JPH0642038B2 - Silver halide photographic light-sensitive material with spot prevention - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material in which so-called spots are less likely to occur.

[Background of the Invention] In various process steps such as a process for producing a silver halide photographic light-sensitive material, for example, production of a support, preparation of a coating liquid for a silver halide emulsion, and coating of a coating liquid on a support, It is well known that black, gray or transparent spots appear on the photosensitive material when the photosensitive material is developed by mixing or adhering fine metal powders such as iron, copper, zinc, aluminum and chromium. There is. This spot is generally called a "spot".

In order to prevent the generation of these spots, the utmost care and effort is made to remove fine dust floating in the air in the manufacturing process of silver halide photographic light-sensitive materials, but it is completely removed. Things are extremely difficult.

In addition to this, the phenomenon in which the fine metal powder is mixed or adhered to the photographic light-sensitive material due to abrasion of various metal devices and equipment used for manufacturing the photographic light-sensitive material and scattering of the fine metal powder due to rust. Even it is difficult to prevent completely.

Conventionally, it has been known to incorporate various spot inhibitors into a light-sensitive emulsion layer or various non-light-sensitive layers of a silver halide photographic light-sensitive material in order to reduce the generation of such spots.

JP-A-60-41037 describes a technique of using a chelating agent as a spot preventive agent.For example, ethylenediaminetetraacetic acid (EDTA) and its salt are other chelating agents in terms of the spot preventive effect and the effect on photographic properties. It has been clarified that it is industrially useful due to its relatively low cost and low cost.

However, EDTA and its salt, when producing a silver halide photographic light-sensitive material in an atmosphere where many spots are generated,
In addition, the effect on the silver halide photographic light-sensitive material in which spots are likely to occur due to contact with the substance causing spots is insufficient.

In addition, other spot-preventing agents often have an adverse effect on photographic characteristics, such as insufficient spot-preventing effect, desensitization, and generation of fog.

[Object of the Invention] An object of the present invention is to provide a silver halide photographic light-sensitive material in which the occurrence of spots is prevented.

Another object of the present invention is, without the loss of photographic properties,
Another object of the present invention is to provide a silver halide photographic light-sensitive material in which generation of spots is prevented.

[Means for Solving Problems] The present inventors have arrived at the present invention as a result of extensive studies to solve the above object.

That is, the silver halide photographic light-sensitive material according to the present invention is a photographic light-sensitive material having a photographic constituent layer containing at least one light-sensitive silver halide emulsion layer on a support, and at least one photographic constituent layer is It is characterized by containing at least one kind of poly (vinyl crown ether).

In the present specification, the photographic constituent layers refer to all hydrophilic colloid layers involved in image formation, for example, a silver halide emulsion layer, an undercoat layer, an intermediate layer (simple intermediate layer, filter layer,
UV absorbing layer, antihalation layer, etc.), protective layer, backing layer, etc.

The present invention will be further described below.

The poly (vinyl crown ether) used in the present invention includes those of polyvinyl type, polyacrylic anilide type, polybenzyl acrylate type, polyalkyl acrylate type, etc., and all of them are radical or anionic polymerization of the corresponding crown ether vinyl monomer. Can be synthesized by, for example, Talanta, 26 945 (1979) or Ma
kromol.Chem., Rapid Commun., 1 263 (1980) and J. Polym. Sc
i., Poly.Chem.Ed., 17 1573 (1979) and Makromol.Chem., 182
1579 (1981) and Macromolecules 6 133 (1973) and Polym.Bul
l., 1 403 (1979) and the like.

Examples of poly (vinyl crown ether) used in the present invention are shown below, but the invention is not limited thereto.

I. Polyvinyl type B. Polyacrylic anilide type C. Polybenzyl acrylate type D. Polyalkyl acrylate type In the above formulas a to d, n is 0 or 1, R ₁ is a hydrogen atom, an optionally substituted alkyl group having 1 to 8 carbon atoms, or an optionally substituted carbon atom having 6 to 10 carbon atoms. Represents an aryl group, R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, an aliphatic or aromatic hydrocarbon group directly or bonded to the ring via -O- or -S-, a cyano group, Amino group, amide group, sulfonamide group, sulfamoyl group, ureido group, thioureido group, hydroxyl group, -COM, -SO ₂ M (M is -CO
- or -SO ₂ - with aldehydes, ketones, acids, esters,
Thioester, amide or salt-forming atom or group), and R ₂ and R ₃ may together form a condensed ring.

