JP2520600B2 - Method for producing silver halide photographic light-sensitive material having good storage stability - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel method for producing a silver halide photographic light-sensitive material, and more specifically, the curing action is stable for a long period immediately after coating and drying of a gelatin-containing layer. And a method for producing a silver halide photographic light-sensitive material having no trouble.

[Conventional technology]

Generally, in silver halide photographic light-sensitive materials, coating,
BACKGROUND ART Polyols have been added for the purpose of suppressing fog during drying, accelerating the curing action, strengthening pressure resistance by bending, and imparting antistatic properties.

Polyhydric alcohol having at least two hydroxyl groups in the molecule belonging to one of the polyols and having a melting point of 40 ° C. or higher is a curing action by a curing agent as compared with polyols other than the polyhydric alcohol, such as diethylene glycol and glycerin. Took some time to stabilize.

In general, in the art, a light-sensitive material having a gelatin-containing silver halide emulsion layer contains a gelatin hardening agent in order to prevent the elution of gelatin into the processing solution by controlling the development processing speed and enhancing the physical properties of the gelatin film. I am using.

Further, it is known to use the polyhydric alcohol and a gelatin hardening agent in combination. There are various types of gelatin hardening agents, but when the polyhydric alcohol with a melting point of 40 ° C or higher is used together, the hardening action is more stable than when it is used with a polyhydric alcohol with a melting point below 40 ° C. It took time to get there. In addition, there is a method of placing the silver halide photographic light-sensitive material in an atmosphere of high temperature and high humidity in order to stabilize the curing action of the curing agent in a short time when used in combination with the polyhydric alcohol. However, this method has problems such as deterioration of photographic characteristics of the light-sensitive materials, scratches between the light-sensitive materials, and cost increase.

That is, it is difficult to obtain a silver halide light-sensitive material in which the action of the hardening agent is constant for a long time immediately after coating and drying the gelatin-containing layer. If the curing action is changed, the photographic characteristics (especially the sensitivity and the maximum density) and the image quality are changed, which is not preferable.

[Object of the Invention]

The first object of the present invention is to solve the above-mentioned problems of the prior art, and to produce a silver halide photographic light-sensitive material having a stable hardening action of a hardening agent from immediately after coating and drying of a gelatin content until use. There is a way to provide.

A second object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material which does not adversely affect photographic characteristics such as increased fog and sensitivity fluctuation.

A third object of the present invention is to provide a method for producing a silver halide photographic light-sensitive material having excellent adhesion resistance, which is free from a scratch defect between the light-sensitive materials.

[Structure and Action of Invention]

The object is to have at least one gelatin-containing silver halide emulsion layer on a support, the gelatin-containing silver halide emulsion layer having 2 to 12 hydroxyl groups in the molecule and having 2 to 12 carbon atoms. An amount of 20 polyhydric alcohols (compound A) having a melting point of 40 ° C. or more and 300 ° C. or less in which hydroxyl groups are not conjugated with a conjugated chain and which satisfies the following formula (1) with respect to gelatin, and halogenated Halogen that is contained in an amount of 5 to 50 g per mol of silver halide with respect to silver and is hardened with at least one curing agent selected from the group of compounds consisting of aldehyde compounds, active vinyl compounds and active halogen compounds. A method for producing a silver halide photographic light-sensitive material, which is a storage for accelerating the hardening action of the silver halide emulsion layer and stabilizing the hardening action of the silver halide emulsion layer after packaging for a long time. The management performed during the period from after the end of application and drying of the gelatin-containing silver halide emulsion layer until the packaging process, the storing process, the temperature 18 ° C. to 30 ° C., relative humidity 47
It is achieved by a method for producing a silver halide photographic light-sensitive material, which comprises storing it in an atmosphere of% RH to 62% RH for at least 24 hours.

Equation (1) The amount of gelatin in the above formula (1) means the total amount of gelatin in all layers of the support on the side containing the compound A. In addition, the amount of the compound A in the above general formula (1) means the amount of the compound A in all layers of the support on the side containing the compound A.

