferably 20 μm or less.
It is more preferably 18 μm or less. Also, the membrane swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% under humidity control (2 hr), and the film expansion _/ swelling rate T _1/2 can be measured according to a method known in the art.

The swelling _/ swelling rate T _1/2 can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. or,
The swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above according to (maximum swelling film thickness-film thickness) / film thickness.

The color photographic material is RD17643 as described above.
Pages 28 and 29 and RD18716 at page 615, left column to right column.

When the color light-sensitive material is used in the form of a roll, it is preferable to take the form housed in a cartridge. The most common cartridge is a 135 format cartridge currently available. Others
The cartridge proposed in the following patent can also be used.

JP-A-58-67329, JP-A-58-67329
181035, U.S. Pat. No. 4,221,479, JP-A Nos. 1-231045 and 2-199451, U.S. Pat. Nos. 4,846,418, 4,848,693, and 4,832,275.

The present invention can be applied to a "small photographic roll film cartridge and film camera" filed on Jan. 31, 1992 (Toshihiko Yagi et al.).

Examples of the sensitizing dye include polymethine dyes including cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, merostyryl and streptocyanin. Can be mentioned.

Examples of antifoggants and stabilizers include tetrazaindenes and azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles and mercaptothiazoles , Mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole (especially 1-phenyl-5-mercaptotetrazole), etc .; Compounds, furthermore benzenethiosulfinic acid,
Benzenesulfinic acid, benzenesulfonamide,
Hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives and ascorbic acid derivatives can be mentioned.

When sensitization is carried out in the presence of a silver halide solvent, good results are often obtained. Examples of the silver halide solvent used include U.S. Pat.
(A) Organic thioethyls described in JP-A-53-12891 and JP-A-3,574,628, JP-A-54-1019, JP-A-54-158917, etc., and JP-A-53-82408. No. 55-77737, No. 55
(B) Thiourea derivatives described in JP-A-2982, and (c) Halogen having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319. Silver halide solvent, JP-A-54-
No. 100717, (d) imidazoles, (e) sulfites, (f) thiocyanates and the like.

[0049]

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

Example 1 On the back of a 120μ cellulose triacetate support,
Each layer having the following composition was sequentially applied.

First layer Alumina sol AS100 (manufactured by Nissan Chemical Industries, Ltd.) 0.8 g / m ² diacetyl cellulose 1.5 g / m ² Second layer diacetyl cellulose 20 mg / m ² SiO ₂ fine particles (average particle size 3 μm) 4 mg / m ² Third layer Carnauba wax (melting point: 83 ° C.) 0.1 g / m ^{2 An} undercoat made of poly (vinyl acetate-maleic anhydride) was applied on the backed support, and each layer having the following composition: A multilayer color photosensitive material was prepared. Incidentally, the amount of additive is indicated in grams per photosensitive material 1 m ^2, a silver halide emulsion and colloidal silver are indicated in terms of silver value. The sensitizing dye is silver halide 1 contained in the same layer.
It was shown in moles per mole. The silver potential of the coating film was adjusted by KBr.