The poly (vinyl crown ether) used in the present invention preferably has a number average molecular weight of 2 × 10 ³ to 15 × 10 ⁴ , more preferably 3 × 10 ^{3 to} 5 × 10 ⁴ .

However, the measurement of the molecular weight shall be carried out by the fast osmotic pressure method in dichloroethane.

Specific compounds include the following.

[Exemplified Compound] 1. 2. 3. 4. 5. 6. 7. 8. 9. Ten. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. twenty one. twenty two. twenty three. twenty four. A synthesis example of poly (vinyl crown ether) used in the present invention will be described below.

Synthesis Example-1 Synthesis of Exemplified Compound 2 (1) Synthesis of 4'-vinylbenzo-18-crown-6 (vinyl monomer) Scheme 1 To 110 g (1.0 mol) of catechol was added 189 ml (1.0 mol) of acetic anhydride, and the mixture was heated under reflux for 4 hours. After refluxing, the mixture was cooled to room temperature and poured into ice water (3) to obtain a precipitate. This precipitate
Recrystallized from n-heptane to give catechol diacetate (I)
149 g (yield 77%) of white needle crystals (mp63-64 ° C.) were obtained.

Next, while introducing high-purity nitrogen gas, 60 g (0.309 mol) of catechol diacetate and 250 ml of nitrobenzene,
While well stirring, 84 g of anhydrous aluminum chloride was added, and the mixture was kept at 75 ° C for 4 hours. Then cool to 40 ℃, 750g
Pour into a mixture of ice and 150 ml of concentrated hydrochloric acid.

Then steam distillation is carried out and the residue is extracted with ether. Distillation of ether from the extract and further extraction with warm benzene gave 2,3-dihydroxyacetophenone (II).
(Mp121-123 ° C) was obtained. (Yield 63%) Dissolve 34.2 g (0.225 mol) of this 2,3-dihydroxyacetophenone in 480 ml of butanol and replace with nitrogen.
19.2 g of NaOH dissolved in 1 l of water are added. After a few minutes, if you see yellow crystals, take 1,14-dichloro-for 15 minutes or longer.
52.5 g (0.191 mol) of 3,6,9,12-tetraoxatetradecane was added, and the mixture was refluxed for 30 hours. After the reaction was completed, the mixture was cooled at room temperature, acidified with hydrochloric acid, the crystals were filtered, washed with methanol, and the filtrate was dried. The oily residue was dissolved in acetone, filtered, dried and extracted with n-heptane to give 31
g of 4'-acetobenzo-18-crown-6 (III) (mp96 ~
97 ° C) was obtained. (Yield 45%) This 4'-acetobenzo-18-crown-6 23.3 g (0.066
Mol) was dissolved in 400 ml of ethanol and 3.5 g of NaBH ₄ was added. The mixture was stirred at room temperature for 24 hours, poured into 400 ml of water, neutralized with acetic acid and extracted with chloroform. Crystals were obtained by extracting chloroform. The crystals were suspended and washed with ether to obtain a hydroxyethyl compound. This hydroxyethyl derivative (6.8 g) was dissolved in 200 ml of benzene, a catalytic amount of p-toluenesulfonic acid (p-TSA) was added, and a dehydration reaction was carried out for 22 hours. Benzene was distilled off from the reaction product, and the product was separated and purified on an alumina column to obtain 4.5 g of the intended vinyl derivative (IV) in a yield of 71%.

(2) Polymerization 5 g of vinyl monomer (IV) is dissolved in 200 cc of benzene and degassed with nitrogen gas. Next, the temperature is raised to 70 ° C., 0.04 g of azobisisobutyronitrile is added, and the reaction is performed for 10 hours.
After completion of the reaction, the mixture was cooled to room temperature, reprecipitated with hexane 2 and purified to obtain 4.8 g of a target poly (vinyl crown ether) (Exemplified compound 2).

Synthesis Example-2 Synthesis of Exemplified Compound 13 Hydroxymethylbenzo-15-crown-5 (5 g) is dissolved in chloroform and passed through HCl gas. After distilling off chloroform, the product was reconstituted from petroleum ether and chloromethylbenzo-15-
I got Crown-5.