Further, in the above formula (1), (gelatin amount [g])
In the case of / (compound A [g])> 12.0, even if the above-mentioned aldehyde compound, active vinyl compound or active halogen compound is used as the curing agent, the curing action becomes slow, which is not preferable. In the above formula (1), (gelatin amount [g]) /
When (Compound A [g]) is less than 3.5, the curing agent may be one used in the present invention described above or one other than the present invention, but the curing action is fast, but the scratch resistance is deteriorated, which is not preferable. That is, the curing action is fast, but the scratch resistance is deteriorated.

In the above formula (1), (gelatin [g]) /
Even in the range of (Compound A [g]) = 3.5 to 12.0, if the relative humidity is less than 47% RH, the curing action is slow even if the above-mentioned curing agent of the present invention is used.
If it exceeds% RH, the curing action is quick even if the curing agent used in the present invention or a curing agent other than the present invention is used, but the resistance to scratches deteriorates, which is not preferable.

The layer containing gelatin is, for example, a hydrophilic colloid layer. Specific examples include an emulsion layer, an intermediate layer and a protective layer.

The silver halide photographic light-sensitive material obtained by the method of the present invention comprises, for example, a support and a hydrophilic colloid layer containing at least one silver halide emulsion layer coated on the support. The silver emulsion may be directly coated on the support, or may be coated through a hydrophilic colloid layer containing no silver halide emulsion,
A hydrophilic colloid layer may be further coated as a protective layer on the silver halide emulsion layer. Further, at least one hydrophilic colloid layer containing silver halide may be provided on at least one surface of the support. Also,
The silver halide emulsion layers may be divided into silver halide emulsion layers of different sensitivities, eg high and low sensitivity. In this case, the silver halide emulsion layer may have an intermediate layer of the hydrophilic colloid layer between the layers, or an intermediate layer between the silver halide emulsion layer and the protective layer. Good.

Having 2 to 12 hydroxyl groups in the molecule used in the present invention,
As a polyhydric alcohol (compound A) having 2 to 20 carbon atoms and having a hydroxyl group not conjugated with a conjugated chain (that is, the oxidized form cannot be written) and a melting point of 40 ° C. or higher and 300 ° C. or lower Further, those having a melting point of 50 ° C. or higher are preferable.

Specific examples of compound A are listed below in Nos. 1 to 50, but the present invention is not limited to these specific examples.

The amount of the compound A represented by the above compound Nos. 1 to 50 is 5 to 50 g per mol of silver halide. The above compound Nos. 1 to 50 may be used in combination with polyols other than those used in the present invention. Then, the compound A represented by the above compound Nos. 1 to 50 is added to the silver halide emulsion layer. The addition timing is arbitrary, but it is preferable to add it after the chemical sensitization and during the coating. As an addition method, it may be dispersed directly in the hydrophilic colloid, or may be added after being dissolved in an organic solvent such as methanol or acetone.

The light-sensitive material of the present invention is hardened with at least one curing agent selected from the group of compounds consisting of aldehyde compounds, active vinyl compounds and active halogen compounds.

In the silver halide photographic light-sensitive material according to the present invention,
For example, the silver halide emulsion layer and other hydrophilic colloid layers can be hardened with hardeners as described above. As these curing agents, compounds that generate formalin as a decomposition product such as formalin, dimethylurea, and trimethylolmelamine, mucochloric acid, mucobromic acid, mucophenoxycycloric acid, glyoxal, 2,3-dihydroxy-1, 4-
Aldehydes such as dioxane, 2,5-dimethoxytetrahydrofuran, glutaraldehyde, vinyl sulfone, N, N'-ethylenebis (vinylsulfonylacetamide), 1,3-bis (vinylsulfonyl)
-2-Propanol, methylene bismaleimide, 5-acetyl-1,3-diacryloyl-hexahydro-S-triazine, 1,3,5-triacryloyl-hexahydro-
Active vinyl compounds such as 3-triazine, 1,3,5-trivinylsulfonyl-hexahydro-S-triazine, 2,4-dichloro-6-hydroxy-S-triazine
Sodium salt, 2,4-dichloro-6-methoxy-S-triazine, 2,4-dichloro-6- (4-sulfoanilino) -S-triazine sodium salt, 2,4-dichloro-6- (2-sulfo Ethylamino) -S-triazine,
Examples thereof include active halogen compounds such as N, N'-bis (2-chloroethylcarbamyl) piperazine.

