JPH0778601B2 - Method for producing silver halide photographic light-sensitive material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a silver halide photographic light-sensitive material, particularly in a system in which an acrylamide polymer and / or dextran is added to a binder. The present invention relates to a method for producing a photographic light-sensitive material having improved adhesion to a support.

(Prior Art) In a silver halide photographic light-sensitive material, silver halide grains are dispersed in a binder such as gelatin, and various compounds are added and mixed for various purposes. Heretofore, silver halide grains have often been improved or new useful compounds have been added to improve photographic performance. Recently, some techniques for improving the performance by adding a compound that changes the properties of the binder have been found. For example, as disclosed in JP-A-61-69061, a method of reducing silver to obtain high sensitivity, a method of enabling rapid development processing as disclosed in JP-A-63-68837, and Japanese Patent Application No.
Improvements in drying unevenness such as those in 63-90908 could be raised.

It has been known that the addition of the polymer to the hydrophilic colloid layer such as the emulsion layer has various effective properties as described above, but there is a demerit due to the addition of these compounds. One of them is the demerit that the adhesion between the support and the hydrophilic colloid layer is poor, and the fact is that the addition amount was set small so as not to cause a problem.

(Object of the present invention) An object of the present invention is to provide a halogen in which adhesion to a support, which is a problem when a polymer typified by polyacrylamide or / and dextran is added to a gelatin binder, is not substantially a problem. It is an object of the present invention to provide a method for producing a silver halide photosensitive material.

(Structure of the present invention) The present inventor has found that in a silver halide light-sensitive material having at least one silver halide emulsion layer on a support, the silver halide emulsion layer or a non-light-sensitive layer in the vicinity of In a method for producing a photographic light-sensitive material containing a polymer containing a repeating unit represented by the formula (I) and / or dextran, the average reduction rate of evaporation components (evaporation) during the constant rate drying period in the coating / drying step of these layers. It was found that the purpose can be achieved by performing high speed drying so that the speed) is 35 g / m ² · min or more over this period.

General formula (I) In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
R ² and R ³ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, an aryl group or an aralkyl group, and may be the same or different. Also, R ² , R ³
May be bonded to each other to form a nitrogen-containing heterocycle with the nitrogen atom. L is a divalent linking group. n is 0 or 1, and m is 1 or 2.

In formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group.

R ² and R ³ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, an aryl group or an aralkyl group, and may be the same or different. Examples of the substituent include a hydroxyl group, a lower alkoxy group, a halogen atom, an amide group, a cyano group, a sulfonic acid group, a carboxylic acid group and the like. R ² and R ³ are preferably a hydrogen atom, a methyl group, an ethyl group or a phenyl group, of which a hydrogen atom is most preferred.

L represents a divalent linking group, for example, having 1 to 10 carbon atoms.
Examples thereof include an alkylene group, an arylene group, and a divalent group obtained by combining them with an ether bond, an ester bond, an amide bond or the like.

n represents 0 or 1, and 0 is preferable.

m represents 1 or 2, and 1 is preferable.

Among the ethylenically unsaturated monomers constituting the repeating unit represented by the general formula (I), specific examples of preferable ones are shown below.

The repeating unit represented by the general formula (I) may contain two or more kinds of monomer units in order to exhibit a composite function as a polymer.

The high molecular weight polymer in the present invention is a compound represented by the following general formula (II) containing a monomer represented by the general formula (I) as a polymer constitutional unit in an amount of 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more. Is.

In the formula, x represents a mole percentage, and x is preferably 70 to 100.

In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer.

Examples of the ethylenically unsaturated monomer in the preferred polymer of the present invention include ethylene, propylene, 1-butene, isobutene, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N, N, N, -trimethyl-
N-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene,
4-vinylpyridine, 2-vinylpyridine, benzylvinylpyridinium chloride, N-vinylacetamide, N-vinylpyrrolidone, 1-vinyl-2-methylimidazole, monoethylenically unsaturated ester of aliphatic acid (eg vinyl acetate, acetic acid Allyl), ethylenically unsaturated monocarboxylic acid or dicarboxylic acid and salts thereof (eg acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate), maleic anhydride, ethylenic Unsaturated esters of monocarboxylic or dicarboxylic acids (eg n-butyl acrylate, n-hexyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate, N, N-diethylaminoethyl acrylate,
Methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate, methoxyethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N, N-triethyl-N-methacryloyloxyethylammonium p-toluenesulfonate , N, N-diethyl-N-methyl-N-methacryloyloxyethylammonium p-toluenesulfonate, dimethyl itaconic acid, maleic acid monobenzyl ester), and the like, and JP-A-56-151937 and JP-A-57157937. -104927, JP-A-56-142
Examples include gelatin-reactive monomers disclosed in 524 and the like. Further, the polymer of the present invention may contain two or more kinds of monomer units as A in order to exert a composite function.