3.68 g of this chloromethylbenzo-15-crown-5 and 0.25 g of polymethylmethacrylic acid were added to 40 m of dimethylformamide.
2.3 g of dichlorohexylmethylamine was added dropwise to the solution while stirring at 60 ° C. The reaction lasts 5 days. After completion of the reaction, the reaction product was poured into 1 of methanol, and the precipitate was filtered and dried to obtain 2.1 g of a target poly (vinyl crown ether) (Exemplified Compound 13).

The poly (vinyl crown ether) used in the present invention is preferably used in the range of 0.001 g to 10 g, and more preferably 0.01 g per 1 m ^{2 of the} silver halide photographic light-sensitive material.
Used in the range of ~ 1g.

In the production of the light-sensitive material of the present invention, these spot inhibitors are usually dissolved in water, methanol, ethanol, propanol, dimethylformamide or a mixed solution thereof to form a photosensitive silver halide emulsion and / or a non-photosensitive solution. Is applied to at least one of these coating solutions and coated on a support.

In the present invention, the non-photosensitive layer that is continued as necessary may be an undercoat layer (undercoat layer), an intermediate layer, a protective layer, a filter layer,
Examples thereof include an antihalation layer, an antistatic layer, and a backing layer (provided for the purpose of curling prevention, halation prevention, antistatic treatment, etc.).

The poly (vinyl crown ether) used in the present invention is preferably used in combination of one kind or two or more kinds of the above-exemplified compounds or salts thereof, and when they are used in combination, in one layer constituting the silver halide photographic light-sensitive material. They may be used in combination or may be contained in separate layers one by one, and may be contained in the photographic constituent layers as a whole as a photographic light-sensitive material.

Explaining a specific mode, as a mode of combined use in one layer, it may be contained in either one of the silver halide emulsion layer or the non-photosensitive layer, but may be contained in combination as necessary. Two or more layers may be provided. As an embodiment in which they are contained one by one in separate layers, for example, a silver halide emulsion layer and a backing layer coated on the back side of the emulsion layer,
The surface coating layer and the undercoat layer on the same emulsion layer side, the backcoat layer, the undercoat layer on the front surface side, and the protective layer may be contained in one layer each in two or more layers. In the various embodiments of the present invention, the silver halide emulsion is less likely to be adversely affected by the poly (vinyl crown ether) used in the present invention such as desensitization and fog formation. However, preferably, these compounds are not It is preferably used for the photosensitive layer. Further, the poly (vinyl crown ether) used in the present invention is effectively used in the layer adjacent to the support.

In addition, a spot inhibitor other than the present invention (for example, ethylenediaminetetraacetic acid or a salt thereof, etc.) other than the present invention can be used in combination within the range of not impairing the effects of the present invention.

The present invention includes the properties of silver halide emulsions such as the composition of silver halide (eg, silver iodobromide, silver bromide, silver chloride, silver chlorobromide, silver chloroiodobromide, etc.), and the crystal form of silver halide. Or crystal habit,
It can be applied regardless of the crystal structure, grain size distribution, latent image distribution (for example, surface latent image type, internal latent image type, etc.), pAg and pH in the emulsion.

The average grain size of silver halide grains used in the present invention is 0.1
˜5 μm is preferable, and more preferably 0.5 to 3 μm.

In the present specification, the average particle diameter means a particle diameter in the case of a particle having a spherical shape or a shape close to a sphere, and in the case of a shape other than a spherical shape, an average value based on the diameter when the projected image is converted into a circular image having the same area. It is the value shown.

The average particle diameter is measured by direct measurement with an electron microscope, by a Coulter counter, or by a centrifugal type particle size distribution analyzer based on the liquid phase sedimentation method.

The silver halide emulsion grains used in the present invention may have a regular crystal form such as a cube, octahedron, tetradecahedron and rhombo dodecahedron, and an irregular shape such as spherical, potato or tabular ( It may be an irregular crystal form. Further, it may consist of a mixture of particles having various crystal forms.

The silver halide emulsion used in the present invention may be a polydisperse emulsion or a monodisperse emulsion. Here, the monodisperse emulsion is an emulsion in which σ / r ≦ 0.20, where r is the average grain size of silver halide grains and σ is its standard deviation.

The photographic emulsion of the present invention may be prepared by any of the acidic method, the neutral method, the ammonia method, etc., and the reaction of the soluble silver salt and the soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, or a combination thereof. You may go in. Alternatively, a method of forming grains in the presence of excess silver ions (so-called reverse mixing method) may be used, and a method of controlling pAg and pH in a liquid phase in which silver halide is produced, which is one type of simultaneous mixing method, is called control. The de-double jet method can also be used.