Examples of particularly preferable curing agents used in the present invention include the following compounds a to i. The present invention is not limited to these compounds.

a.HCHO b. (CHO) ₂ d.Cl-CH ₂ COCH ₂ Cl g.CH ₂ = CHSO ₂ (CH ₂ ) ₂ SO ₂ CH = CH ₂ hC (CH ₂ SO ₂ CH = CH ₂ ) ₄ You may use the said compound individually or in mixture of 2 or more types. Further, the above curing agent used in the present invention may be used in combination with a curing agent other than the above curing agent of the present invention.

In the production method of the present invention, the curing agent may be added to any layer at any time, but it is most preferable to add it to the coating solution immediately before coating.

As the silver halide in the emulsion used in the present invention, specifically, silver chloroiodide, silver iodobromide, silver chloride, silver chlorobromide, silver bromide, silver chloroiodobromide and the like can be used. . The content of silver iodide is preferably 0.1 to 30 mol%, particularly 0.5 to 10 mol%.
Is preferably within the range. The average grain size of the silver halide grains is preferably 0.6 μm or more. The particle size distribution may be narrow or wide. The silver halide grains in the emulsion may have a regular crystal form such as a cube, octahedron or tetradecahedron,
In addition, irregular shapes such as spherical shapes, plate shapes, and potato shapes (irre
It may have a gular) crystal form or a composite form of these crystal forms. It may consist of a mixture of particles of different crystal forms. Further, tabular grains having a grain size of 3 times or more the grain thickness are preferably used in the present invention.

The photographic emulsion used in the present invention is described by P. Glafkides in Chemie e Physik Fethigraque.
t Physique Photographique, published by Paul Montel, 1967
Year), by GHDuffin, Photographic Emulsion Chemistr
y), The Focal Press, 1966), VLZelikman et
al., Making and Coating Photograp
hic Emulsion, The Focal Press, 1964) and the like. That is,
Any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method, a combination thereof or the like.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PA in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
A method of keeping g constant, that is, a so-called controlled double jet method can also be used.

According to this controlled double jet method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a 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 an iron complex salt may be present together.

The emulsion used in the present invention usually removes soluble salts after the formation of a precipitate or after physical ripening. As a means therefor, a Nudell washing method in which gelatin is gelatinized may be used, and a polyvalent anion is used. Inorganic salts such as sodium sulfate, anionic surfactants, anionic polymers (eg polystyrene sulfonic acid), or gelatin derivatives (eg aliphatic acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) are used. The sedimentation method (flocculation) may be used. The process of removing soluble salts may be omitted.

The light-sensitive silver halide emulsion may be used as it is as a so-called unripened (Primitive) emulsion without chemical sensitization, but it is usually chemically sensitized. For chemical sensitization, Glafkides or Zelikman et al., Or D. Grundlagen der Photographischen Prozesse, edited by H. Frieser, de Grundlagen der Photographischen Prozesse.
mit Silberhalogeniden, Akademische Verlagsgesellsc
haft, 1968) can be used.

That is, a sulfur sensitizing method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitizing method using a reducing substance, a noble metal sensitizing method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof are described in U.S. Patent No. 1,574,944, 2,410,6
89, 2,278,947, 2,728,668, 3,656,955. Examples of the reduction sensitizers include primary tin salts, amines, hydrazine derivatives, formamidinesulfinic acid,
Silane compounds and the like can be used, and specific examples thereof are U.S. Pat.Nos. 2,487,850, 2,419,974, 2,518,698, 2,9.
83,609, 2,983,610, 2,694,637. In addition to gold complex salts for sensitizing noble metals, platinum, iridium, complex salts of metals of Group VII of the periodic table such as palladium can be used, and specific examples thereof are U.S. Pat.No. 2,399,083,
2,448,060, British Patent 618,061 and the like.

In the silver halide photographic light-sensitive material of the present invention, various hydrophilic colloids can be used as a binder.