First layer: Antihalation layer Black colloidal silver 0.15 Ultraviolet absorber (UV-1) 0.30 High boiling solvent (Oil-1) 0.16 Gelatin 1.64 Second layer: Intermediate layer Gelatin 0 .80 third layer: low-sensitivity red-sensitive layer silver iodobromide emulsion (average particle size 0.20 μm) 0.44 silver iodobromide emulsion (average particle size 0.40 μm) 0.11 sensitizing dye (SD-1) ) 2.6 × 10 ^-5 sensitizing dye (SD-2) 2.6 × 10 ^-5 sensitizing dye (SD-3) 3.1 × 10 ^-4 sensitizing dye (SD-4) 2.3 × 10 ^-5 sensitizing dye (SD-5) 2.8 × 10 ^-4 cyan coupler (C-1) 0.35 colored cyan coupler (CC-1) 0.065 compound (GA-1) 2.0 × 10 ^-3 High boiling point solvent (Oil-1) 0.33 Gelatin 0.73 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 0.49 μm) 0.39 sensitizing dye (SD-1) 1.3 × 10 ^-4 sensitizing dye (SD-2) 1.3 × 10 ^-4 sensitizing dye (SD-3) 2.5 × 10 ^-4 sensitizing dye (SD-4) 1.8 × 10 ^-5 cyan coupler (C-1) 0.24 colored cyan coupler (CC-1) 0.040 DIR compound (D-1) 0.025 compound ( GA-1) 1.0 × 10 ⁻³ High boiling point solvent (Oil-1) 0.30 Gelatin 0.59 Fifth layer: High-sensitivity red-sensitive layer Silver iodobromide emulsion (average particle size 0.55 μm) 91 sensitizing dye (SD-1) 8.5 × 10 ^-5 sensitizing dye (SD-2) 9.1 × 10 ^-5 sensitizing dye (SD-3) 1.7 × 10 ^-4 sensitizing dye ( SD-4) 2.3 × 10 ^-5 cyan coupler (C-2) 0.10 colored cyan coupler (CC-1) 0.014 DIR compound (D-1) 7 5 × 10 ^-3 Compound (GA-1) 1.4 × 10 -3 High boiling solvent (Oil-1) 0.12 Gelatin 0.53 Sixth Layer: Intermediate Layer Gelatin 1.14 Seventh Layer: Low Sensitivity Green Sensitive layer Silver iodobromide emulsion (average particle size 0.40 μm) 0.32 Silver iodobromide emulsion (average particle size 0.30 μm) 0.74 Sensitizing dye (SD-7) 5.5 × 10 ^-4 increase Sensitizing dye (SD-1) 5.2 × 10 ^-5 Sensitizing dye (SD-12) 4.8 × 10 ^-5 Magenta coupler (M-1) 0.15 Magenta coupler (M-2) 0.37 Colored Magenta coupler (CM-1) 0.20 DIR compound (D-2) 0.020 Compound (GA-1) 4.0 × 10 ^-3 High boiling solvent (Oil-2) 0.65 Gelatin 1.65 8th Layer: Highly sensitive green-sensitive layer Silver iodobromide emulsion (average particle size 0.62 μm) 0.79 Sensitizing dye (SD-8) 1.4 × 10 ^-4 sensitizing dye (SD-9) 1.5 × 10 ^-4 sensitizing dye (SD-10) 1.4 × 10 ^-4 sensitizing dye (SD-12) 7.1 × 10 ^-5 magenta Coupler (M-2) 0.065 Magenta coupler (M-3) 0.025 Colored magenta coupler (CM-2) 0.025 DIR compound (D-3) 7.0 × 10 ^-4 compound (GA-1) 1.8 × 10 ^-3 high boiling point solvent (Oil-2) 0.15 gelatin 0.46 ninth layer: yellow filter layer yellow colloidal silver 0.10 compound (SC-1) 0.14 compound (FS-1) 0.20 High boiling point solvent (Oil-2) 0.18 Gelatin 1.20 10th layer: low-sensitivity blue-sensitive layer Silver iodobromide emulsion (average particle size 0.40 μm) 0.17 Silver iodobromide emulsion (average particle size 0.30 .mu.m) 0.20 sensitizing dye (SD-11) 5.4 × 10 -4 sensitization Containing ^{(SD-12) 2.0 × 10} -4 Yellow coupler (Y-1) 0.62 Yellow coupler (Y-2) 0.31 Compound ^{(GA-1) 4.5 × 10} -3 High boiling solvent ( Oil-2) 0.20 gelatin 1.27 11th layer: high-sensitivity blue-sensitive layer Silver iodobromide emulsion (average particle size 0.70 μm) 0.66 sensitizing dye (SD-11) 2.5 × 10 ^{− 4} Sensitizing dye (SD-12) 2.0 × 10 ^-4 Yellow coupler (Y-1) 0.10 Compound (GA-1) 2.0 × 10 ^-3 High boiling point solvent (Oil-2) 0.04 Gelatin 0.57 Twelfth layer: First protective layer Silver iodobromide emulsion (average particle size 0.04 μm, silver iodide content 4.0 mol%) 0.30 Ultraviolet absorber (UV-2) 0.030 UV absorber (UV-3) 0.015 UV absorber (UV-4) 0.015 UV absorber (UV- ) 0.015 UV absorber (UV-6) 0.10 Compound (FS-1) 0.25 High boiling solvent (Oil-1) 0.07 High boiling solvent (Oil-3) 0.07 Gelatin 1.04 Thirteenth layer: Second protective layer Polyco (methyl methacrylate-ethyl methacrylate-methacrylic acid) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Slip agent (WAX-1) 0.04 Fluorosurfactant Agent (F-1) 0.01 Fluorosurfactant (F-2) 0.01 Gelatin 0.55 In addition to the above composition, a coating aid Su-1, a dispersion aid Su-2, Viscosity modifiers, dyes AI-1, AI-2, stabilizers ST-1, antifoggants AF-1, AF-2, AF-
3 and preservative DI-1 were added as appropriate. Gelatin having a calcium content of 10 ppm or less was used.