Examples of preferable compounds of the polymer in the invention include the following. (The number of degree of polymerization represents the mole percentage.) In the present invention, the polymer having a repeating unit represented by the general formula (I) added to the photographic emulsion layer has a weight average molecular weight (w) of 5,000 to 200,000, preferably 7,000 to 100,0.
00, and more preferably 15,000 to 70,000.

The addition amount of such a polymer can be selected arbitrarily.

Dextran added to the photographic emulsion layer in the present invention is
Leuconostok, dextran-producing bacteria such as Mesenteroides, or native dextran obtained by acting dextran cyclase isolated from the culture solution of these bacteria on the sucrose solution is treated with acid, alkali or enzyme to determine the molecular weight. It has been lowered. The weight average molecular weight of dextran used in the present invention is 5,000 to 30.
0,000, preferably 10,000 to 100,000, more preferably
20,000 to 70,000.

The polymer having a repeating unit represented by the general formula (I) and / or dextran used in the present invention is added in an amount of 3 to 50% by weight, particularly 5 to 30% by weight, based on the total binder in the photographic emulsion. preferable.

The photographic emulsion containing the polymer used in the present invention may be in any layer.

Of course, the non-light-sensitive gelatin layer adjacent to the photographic emulsion layer may also contain the polymer of the present invention.

When the polymer of the present invention is added to each layer of the photographic material, it is preferable that the binder ratio of the polymer / addition layer with respect to the adjacent layer is not significantly different.

The polymer of the present invention may be added to the outermost non-photosensitive gelatin layer, in which case the polymer density of the outermost layer (weight of the polymer used in the present invention / binder weight of the layer to which the polymer is added is ) Is preferably smaller than any other layer of photographic material.

The polymer may be added to the emulsion at any time, but it is suitable to add it after the second ripening and before coating.

The polymer may be added as a powder, but it is convenient to use it as a 5-20% aqueous solution.

Examples of the binder used in the present invention include commonly used gelatin. For example, lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, or a gelatin hydrolyzate may be used.

As the silver halide of the photosensitive silver halide emulsion used in the present invention, silver chlorobromide, silver bromide, silver iodobromide and silver chloroiodobromide can be used, but silver iodobromide is preferably used. To be Here, the content of silver iodide is preferably 30 mol% or less, and particularly preferably 10 mol% or less. The distribution of iodine in the silver iodobromide grains may be uniform, or may be different between the inside and the surface. The average particle size is preferably 0.2 μm or more. It is particularly preferably 0.4 to 2.0. The particle size distribution may be narrow or wide.

The silver halide grains in the emulsion are cubic, octahedral, tetrahedral,
It may have a regular crystal form such as a rhombodecahedron, or may have an irregular crystal form such as a sphere, a plate, a string or a potato, or the like. It may consist of a mixture of grains of different crystalline forms, which may have a composite form of crystalline forms. Further, tabular grains having a grain size of 5 times the grain thickness or more are preferably used in the present invention (specifically, RESEARCH DISCLOSURE 225
Volume Item 22534 P.20 to P.58, January issue, 1983, and JP-A-58-127921 and 58-113926).

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more kinds of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. The light-sensitive emulsion may be used as a mixture of a substantially non-light-sensitive emulsion (the surface or inside may or may not be fogged), or it may be divided into different layers ( Details are described in US Pat. Nos. 2,996,382 and 3,397,987). For example, in the same layer as a light-sensitive silver halide emulsion comprising a spherical or jelly-shaped light-sensitive emulsion and tabular grains having a grain size of 5 times or more the grain thickness, or as described in JP-A-58-127921. It may be used for different layers. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support or conversely on the side farther from the support.