Examples of colloids used for this purpose include hydrophilic colloids generally used in the photographic field, such as gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, and the like. be able to. In addition to the hydrophilic colloid, a hydrophobic colloid, for example, a dispersed polymerized vinyl compound, especially one which increases the dimensional stability of the silver halide photographic light-sensitive material, can be contained. Suitable compounds of this type include water-insoluble polymers made by polymerizing vinylic monomers such as alkyl acrylates or alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates.

Various compounds can be added to the above photographic emulsion in order to prevent the deterioration of sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the silver halide photographic light-sensitive material. 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 (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyridines, the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group and a sulfone group, and a thioketo compound For example, oxazoline thione, azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), benzenethiosulfonic acids, benzenesulfinic acid and many other compounds known as stabilizers can be added.

An example of a compound that can be used is the Theory of the Photographic Process by K. Mees.
of the Photographic Process, 3rd edition, 1966).

For more detailed specific examples of these and methods for using them, reference can be made to the descriptions in U.S. Pat. Nos. 3,954,474, 3,982,947 and 4,021,248 or JP-B-52-28660.

In the production method of the present invention, the pH of the coating liquid is preferably in the range of 5.8 to 7.5. In the case of multi-layer coating, the pH of the coating liquid prepared by mixing the coating liquids of the respective layers in the coating amount ratio is preferably in the above range of 5.8 to 7.5. pH is 5.8
If it is smaller, the dura mater progresses slowly, which is not preferable, and the pH is
If it is larger than 7.5, the photographic performance is often adversely affected, which is not preferable.

The photographic emulsion layer or other constituent layers of the silver halide photographic light-sensitive material according to the present invention include a coating aid, an antistatic agent, a slip property improving agent, an emulsion dispersion agent, an adhesion preventing agent and a photographic characteristic improving agent (for example, development acceleration, contrast enhancement, A surfactant other than the present invention may be included for various purposes such as sensitization).

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Nonionic surfactants such as alkyl amides or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Agent, alkyl carboxylate, alkyl sulfonate,
Alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurate sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene Anionic surfactants containing amino groups such as carboxy groups such as alkyl phosphates, sulfo groups, phospho groups, sulfate groups, phosphate groups, amino acids, aminoalkyl sulfonates, aminoalkyl sulfates or phosphate esters , Alkylbetaines, amphoteric surfactants such as amine oxides, alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and aliphatic or Cationic surfactants such as phosphonium or sulfonium salts containing heterocyclic ring can be used.

The silver halide photographic light-sensitive material according to the present invention may contain a water-soluble dye as a filter dye in the hydrophilic colloid layer or for various purposes such as prevention of irradiation and prevention of halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful.

In the silver halide photographic light-sensitive material according to the present invention, when the hydrophilic colloid layer contains a dye, an ultraviolet absorber or the like, they may be mordanted with a cationic polymer or the like.

Further, the silver halide photographic light-sensitive material of the present invention can contain the alkyl acrylate latex described in U.S. Pat. Nos. 3,411,911, 3,411,912 and JP-B-45-5331 in the photographic constituent layers.

Other additives, especially those useful for photographic emulsions, such as lubricants, sensitizers, and light absorbing dyes can be added to the silver halide emulsion.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion may be spectrally sensitized to blue light, green light, red light or infrared light having a relatively long wavelength by a sensitizing dye. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, 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, a selenazole nucleus, an imidazole nucleus,
Nuclei in which alicyclic hydrocarbon rings are fused to these nuclei such as tetrazole nucleus and pyridine nucleus, and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, that is, indolenine nucleus, benzindolenine 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 are
It may be substituted on the carbon atom.

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

The sensitizing dye used in the present invention is used in the same concentration as that used in a normal negative type silver halide emulsion. In particular,
It is advantageous to use at a dye concentration that does not substantially reduce the intrinsic sensitivity of the silver halide emulsion. The amount of the sensitizing dye is preferably about 1.0 × 10 ⁻⁵ to about 5 × 10 ⁻⁴ mol per mol of the silver halide, and particularly about 4 × 10 5 of the sensitizing dye per mol of the silver halide.
It is preferably used at a concentration of ^{-5 to} 2 x 10 ^-4 molar.

The silver halide emulsion used in the present invention contains a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) which reacts with an oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. May be included. The coupler is
A non-diffusible substance having a hydrophobic group called a ballast group in the molecule is desirable. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, a colored coupler having a color correcting effect or a coupler releasing a development inhibitor upon development (so-called DIR coupler) may be contained. The coupler may be such that the product of the coupling reaction is colorless.

