JPH10177231A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance the physical film properties of the silver halide photographic sensitive material in a developing solution. SOLUTION: The hydrophilic colloidal layer formed on a support is hardened by using vinylsulfone type hardening agent having a hydroxyl group in a weight ratio of (0.5-15):1 to the hardening agent represented by the formula in which M is an H or alkali metal atom. A calcium-freed gelatin is used as the hydrophilic colloid and the hydrophilic colloidal layers on the emulsion layer side of the support have a total thickness of 10-25μm.

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 material, and more particularly, to a silver halide photographic material having excellent film properties when swollen in a developer.

[0002]

2. Description of the Related Art Generally, a silver halide photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material) has a silver halide emulsion layer in which silver halide grains are dispersed using a hydrophilic colloid such as gelatin as a binder. Since the development is generally carried out by a wet method, the hydrophilic colloid is cross-linked by a hardening agent so that dissolution during development and damage to the silver halide emulsion layer do not occur.

Since the degree of crosslinking by the hardener also affects the sensitivity of the silver halide, the hardener basically has no effect on the silver halide emulsion. Since it has a multilayer structure having a green-sensitive layer and a red-sensitive layer, a material having high solubility in water and capable of uniformly diffusing water in the hydrophilic colloid layer is desired.

[0004] Vinyl sulfone compounds are well known as having little effect on silver halide emulsions, and water-soluble compounds are disclosed in JP-A-53-41221, JP-A-61-128240 and JP-A-64-2475. Are described. Further, JP-A-53-57257 describes that a vinyl sulfone hardener having a hydroxyl group is excellent in reactivity and water solubility and has little influence on photographic performance.

[0005]

However, a common drawback of these known hardeners is that the film properties of the photosensitive material in a developing solution are inferior due to its high water solubility.

Accordingly, it is an object of the present invention to improve the physical properties of a silver halide photographic material in a developer.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to provide a vinyl sulfone-based hardening film in which a hydrophilic colloid layer on a support has a hydroxyl group with respect to the hardening agent represented by the general formula (1). Silver halide photographic light-sensitive material which is hardened by using an agent at a weight ratio of 0.5 to 15, the light-sensitive material is a color photographic light-sensitive material, and calcium-free gelatin is used as a hydrophilic colloid. The total thickness of the hydrophilic colloid layer on the side having the silver halide emulsion having a thickness of 10 to 2
5 μm.

Hereinafter, the present invention will be described in detail.

The light-sensitive material of the present invention comprises a hydrophilic colloid, a vinyl sulfone hardener having a hydroxyl group with respect to a hardener represented by the following general formula (1) in a weight ratio of 0.5 to 15. It is characterized by being hardened.

[0010]

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The hardener represented by the general formula (1) is used in an amount of about 0.5 to 15 mg, preferably 1 to 10 mg per gram of the hydrophilic colloid. In the formula, sodium is preferable as M.

In the present invention, the vinyl sulfone hardener having a hydroxyl group is preferably a compound represented by the following general formula (2).

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

A in the general formula (2) represents n-valent acyclic hydrocarbon group having 1 to 10 carbon atoms (preferably alkylene group having 1 to 8 carbon atoms), 5 or 5 having nitrogen, oxygen or sulfur atom. Examples thereof include a 6-membered heterocyclic ring, a 5- or 6-membered alicyclic group, or an aralkylene group having 7 to 10 carbon atoms. These include carboxy groups (methoxy groups, ethoxy groups, etc.),
May be substituted with an alkyl group, a halogen atom, an acetoxy group, or the like, and may be bonded to each other via the hetero atom, carbonyl group, or carbamide group.

Specific examples of the hardener represented by the general formula (2) are shown below, but the present invention is not limited thereto.

VS-1 CH ₂ ＣＨCHSO ₂ CH ₂ C (OH) HCH ₂ SO ₂ CH =
_{CH 2 VS-2 CH 2 =} CHSO 2 CH 2 C (OH) HC (OH) HCH 2
_{SO 2 CH = CH 2 VS-} 3 CH 2 = CHSO 2 CH 2 C (OH) HCH 2 C (OH) H
_{CH 2 SO 2 CH = CH 2} VS-4 (CH 2 = CHSO 2 CH 2 C (OH) HCH 2) 2 CO VS-5 (CH 2 = CHSO 2 CH 2 C (OH) HCH 2) 3 CCH 3 VS _{-6 (CH 2 = CHSO 2 CH} 2 C (OH) HCH 2) 2 O VS-7 (CH 2 = CHSO 2 CH 2 C (OH) HCH 2) 2 NH

[0017]

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These hardeners are disclosed in US Pat.
3,481 and the like. Moreover, about 1 to 25 mg per 1 g of hydrophilic colloid,
Preferably, it is used at 2 to 20 mg.