Various silver halide solvents can be used to control the grain growth of the silver halide. Examples thereof include ammonia, potassium thiocyanate, ammonium thiocyanate, thioether compounds, thione compounds, amine compounds, thioureas, thioureas such as tetrasubstituted thioureas, and imidazole derivatives. In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt,
A lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof may be present together.

The silver halide emulsion used in the present invention can be chemically sensitized by a known method. Chemical sensitization includes, for example, thiosulfate, allyl thiocarbamide, thiourea, allyl isothiocyanate, cystine, p-toluene thiosulfonate, rhodanine, sulfur sensitization using mercapto compounds, and chloroaurate, There is gold sensitization using potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric acid and the like, and these may be used in combination.

The addition amount of the sulfur sensitizer varies in a considerable range under various conditions, but is usually about 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver. The amount of gold sensitizer added varies over a considerable range under various conditions, but it is usually 1 × 10 6 per 1 mol of silver.
It is about ^-9 to 1 × 10 ^-2 mol.

Further, in the sulfur / gold sensitization, the compounding ratio of both is changed depending on the aging conditions and the like, but usually the sulfur sensitizer is about 1 to 1000 mol per mol of the gold sensitizer. The gold sensitizer may be added simultaneously with the sulfur sensitizer, during the sulfur sensitization, or after the sulfur sensitization is completed.

These chemical sensitizers include water-soluble compounds as aqueous solutions,
Organic solvent soluble compounds are organic solvents that are easily mixed with water,
For example, it is added as a solution of methanol, ethanol or the like.

The conditions such as pH, pAg and temperature during chemical sensitization are not particularly limited, but the pH value is preferably 4-9, particularly 5-8.
The g value is preferably maintained at 5 to 11, particularly 8 to 10.
Further, the temperature is preferably 40 to 90 ° C, particularly preferably 45 to 75 ° C.

The photographic emulsion used in the present invention includes, in addition to the above-described sulfur sensitization and gold / sulfur sensitization, a reducing substance (for example, a primary tin salt, an amine salt, a hydrazine derivative, formamidinesulfinic acid,
Reduction sensitization method using a silane compound: A noble metal sensitization method using a noble metal compound (for example, a complex salt of a Group VIII metal such as Pt, Ir, or Pd other than a gold complex salt) can be used in combination. .

Photographic emulsions may be spectrally sensitized with methine dyes and the like. The dyes include cyanine dyes, merocyanine dyes,
It contains complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus,
Selenazole nuclei, imidazole nuclei, tetrazole nuclei, pyridine nuclei, etc .: Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei: and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, indolenine nuclei, benzines Indolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus and the like can be applied. These nuclei may be substituted on carbon atoms.

As a nucleus having a ketomethylene structure, a merocyanine dye or a complex merocyanine dye has a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and 2-thiooxazolidine-2,4-
A 5- or 6-membered heterocyclic nucleus such as a dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus or a thiobarbituric acid nucleus can be applied.

The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

The sensitizing dye used in the present invention is preferably 1 × 10 ^-6 mol to 5 × 10 ^-3 mol per mol of silver halide, more preferably 1 × 10 ^-5 mol to 2.5 × 10 ^-3 mol, and particularly preferably. Is contained in the silver halide emulsion in a ratio of 4 × 10 ⁻⁵ mol to 1 × 10 ⁻³ mol.

In the present invention, various compounds can be contained in order to prevent fog during the manufacturing process of the photographic light-sensitive material, during storage or during photographic processing, and stabilize photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds): heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), mercaptopyrimidines: the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group: thioketo compounds such as oxazoline thione: azaindenes such as tetraazaindenes (especially 4-hydroxy) Substitution (1,
3,3a, 7) Tetraazaindenes): benzenethiosulfonic acids: benzenesulfinic acid: etc. can be contained.

The photographic light-sensitive material may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in a photographic emulsion layer or other hydrophilic colloid layer for improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination with methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, etc. can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or a derivative thereof such as an ether, an ester or an amine, a thioether compound, a thiomorpholine compound, or a quaternary phosphine compound for the purpose of increasing sensitivity, increasing contrast, or promoting development. Grade ammonium salt compound, urethane derivative,
It may contain a urea derivative, an imidazole derivative, 3-pyrazolidones and the like.