As the yellow color-forming coupler, various open-chain ketomethylene type couplers can be used. Of these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

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

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

The protective layer of the silver halide photographic light-sensitive material according to the present invention comprises
It is a layer composed of a hydrophilic colloid, and as the hydrophilic colloid used, those mentioned above are used. Further, the protective layer may be a single layer or multiple layers.

In the emulsion layer or protective layer of the silver halide photographic light-sensitive material according to the present invention, preferably in the protective layer, a matting agent and / or
Alternatively, a leveling agent or the like may be added. Examples of the matting agent include polymethylmethacrylate having an appropriate particle size (particle size of 0.3 to 5 μm, or preferably 2 times or more, more preferably 4 times or more the thickness of the protective layer). An organic compound such as a water-dispersible vinyl polymer or an inorganic compound such as silver halide or strontium barium sulfate is preferably used. Similar to the matting agent, 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. Specific examples include liquid paraffin. Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, polyalkyl polysiloxanes, polyarene polysiloxanes, polyalkylaryl polysiloxanes, or silicones such as their alkylene oxide addition derivatives. Is preferably used.

The silver halide photographic light-sensitive material obtained by the present invention may be optionally provided with an antihalation layer, an intermediate layer, a filter layer and the like.

Specific examples of the silver halide photographic light-sensitive material using the silver halide emulsion according to the present invention include X-ray light-sensitive materials, lith light-sensitive materials, black-and-white photographic light-sensitive materials, color negative light-sensitive materials,
Examples thereof include color reversal light-sensitive materials and color photographic paper.

Various additives may be used in the silver halide photographic light-sensitive material used in the present invention, if necessary. Examples thereof include dyes, development accelerators, optical brighteners, antifoggants, and ultraviolet absorbers. Specifically, RESEARCH DISCLOSURE No. 176, No. 28-
Those described on page 30 (RD-17643, 1978) can be used.

Further, in the present invention, a compound capable of releasing iodide ions (eg potassium iodide) can be contained in the silver halide emulsion, and a desired image can be obtained by using a developing solution containing iodide ions. .

In the implementation of the silver halide photographic light-sensitive material of the present invention,
For example, the emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for photographic light-sensitive materials. What is useful as a flexible support is a film made of a semi-synthetic or synthetic polymer such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, and polycarbonate.
Examples thereof include a baryta layer or paper coated with or laminated with an α-olefin polymer (eg, polyethylene, polypropylene, ethylene / butene copolymer). The support may be colored with a dye or pigment. It may be black for the purpose of light shielding. The surface of these supports is generally subbed to improve adhesion with emulsion layers and the like. The undercoat treatment is described in JP-A-52-104913 and 59-18949.
The treatments described in JP-B Nos. 59-19940 and 59-19941 are preferable.

The support surface is corona discharge before or after the undercoat treatment,
You may perform ultraviolet irradiation, a flame treatment, etc.

In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or other layers by various coating methods. For application,
A dip coating method, a roller coating method, a curtain coating method, an extrusion coating method or the like can be used.

The present invention can be used for any photographic light-sensitive material that requires high sensitivity or high contrast. For example, it is used for an X-ray photographic light-sensitive material, a lith type photographic light-sensitive material, a black and white negative photographic light-sensitive material, a color negative light-sensitive material, a color paper light-sensitive material.

Further, it can also be used for a diffusion transfer photosensitive material, a color diffusion transfer photosensitive material, etc., which forms a positive image by dissolving undeveloped silver halide and precipitating it on the image receiving layer adjacent to the silver halide emulsion layer.