The photographic emulsion used in the present invention is described by P. Glafkides, Chimie et.
Phisique Photographique (published by Paul Montel, 1967
), GF Duffin Photographic Emulsion Chemistry
(The Focal Press, 1966), VLZelikman et al
By Making and Coting Photographic Emulsion (The Foc
al Press, 1964), JP-A-58-127921 and 58-11.
It can be adjusted using the method described in Japanese Patent No. 3926 or the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. .

It is also possible to use a method of forming silver halide grains in the presence of excess silver ions (so-called reverse mixing method). As one form of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a so-called controlled double jet method can be used.
According to this method, a silver halide emulsion comprising silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained.

Even if the crystal structure of the silver halide grains is uniform to the inside, it also has a layered structure in which the inside and the outside are heterogeneous, as described in British Patent 635,841 and U.S. Patent 3,622,318, It may be a so-called conversion type. Further, silver halides having different compositions may be bonded by epitaxial bonding, or may be bonded with a compound other than silver rhodanide and silver oxide, for example.
Further, it may be either a surface latent image type or an internal latent image type. In the process of silver halide grain formation or physical ripening during the production of silver halide, 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, an iron complex salt or the like may coexist.

During grain formation, so-called silver halide solvents such as ammonia, thioether compounds, thiazolidine-2-thione, tetra-substituted thioureas, rhodancali, rhodammone and amine compounds may be present to control grain growth.

The silver halide emulsion used in the present invention may or may not be chemically sensitized. As the chemical sensitization method, known methods such as a sulfur sensitization method, a reduction sensitization method and a gold sensitization method can be used, and they can be used alone or in combination.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts of platinum, palladium, iridium, etc. may be contained. Specific examples thereof are described in US Pat. No. 2,448,060 and British Patent 618,061.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanins and the like can be used in addition to the sulfur compounds contained in gelatin.

As the reduction sensitizer, a primary tin salt, amines, formamidine sulfinic acid, a silane compound or the like can be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles {eg benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {eg mercapto Tothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines, mercaptotriazines, etc.}; for example, oxadrinethione Thioketo compounds; azaindenes (eg triazaindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), Such Taazainden such}; benzenethiosulfonate benzenesulfonic fins acid, known as antifoggants or stabilizers such as benzenesulfonic acid amide, can be added to many compounds.

Specifically, RESERCH DISCLOSURE Item 17643 VI (1978
December issue, P.24 to P.25).

Particularly, nitrones and their derivatives described in JP-A-60-76743 and JP-A-60-87322, mercapto compounds described in JP-A-60-80839, and heterocycles described in JP-A-57-164735. Compounds, and complex salts of silver with a heterocyclic compound (for example, 1
-Phenyl-5-mercaptotetrazole silver) and the like can be preferably used.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized by a sensitizing dye to blue light, green light, red light or infrared light having a relatively long wavelength. As sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanine dyes,
Complex merocyanine dyes, holoholer cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes and the like can be used.

Useful sensitizing dyes used in the present invention are, for example, RESERCH DI
SCLOSURE Item 17643IV-A Item (P.23, December 1978), Item
18431X (P.437, August 1979) or cited.

Here, the sensitizing dye can be used by being present in any step of the production process of the photographic emulsion, or can be present in any stage after production until immediately before coating. Examples of the former include a silver halide grain forming step, a physical ripening step and a chemical ripening step.

For the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, a coating aid, antistatic, slip property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). Various surfactants may be included for various purposes such as.

For example, saponin (steroidal), nonionic surfactants such as alkyl esters of sugars; alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N-
Anionic surfactants such as acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers; amphoteric surfactants such as alkyl betaines, alkyl sulfobetaines; aliphatic or aromatic Cationic surfactants such as quaternary ammonium salts, pyridinium salts and imidazolium salts can be used. Of these, saponin, sodium dodecylbenzene sulfonate, di-2-ethylhexyl α-sulfosuccinic acid Na salt, p-octylphenoxyethoxyethoxyethaneethanesulfonic acid Na salt, dodecyl sulfate Na salt, triisopropylnaphthalene sulfonic acid Na
Salt, anion such as N-methyl-oleoyl taurine Na salt, dodecyltrimethylammonium chloride, N-
Oleoyl-N ', N', N'-trimethylammoniodiaminopropane bromide, cations such as dodecylpyridinium chloride, N-dodecyl-N, N-dimethylcarboxybetaine, N-oleoyl-N, N-dimethylsulfone Betaine such as butyl betaine can be particularly preferably used.