As the binder or protective colloid of the photographic emulsion, it is preferable to use gelatin such as lime gelatin, acid-treated gelatin, derivative gelatin, and gelatin / graft polymer, but hydrophilic colloids such as hydroxyethyl cellulose, polyvinyl alcohol, polyvinyl imidazole, etc. Can be used.

In the light-sensitive material of the present invention, the silver halide emulsion layer and the other hydrophilic colloid layer can be hardened by a suitable hardener.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3 4-dichlor
-6-hydroxy-s-triazine, etc.), mucohalogenates (mucochloric acid, mucophenoxycycloric acid, etc.),
Etc. can be used alone or in combination.

For the photographic emulsion layer or other hydrophilic colloid layer of the photographic light-sensitive material, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion,
Prevention of adhesion and improvement of photographic characteristics (for example, development acceleration, hardening,
For sensitization), the following surfactants may be contained.

That is, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl or alkyl aryl ethers, ethers, polyethylene glycol, polyethylene glycol esters, polyethylene glycol sorbitan esters, poly (ethylene glycol)). Alkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Surfactants: alkyl carboxylates, alkyl sulfonates, alkyl benzes Carboxy such as sulfonates, alkyl naphthalene sulfonates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as groups, sulfo groups, phospho groups, phosphoric acid ester groups, and sulfuric acid ester groups: amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or sulfuric acid esters, alkylbetaines, amine oxides, etc. Amphoteric surfactants: alkyl amine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary compounds such as pyridinium and imidazolium
Cationic surfactants such as primary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

In the light-sensitive material of the present invention, the silver halide emulsion layer may be provided not only on one side but also on both sides of the support.

The protective layer of the light-sensitive material of the present invention is a layer composed of a hydrophilic colloid, and as the hydrophilic colloid to be used, those described above are used. The protective layer may be a single layer or a multilayer. An antistatic agent may be contained in the protective layer.

The emulsion layer or the protective layer may contain at least one selected from a matting agent and a smoothing agent.
It is preferably contained in the protective layer. The matting agent has a particle size of 0.
A water-dispersible vinyl polymer having a thickness of 3 to 5 μm or twice or more the thickness of the protective layer (for example, polymethyl methacrylate), silver halide, strontium barium sulfate or the like is used.

The leveling agent is useful for preventing adhesion failure, and is particularly effective for improving the frictional characteristics related to the camera suitability during shooting or projection of motion picture film. Waxes such as liquid paraffin and higher fatty acid esters are used as leveling agents,
Polyfluorinated hydrocarbons or derivatives thereof, polyalkylpolysiloxanes, polyarylpolysiloxanes, polyalkylarylpolysiloxanes, or silicones such as alkylene oxide addition derivatives thereof are used.

The silver halide photographic light-sensitive material of the present invention, if necessary,
An antihalation layer, an intermediate layer, a filter layer, etc. can be provided.

The silver halide photographic light-sensitive material of the present invention is an Xray light-sensitive material,
It can be applied to any of a lith light-sensitive material, a black-and-white photographing light-sensitive material, a color negative or a paper light-sensitive material.

The silver halide photographic light-sensitive material of the present invention may contain a coating material, a fluorescent whitening agent, an antifoggant, an ultraviolet absorber, etc., if necessary.

The photographic emulsion is applied to a flexible support such as plastic film, paper or cloth or a rigid support such as glass, pottery or metal by dip coating method, roller coating method, curtain coating method, extrusion coating method or the like. To be done.

The flexible support may be a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, a baryter layer or an α-olefin polymer (for example, polyethylene, Examples thereof include paper coated or laminated with polypropylene, ethylene / butene copolymer, etc.

The photographic emulsion may contain a color image-forming coupler. The color image forming coupler is preferably a non-diffusion type coupler having a hydrophobic ballast group in the molecule. The color image-forming coupler may then be 2-equivalent or 4-equivalent with respect to silver ions. The color image-forming coupler may be such that the product of the coupling reaction is colorless. Also, a colored coupler having a color correction effect, a so-called DI that releases a development inhibitor or its precursor with development.
It may contain an R coupler. Besides the DIR coupler,
The light-sensitive material may contain a compound that releases a development inhibitor upon development.

As the yellow color coupler, a closed ketomethylene type coupler can be used. Of these, benzoylacetanilide compounds and bivaloylacetanilide compounds are preferable.