For the photographic processing of the silver halide photographic light-sensitive material according to the present invention, for example, Research Disclosure (Research D
isclosure) No. 176, pages 28 to 30 (RD-17643), any of various methods and various processing solutions can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually selected between 18 ° C and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

For example, the developer used for black and white photographic processing may contain a developing agent. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-o-aminophenol) and the like are used alone or in combination. be able to. The photographic processing of the silver halide photographic light-sensitive material of the present invention can be carried out by a developing solution containing imidazoles as a silver halide solvent described in Japanese Patent Application No. 55-155489. Further, it can be processed with a developing solution containing a silver halide solvent described in Japanese Patent Application No. 56-136267 and an additive such as indazole or triazole. Generally, various other preservatives, alkaline agents, pH buffers,
Including an antifoggant, etc., if necessary, further dissolution aids, color tones, development accelerators, surfactants, defoamers, water softeners,
A hardener, a viscosity imparting agent and the like may be included.

A so-called "lith type" development process can be applied to the photographic emulsion of the present invention. What is a "lith type" development process?
For the photographic reproduction of line images or the reproduction of halftone images with halftone images, dihydroxybenzenes are usually used as a developing agent, and the development process is carried out under a low sulfite ion temperature to contagiously carry out the development process. (For details, see Mason's "Photographic Processing Chemistry" (1966) pp. 163-165.) As a special form of development processing, a developing agent is used in a light-sensitive material, for example, in an emulsion layer. Alternatively, a method in which the photosensitive material is processed in an alkaline aqueous solution to be developed may be used. Hydrophobic developing agents can be incorporated into the emulsion layer by various methods described in Research Disclosure 169 (RD-16928) U.S. Patent No. 2,739,809, British Patent No. 813,253, or West German Patent No. 1,547,763. Can be included. Such a development treatment may be combined with a silver salt stabilization treatment with thiocyanate.

As the fixer, a fixer having a generally 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 fixer may contain a water-soluble aluminum salt as a hardening agent.

When performing color photographic development processing, for example, a negative / positive method, a color reversal method, a silver dye bleaching method or the like is used.

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
-Methanesulfamidoethylaniline, 4-amino-3
-Methyl-N-ethyl-N-β-methoxyethylaniline and LFA Mason: Photographic Proceeding Chemistry, published by Focal Press (Photog
raphic Processing Chemistry.Focal Press), 1966
Year, pages 226-229, U.S. Pat.Nos. 2,193,015 and 2,592,364
Nos. 48-64933, and the like.

The color developing solution may further contain a pH buffer, a development inhibitor or an antifoggant. If necessary, a water softener, a preservative, an organic solvent, a development accelerator, a dye-forming coupler, a competitive coupler, a fogging agent, an auxiliary developing solution, a viscosity imparting agent, a polycarboxylic acid chelating agent, an antioxidant. Etc. may be included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process or may be performed individually. Bleaching agents include Fe ⁺³ , Co ⁺⁴ , Cr ⁺⁶ , Cu
Compounds of polyvalent metals such as ⁺² , peracids, quinones, nitroso compounds and the like are used.

For bleaching or bleach-fixing solution, U.S. Patent 3,042,520,
In addition to the bleaching accelerators described in JP-B No. 3,241,966, JP-B-45-8506, JP-B-45-8836, and the thioether compound described in JP-A-53-65732, various additives can be added.

The exposure to the photographic emulsion used in the present invention varies depending on the state of optical sensitization, purpose of use, etc., but is not limited to tungsten, fluorescent lamp, mercury lamp, arc lamp, xenon, sunlight, xenon flash, cathode ray tube flying spot, laser beam, electron. Various light sources such as X-rays, X-rays, and fluorescent screens for X-ray imaging can be used as appropriate.

Exposure time is 1 / 1,000 to seconds of the addition to the normal exposure, 1/10 ⁴ to 1 in xenon flash, a cathode ray tube, the laser beam
/ 10 ⁹ second short time exposure can be applied.

〔Example〕

Hereinafter, the present invention will be further described with reference to examples. Needless to say, the present invention is not limited to the examples.

Example 1 Inner core of monodispersed silver chloroiodobromide containing 2 mol% of iodine and 0.2 mol% of chlorine having an average particle size of 0.18 μm, and on the outside thereof, iodide at a ratio of 40 mol% iodine and 60 mol% bromine. A silver iodide layer is provided to grow to a grain size of 0.5 μm, and then a silver iodobromide layer is grown to 0.85 μm at a ratio of 1 mol% iodine and 99 mol% bromine. A silver halide grain having a shape of a circle was obtained.

Chloroaurate, rhodan ammonium, sodium thiosulfate and thiourea compound were added to these particles and chemically aged.