In the present invention, a vinyl sulfone hardener having a hydroxyl group represented by the compound represented by the general formula (2) is added to the hardener represented by the general formula (1) in a weight ratio of 0. It is used in the range of 0.5 to 15, preferably 0.7 to 10. When it exceeds 15, the film properties at the time of swelling are not sufficiently improved, and when it is less than 0.5, the required basic film properties cannot be obtained.

Examples of the hydrophilic colloid used in the light-sensitive material of the present invention include water-soluble polymers such as gelatin, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone and dextran sulfate, and gelatin is particularly preferable. As the gelatin, any of alkali-treated gelatin and acid-treated gelatin can be preferably used. Further, those from which salts such as calcium are removed are preferable, and those having a calcium concentration of 100 ppm or less, more preferably 50 ppm or less are preferable. Gelatin is about ^{2 to} 25 g, preferably 3 to 20 g per m ² of the light-sensitive material.
Used in

In the present invention, the silver halide emulsion is a Research Disclosure No. 308119 (hereinafter, referred to as
RD308119) can be used. 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 are also RD308119 and RD
17643, RD18716 and the like.

Various couplers can be used in the light-sensitive material of the present invention, and specific examples thereof are also described in the above-mentioned Research Disclosure.

The additives used are RD308119 XI
V. RD17643, p. 28, RD18716.
The supports described on pages 647-8 and XIX of RD308119 can be used. The light-sensitive material of the present invention can be provided with auxiliary layers such as a filter layer and an intermediate layer described in the above-mentioned RD308119VII-K, and can have various layer constitutions such as a normal layer, a reverse layer, and a unit constitution. Can be taken.

The present invention can be applied to various color light-sensitive 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 light-sensitive materials, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 25 μm or less, 10 μm or more, more preferably 20 μm or less, even more preferably 18 μm or less. Further, the film 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 under humidity control (2 hours) at 25 ° C. and a relative humidity of 55%.
_1/2 can be measured according to techniques 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.
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 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 that the color light-sensitive material is housed in a cartridge. The most common cartridge is a 135 format cartridge currently available. Others
JP-A-58-67329, JP-A-58-181035
No. 4,221,479;
No. 1045, No. 2-199451, U.S. Pat.
Nos. 46,418, 4,848,693, 4,83
A cartridge proposed in US Pat. No. 2,275 or the like can be used. Further, 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.).

In the present invention, when the chemical sensitization is performed in the presence of a silver halide-adsorbing compound, the effect of the present invention is further enhanced. As the silver halide-adsorbing compound, a sensitizing dye containing the compound of the formula (1) of the present invention, an antifoggant and a stabilizer can be used.

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, merostyril 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, ascord It may be mentioned phosphate derivative.

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.

[0032]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto. In the following, unless otherwise specified, the amounts of additives used are shown in grams per 1 m ² of the light-sensitive material, and silver halide emulsions and colloidal silver are shown in terms of silver. Further, the sensitizing dye was represented by the number of moles per mole of silver halide contained in the same layer.

Example 1 << Preparation of Photosensitive Material Sample >> On the one surface of a cellulose triacetate film support having a thickness of 120 μm, each layer having the following composition was applied and subjected to back processing.

Back first layer Alumina sol (AS-100, manufactured by Nissan Chemical Industries, Ltd.) 0.8 Diacetyl cellulose 1.5 Back second layer Diacetyl cellulose 20 mg / m ² SiO ₂ fine particles (average particle size 3 μm) 0. 4 mg / m ² Back third layer Carnauba wax (melting point: 83 ° C.) 0.1 An undercoat made of poly (vinyl acetate-maleic anhydride) is applied to the surface on the opposite side of the above support, and a multi-layer color consisting of the following layers The photosensitive material No. Nos. 1 to 10 were prepared using the hardeners shown in Table 1 in the amounts shown in Table 1 so as to have the same degree of swelling. The gelatin used had 10 ppm calcium.