As the magenta coupler, a pyrazolone compound, an indazolone compound, a cyanoacetyl compound or the like can be used, and a pyrazolone compound is particularly preferable.

As the cyan coupler, a phenol compound, a naphthol compound or the like can be used.

Two or more kinds of the above couplers may be contained in the same layer, and the same compound may be contained in at least two different layers. The coupler can be incorporated into the silver halide emulsion layer by the method disclosed in US Pat. No. 2,322,027.

For the photographic processing of the silver halide photographic light-sensitive material of the present invention, various methods can be applied using various processing solutions. The treatment temperature is preferably 18 ° C to 50 ° C, but may exceed this range. As the photographic processing, either black-and-white photographic processing or color photographic processing can be applied depending on the purpose.

For black-and-white photographic processing, dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg
1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol), 1-phenyl-
3-Pyrazolines, ascorbic acid and the like can be contained in the developer alone or in combination. The developer contains other preservatives, alkali agents, pH buffers, antifoggants (for example, methylbenzotriazole, nitroindazole, etc.) and, if necessary, dissolution aids,
A color tone agent, a development accelerator, a surfactant, a defoaming agent, a water softener, a film hardening agent, a viscosity imparting agent and the like may be contained. Of developer
The pH is preferably 9 to 11, and particularly preferably pH 9.5 to 10.5.

The silver halide photographic light-sensitive material of the present invention comprises a processing solution (eg, a developing bath, its prebath, etc.) containing a dialkyl aldehyde type hardener (eg, glutaraldehyde, β-methylglutaraldehyde, succinic dialdehyde, etc.). It is one of the preferable embodiments that the treatment is carried out with 1 to 20 g per 1 addition amount). Further, it can be processed by an automatic roller developing machine.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are primary aromatic amine developers such as phenylenediamines (eg 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl). -N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfoamidoethylaniline, 4-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) be able to.

Color developing solutions should also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors such as bromides, iodides and organic antifoggants, and antifoggants. You can If necessary, a water softener, a preservative such as hydroxylamine,
Organic solvents such as benzyl alcohol and diethylene glycol, polyethylene glycol, quaternary ammonium salts,
A development accelerator such as amines, a dye-forming coupler, a competing coupler, a fogging agent such as sodium borohydride, an auxiliary developing agent such as 1-phenyl-3-pyrazolidone, and a tackifier may be contained.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as Fe ³⁺ , Co ⁴⁺ , Cr ³⁺ , Cu ²⁺ , peracids, quinones, nitrone compounds and the like are used. For example, ferricyanide, chromium (III) salt, organic complex salt of Fe ²⁺ or Co ³⁺ , such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino
It is possible to use aminopolycarboxylic acids such as -2-propanoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid: persulfate, permanganate: nitrosophenol. Of these, potassium ferricyanide, sodium iron (III) diamine tetradiamine tetraacetate and ammonium iron (III) triamine diamine tetraacetate are particularly useful. The ethylenediaminetetraacetic acid iron (III) complex salt is useful both in a stand-alone bleaching solution and in a one-bath bleach-fixing solution.

Various additives may be added to the bleaching or bleach-fixing solution.

[Effects of the Invention] According to the present invention, it is possible to provide a silver halide photographic light-sensitive material in which the occurrence of spots is prevented without deteriorating photographic characteristics.

[Examples of the Invention] Hereinafter, the present invention will be further described with reference to Examples.

Needless to say, the present invention is not limited to this embodiment.

Example 1 Iron dust was uniformly sprinkled on one surface of an undercoated cellulose triacetate film as a substance causing spots, and the compounds and vinyl sulfone type hardeners shown in Table 1 were further sprinkled thereon. An aqueous gelatin solution containing a surface active agent was applied to form an undercoat layer.

Next, a silver iodobromide emulsion (silver iodide content: 5 mol%) prepared by the ammonia method was subjected to sulfur sensitization and gold sensitization on the undercoat layer, and then to a green-sensitive carbocyanine sensitization. Spectral sensitization was performed by adding a dye, 2-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and silver 0.9 g / m ² , gelatin 2.1 g / m ^{2 and} 0.8 g / m ² 1- (2,4,6-trichlorophenyl) -3-{[α- (2,4-di-t-amylphenoxy)-
Acetamido] benzamido} -5-pyrazolone (magenta coupler), 0.15 g / m ² of 1- (2,4,6-trichlorophenyl) -4- (1-naphthylazo) -3- (2-chloro-5-octa Decenylsuccinimidoaniline) -5-pyrazolone (colored magenta coupler), 0.016g / m ² of 4-octadecylsuccinimido-2- (1-phenyl-5-tetrazolylthio)
A gelatin-silver halide emulsion was coated to contain 0.95 g / m ² of tricresyl phosphate (TCP) in which 1-indanone (DIR compound) was dissolved. The silver halide photographic light-sensitive material obtained by the above method was subjected to full-surface exposure, processed as described below, and dried for each sample. The number of spots generated per 1,000 cm ² is shown in Table 1.