No. 20, 30, 44 of compound A, ratio compound B (diethylene glycol), compound C (glycerin), compound D (1,4-butanediol) or comparative compound E (1,2,6-hexane) per 70 g of these particles Triol) was added in an amount of 30 g of lime-processed gelatin in an amount shown in Table 1, and a stabilizer and a thickener were further added to prepare an emulsion preparation liquid. At this time, the pH of the emulsion was 6.52 at 40 ° C.

This emulsion preparation liquid and the protective layer liquid described below were used in an emulsion liquid having a silver amount of 4.8 g / m ² and a protective layer liquid having a gelatin amount of 1.0 g / m ²
At a coating speed of 150 m / min and simultaneously coated on a polyethylene terephthalate support, and dried for 2 minutes and 30 seconds to obtain samples No. 1 to 24 in Table 1.

<Protective layer liquid> (B) ・ Ludox AM (manufactured by DuPont) is added as solid component in an amount corresponding to 5 wt% of all binders, 0.5 g of Exemplified curing agent e and water to make 2 l (pH of protective layer solution is 6.0 at 40 ° C).
3).

All samples No. 1 to 24 shown in Table 1 were left at 25 ° C and 55% RH immediately after coating and drying, and after 24 hours and 30 days, sensitometry ,
The scratch resistance test of the emulsion film and the heat treatment test for a period of time (Kutsuki resistance test) were performed. The heat treatment test for a period (Kutsuki resistance test) was performed after the sample was cut into an appropriate size and re-humidified in order to put the sample in an incubator for testing.

Based on JIS method, after continuous white exposure with KS-1 type sensitometer (Konishi Rokusha Kogyo Co., Ltd.), continuous roller transfer type automatic that can perform developer, fixing, washing and drying consistently It processed in the developing machine. The developers used are as follows.

Developer formulation (development time: 35 ° C, 30 seconds) Sensitometry was performed on each of the samples thus obtained, and the photographic characteristics obtained are shown in Table 1. The sensitivities shown in the table are the sample No. 6 according to the present invention at 25 ° C. and 55% RH
It is a relative sensitivity value with the sensitivity of the sample left to stand for 30 days as 100.

As a measure of the degree of gelatin hardening, the maximum concentration of the sample obtained by the above sensitometry method and the scratch resistance test after the sample was immersed in the above developing solution (25 ° C. for 1 minute) were carried out as follows. It was In addition, the scratch resistance of the film was evaluated as follows.

Test Method for Scratch Resistance of Emulsion Film After immersing the sample in a developing solution, a continuously changing load was scratched on a sapphire needle of 0.2R on the swollen layer. The strength (hardness) was expressed by the load at which scratches started.

Heat treatment test for a period of time (Kutsuki resistance test) Overlap the same samples that had been conditioned at 25 ° C and 55% RH for 12 hours, apply a load so that a pressure of 20 g / cm ² was applied, and shield the film. The film was placed in a thermostat at 4 ° C. for 4 days for heat treatment, and the Kutsuki degree between the films was evaluated in four grades A to D as follows.

A: No tsukitsuki B: Kutuki area less than 5% C: Kutuki area less than 15% D: Kutuki area of 15% or more From Table 1, sample No. 2,3,6,7,10,11 according to the present invention It is understood that all of them have a stable curing action immediately after coating for a long time and have good resistance to scratches. Thus, from Table 1, the sample according to the present invention is a sample that is left at 25 ° C and 55% RH for 24 hours after coating and drying and then left at 25 ° C and 55% RH for 30 days. It can be seen that the performance almost equal to is obtained. That is, when a polyhydric alcohol compound corresponding to the present invention is added in an amount falling within the scope of the present invention of the formula (1), if it is allowed to stand at 25 ° C. and 55% RH for 24 hours, % RH Samples that have been aged for 30 days have the same scratch resistance and scratch resistance, and almost the same sensitivity, so that a product with stable performance can be obtained at an early stage.

Example 2 The gelatin hardening agent Exemplified Compound e in Example 1, Table 1, Sample No. 6 was used as an equimolar mixture of Exemplified Compounds a and b, Exemplified Compound e, Exemplified Compound g or the following comparative Gelatin Hardening Agent a. Change the amounts of these gelatin hardeners to those of 30 and 30% in a 25 ° C, 55% RH atmosphere.
Got 27.