The structure of the compound used for preparing the above sample is shown below.

[0054]

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[0055]

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[0056]

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[0057]

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[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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The samples having this layer constitution were hardened with various hardeners so as to have the same degree of swelling. Table 1 shows the types of hardeners. Evaluation of photographic performance and latent image stability of the sample thus prepared was performed as follows. Photographic performance was represented by sensitivity.

(Photographic Performance) The sample was exposed to white neutral wedge and subjected to the following standard color development processing. For the developed sample, a densitometer X-RITE manufactured by X-RITE
The green density was measured at to obtain a sensitometric curve.
The sensitivity was determined from the reciprocal of the exposure amount giving the minimum density of the sample +0.5. The relative sensitivity was shown with the sensitivity of the blank sample as 100.

(Stability of Latent Image) Two sets of samples subjected to white neutral wedge exposure were prepared.
It was stored for 7 days under RH conditions, and the other set was stored under frozen conditions for the same period. The two sets of samples were subjected to the following standard color development processing and density measurement to determine a sensitivity difference of minimum density + 0.5 (sensitivity of a frozen storage product-sensitivity of a heated and humidified storage product).

(Processing Step) Color development (38.0 ± 0.1
° C for 3 minutes 15 seconds) → Bleaching (38.0 ± 3.0 ° C for 6 minutes 3)
0 seconds) → Washing (3 minutes 15 seconds at 24 ° C. to 41 ° C.) → Fixing (6 minutes 30 seconds at 38.0 ± 3.0 ° C.) → Washing (24 ° C.
3 minutes and 15 seconds at 41 ° C) → stable (38.0 ± 3.0 ° C at 3 ° C)
15 minutes) → Drying (50 ° C. or less) (Color developing solution) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline sulfate 4.75 g 4.25 g of anhydrous sodium sulfite 4.25 g hydroxyl Amine 1/2 sulfate 2.00 g Anhydrous potassium carbonate 37.5 g Sodium bromide 1.30 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.50 g Potassium hydroxide 1.00 g Add water to make 1 liter, Adjust pH to 10.1.

(Bleaching Solution) Iron Ammonium Ethylene Diamine Tetraacetate 100.0 g Diammonium Ethylene Diamine Tetraacetate 10.0 g Ammonium Bromide 150.0 g Glacial acetic acid 10.0 g Water was added to make 1 liter, and the pH was adjusted to 6.0 using ammonia water. Adjust to 0.

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

(Stabilizing Solution) Formalin (37% aqueous solution) 1.5 cc KONIDAX (manufactured by Konica Corporation) 7.5 cc Add water to make 1 liter.

The above results are summarized in Table 1.

[0071]

[Table 1]

Example 2 The same evaluation was carried out using gelatin having a calcium content of 500 ppm instead of the gelatin having a calcium content of 10 ppm or less used in Example 1. Table 2 shows the results.

[0073]

[Table 2]

[0074]

As demonstrated in the examples, the samples using the vinyl sulfone hardener having at least one hydroxyl group of the present invention are silver halides having high sensitivity and excellent latent image stability. You can see that it is a photographic material.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideo Ota 1 Konica Corporation, Sakura-cho, Hino-shi, Tokyo

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide photographic emulsion layer on a support, wherein the silver halide emulsion layer has at least one hydroxyl group. A silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material has a film potential of 50 mv or more and 125 mv or less. 2. The silver halide photographic material according to claim 1, wherein said silver halide photographic material is a silver halide color photographic material. 3. The silver halide photographic material according to claim 1, wherein the hydrophilic colloid used in the silver halide photographic material is decalcified gelatin. 4. The film thickness of the hydrophilic colloid layer on the support is 1
4. The silver halide photographic light-sensitive material according to claim 1, wherein the thickness is 0 to 25 [mu] m.