Incidentally, as a comparative compound ethylenediaminetetraacetic acid (EDTA)
Was used.

Development recipe 1. Color development 3 minutes 15 seconds (38 ℃) 2. Bleach 6 minutes 30 seconds 3. Washing with water 3 minutes 15 seconds 4. Fixation 6 minutes 30 seconds 5. Washing with water 3 minutes 15 seconds 6. Stabilization 3 minutes 15 seconds The treatment liquid composition used in each step is as follows.

Color developer Bleach Fixer Stabilizer As is clear from Table 1, the samples of the present invention show a remarkable effect in preventing spots.

Example 2 A 180 μm polyester support was subjected to corona discharge treatment, and butadiene / styrene / acrylic acid = 48: 50:
2 (weight ratio) 100 ml of copolymerized latex (40 wt%), 890 ml of distilled water, and 10 ml of 10 wt% solution of sodium salt of 2,4-dichloro-6-hydroxy-5-triazine were mixed, and the mixture was mixed with 7 ml /
It was applied so as to have a surface area of m ² and dried at 140 ° C. for 5 minutes. This treatment and coating were performed on both sides of the support.

On both surfaces of the support treated as described above, as a substance causing spots, an iron duct was sprinkled uniformly, and a triazine hardener and an aqueous gelatin solution containing an anionic surfactant were applied thereon. It was used as the undercoat layer.

Next, a solution containing 12 g of gelatin, 0.3 g of potassium bromide and 720 ml of water at 70 ° C., a solution containing 36 g of silver nitrate in 240 ml of water and a solution containing 25.4 g of potassium bromide in 240 ml of water were simultaneously added to 30 After adding for 2 seconds, oswald ripening for 5 minutes,
A tabular silver bromide emulsion in the form of fine particles was obtained.

Further, an aqueous solution of silver nitrate and an aqueous solution of potassium bromide containing 2.0 mol% of potassium iodide were added to the above emulsion by the double jet method. During this period, pBr was kept at 0.7 and pH was kept at 2.0. The obtained tabular grains had an average grain size of 1.2 μm and a grain size / thickness of 12.

This tabular silver iodobromide emulsion was then chemically sensitized with chloroauric acid salt and sodium thiosulfate.

To the emulsion of the chemical ripening agent thus obtained, 9 g of diethylene glycol per 70 g of silver halide grains, a stabilizer and a thickening agent were added, and the compound of the present invention shown in Table 2 was added to the emulsion to prepare an emulsion. As a liquid, this and the protective layer liquid shown below, the emulsion liquid has a silver amount of 4.8 g / m ² , the gelatin amount of 3.5 g / m ² , and the protective layer liquid has a gelatin amount of 1.0 g / m ^2. So that it was applied to both sides.

The entire surface of the silver halide photographic light-sensitive material obtained by the above method was exposed to light, and an automatic processor GX-300 (manufactured by Konishi Rokusha Kogyo KK) was used.
1,000 cm after development using XD-90 (manufactured by the same company)
^The number of ² spots generated is shown in Table 2. Incidentally, ethylenediaminetetraacetic acid (EDTA) as a comparative compound,
The silver halide photographic light-sensitive material obtained by the above method was used.

After standing for 4 hours at 25 ° C and 20% RH, the surface resistance of the sample surface is measured with an insulation resistance tester (Kawaguchi Denki VE-30
Type).

The results are shown in Table 2.

From Table 2, the samples of the present invention not only show a remarkable effect in preventing spots, but also have a low surface resistivity and are good.

Claims (1)

[Claims] 1. A photographic light-sensitive material having a photographic constituent layer containing at least one light-sensitive silver halide emulsion layer on a support, wherein at least one photographic constituent layer is at least one of poly (vinyl crown ether). A silver halide photographic light-sensitive material containing a seed.