Comparative gelatin hardener Each of these samples was conditioned for 12 hours in the atmosphere of temperature and humidity shown in Table 2, sealed in an airtight manner and sealed, and the sealed sample was left at the storage temperature shown in Table 2 for 24 hours and 30 days. Then, in the same manner as in Example 1, 24 at 25 ° C, 55% RH
After being left for 30 days, the sensitometry was performed in the same manner as in Example 1 and the scratch resistance was evaluated in the same manner as in Example 1. Further, the resistance to scratches was evaluated after 30 days by applying a pressure of 50 g / cm ² to the enclosed film after humidity control as shown in Table ² .

The evaluation samples are shown in Table 2. Table 2 shows that the samples with different curing agents were applied and dried immediately after the samples were sealed under the same conditions for 12 hours under the storage conditions of the enclosed temperature and humidity shown in Table 2 and then sealed under the same conditions.・ Temperature sealed under the same temperature
After the lapse of 24 hours and 30 days, the results of testing the sensitometry, the scratch resistance and the knack resistance in the same manner as in Example 1 are described.
It can be seen that sample Nos. 1, 7, 8 and 12 according to the present invention have sensitometric performance and scratch resistance after 24 hours and near 30 days. It is also understood that the sensitivity and resistance to scratches after 30 days are excellent. As described above, according to the present invention, the coating and drying of the sample is completed, and the sample is dried at 25 ° C and 55%
If it is left under H for 24 hours, almost the same performance as that of the sample aged at 25 ° C and 55% RH for 30 days can be obtained.

As is clear from Examples 1 and 2 described above, the silver halide photographic light-sensitive materials produced according to the present invention have a rapid hardening action, so that the photographic performance is stable one day after coating and drying. It was also found that the photographic performance was stable even after one year or more.

According to the present invention, a silver halide photographic light-sensitive material having further improved photographic performance, scratch resistance, scratch resistance, etc. from the initial stage by further promoting the hardening action of a gelatin hardening agent can be produced. The light-sensitive material obtained by the present invention does not cause deterioration in photographic performance even if the packaged product is exposed to a high temperature (30 to 40 ° C.) during transportation or storage for a long time, and does not cause a scratch failure.

〔The invention's effect〕

As described above, according to the present invention, it is possible to produce a silver halide photographic light-sensitive material having a hardening effect in which a hardening agent is stable from immediately after coating and drying a gelatin layer until use.

Further, according to the present invention, a silver halide photographic light-sensitive material having good photographic characteristics such as Fog increase and sensitivity fluctuation can be manufactured.

Further, according to the present invention, a silver halide photographic light-sensitive material can be produced which does not cause a scratch failure between the light-sensitive materials.

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Claims (1)

(57) [Claims] 1. A support having at least one gelatin-containing silver halide emulsion layer, wherein the gelatin-containing silver halide emulsion layer has 2 to 12 hydroxyl groups in the molecule and has 2 carbon atoms. The amount of the polyhydric alcohol (compound A) having a melting point of 40 ° C. or higher and 30 ° C. or lower in which the number of the hydroxyl groups is not conjugated with a conjugated chain and the hydroxyl group is not conjugated with a conjugated chain, and the amount thereof satisfies the following formula (1) with respect to gelatin; It is contained in an amount of 5 to 50 g per mol of silver halide with respect to silver halide, and is hardened with at least one curing agent selected from the group of compounds consisting of aldehyde compounds, active vinyl compounds and active halogen compounds. A method for producing a silver halide photographic light-sensitive material, which is a storage for accelerating the hardening action of a silver halide emulsion layer and stabilizing the hardening action of a silver halide emulsion layer after packaging for a long time. The management performed during the period from after the end of application and drying of the gelatin-containing silver halide emulsion layer until the packaging process, the storing process, the temperature 18 ° C. to 30 ° C., a relative humidity of 47%
A method for producing a silver halide photographic light-sensitive material, characterized in that it is stored in an atmosphere of RH to 62% RH for at least 24 hours. Equation (1)