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 point 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) 74 sensitizing dye (SD-7) 5.5 × 10 ^-4 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) .020 Compound (GA-1) 4.0 × 10 -3 High boiling solvent (Oil-2) 0.65 Gelatin 1.65 8th layer: high sensitivity green-sensitive layer Silver iodobromide emulsion (average grain 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) 17 silver iodobromide emulsion (average particle size 0.30 μm) 0.20 sensitizing dye (SD-11) 5.4 × 10 ^-4 sensitizing dye (SD-12) 2.0 × 10 ^-4 yellow coupler ( Y-1) 0.62 Yellow coupler (Y-2) 0.3 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 grain size 0.70 .mu.m) 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 solvent (Oil-2) 0.04 gelatin 0.57 12th layer: first protective layer silver iodobromide emulsion (average grain size 0.04 .mu.m, silver iodide content 4.0 0.30 Ultraviolet absorber (UV-2) 0.030 Ultraviolet absorber (UV-3) 0.015 Ultraviolet absorber (UV-4) 0.015 Ultraviolet absorber (UV-5) 0.015 UV absorber (UV-6) 0.10 Compound (FS-1) 0.25 High boiling solvent (Oil-1) 7 High boiling point solvent (Oil-3) 0.07 Gelatin 1.04 13th layer: 2nd protective layer Matting agent: poly (methyl methacrylate-ethyl methacrylate-methacrylic acid) (average particle size 2 μm) 0.15 polymethyl methacrylate (Average particle diameter 3 μm) 0.04 Slip agent (WAX-1) 0.04 Surfactant: F-1 0.01 F-2 0.01 Gelatin 0.55 In addition to the above composition, coating Auxiliary agent Su-1, dispersing agent Su-2, viscosity modifier, dyes AI-1, AI-2, stabilizer ST-1, antifoggants AF-1, AF-2, AF-
3 and preservative DI-1 were added as appropriate.

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

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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[0045]

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<< Evaluation >> Each of the obtained samples was heated at 40 ° C. and 65%
After storage under RH conditions for 3 days, the photographic performance and physical properties of the film when swollen were evaluated. Here, 3 per 1 g of the hydrophilic colloid is used.
The amount of water absorption at 8 ° C. for 3 minutes was determined, and 100+ (water absorption / weight of hydrophilic colloid layer) × 100 was defined as the degree of swelling. The degree of swelling of each sample was adjusted to 200 ± 5.

(Evaluation of physical properties of film upon swelling to scratch strength) Each sample was cut into a size of 35 mm in width and 14 cm in length, immersed in a color developing solution at 38 ° C for 3 minutes, and then 0.5 mm in diameter. Sapphire needle is pressed against the membrane surface and 5 mm /
The needle load changes continuously while moving at the speed of seconds,
The load was evaluated when the film was broken.

(Evaluation of photographic performance) Each sample was subjected to wedge exposure according to a conventional method, and developed according to the following processing steps.

(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 lower) (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 2.00 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 and add 1 liter And adjust the pH to 10.1.

(Bleaching solution) Iron ammonium diaminediaminetetraacetate 100.0 g Diammonium ethylenediaminetetraacetate 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 using aqueous ammonia. Adjust to .0.

(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 cc KONIDAX (manufactured by Konica Corporation) 7.5 cc Add water to make 1 liter.

Table 1 shows the results.

[0054]

[Table 1]

Example 2 The same evaluation as in Example 1 was performed using gelatin having a calcium content of 500 ppm. Table 2 shows the results.

[0056]

[Table 2]

[0057]

As has been demonstrated in the examples, according to the present invention, it is possible to increase the film strength at the time of swelling in the development processing while maintaining the photographic performance.

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

Claims (4)

[Claims] 1. A method according to claim 1, wherein the hydrophilic colloid layer on the support comprises a vinyl sulfone hardener having a hydroxyl group with respect to the hardener represented by the following general formula (1) in a weight ratio of 0.5 to 15: A silver halide photographic material characterized by being hardened using the same. Embedded image [In the formula, M represents a hydrogen atom or an alkali metal atom. ] 2. The silver halide photographic material according to claim 1, which is a color photographic material. 3. The method of claim 1, wherein decalcified gelatin is used as the hydrophilic colloid.
3. The silver halide photographic light-sensitive material described in 1. above. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the total thickness of the hydrophilic colloid layer on the side having the silver halide emulsion is 10 to 25 μm. material.