As the antistatic agent, perfluorooctanesulfonic acid K salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n = 3) oxyethylenebutane Such as sulfonic acid Na salt, N-perfluorooctanesulfonyl-N ', N', N'-trimethylammoniodiaminopropane chloride, N-perfluorodecanoylaminopropyl N ', N'dimethyl-N'-carboxybetaine. Fluorine-containing surfactants, alkali metal nitrates, conductive tin oxides, zinc oxides, vanadium pentoxides, or complex oxides obtained by doping these with antimony or the like can be preferably used.

In the present invention, as a matting agent, a homoponomer of polymethylmethacrylate or a polymer of methylmethacrylate and methacrylic acid, an organic compound such as starch, and fine particles of an inorganic compound such as silica, titanium dioxide, sulfuric acid, strontium, and barium can be used. it can. The particle size is preferably 1.0 to 10 μm, particularly preferably 2 to 5 μm.

In the surface layer of the photographic light-sensitive material of the present invention, a paraffin wax, a higher fatty acid ester, a starch derivative and the like can be used in addition to the lubricant silicone compound and the colloidal silica described in JP-B-56-23139.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer of the photographic light-sensitive material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic light-sensitive material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid, a copolymer with acrylic acid, a styrene-butadiene copolymer, or a polymer or copolymer comprising a monomer having an active methylene group can be preferably used.

The photographic emulsion layer and / or the other hydrophilic colloid layer of the present invention may contain the composite latex described in Japanese Patent Application No. 62-335570.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salt (chrome alum), aldehydes (formaldehyde,
Glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, etc.), dioxane derivatives (2,3
-Dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N,
N'-methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, etc.) isoxazoles , Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-41220 and JP-A-53-572
57, 59-162546 and 60-80846, and the active halides described in US Pat. No. 3,325,287 are preferred.

The hardener of the hydrophilic colloid layer is preferably hardened by these hardeners so that the swelling rate in water is 280% or less.

The photographic light-sensitive material of the present invention may have two or more silver halide emulsion layers. In this case, the two or more silver halide emulsion layers may differ in sensitivity, gradation and the like. Further, it may have one or more silver halide emulsion layers or a non-photosensitive layer on both sides of the support.

A cellulose triacetate film is preferable as a support for a general light-sensitive material, and either may be colored or may not be colored for antihalation.

A polyethylene terephthalate film or a cellulose triacetate film is preferable as the support for the X-ray photographic light-sensitive material, and particularly preferably colored blue.

In addition to the present invention, the support has a corona discharge treatment on its surface in order to further improve the adhesive force with the hydrophilic colloid layer,
Alternatively, a method of claw discharge treatment or ultraviolet irradiation treatment is preferable, or an undercoat layer made of styrene-butadiene type latex, vinylidene chloride type latex or the like may be provided, or a gelatin layer may be further provided on the undercoat layer. An undercoat layer using an organic solvent containing a polyester swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrophilic colloid layer can be further improved.

The coating solution prepared as described above is uniformly coated on the support and then dried to complete a silver halide photographic material. As described in Yuji Harazaki, "Coating Engineering" (1965, Asakura Shoten), pages 278-281, this drying process is based on the preheating period of the material, the evaporation amount of the solvent per unit time, that is, the evaporation rate of the solvent. Is a constant rate drying period of the drying process, and thereafter, a rate-decreasing drying period of the drying process until the evaporation rate of the solvent is gradually reduced to almost no evaporation, and a humidity conditioning period.

The constant rate drying step of the present invention is a period during which the solvent evaporates at a constant evaporation rate when dried under certain defined drying conditions. The characteristic of this period is that the temperature of the film surface of the photosensitive material is almost the same as the wet-bulb temperature under the drying condition when the solvent is almost water.

On the other hand, when drying photographic light-sensitive materials in the photographic industry, it is rare that drying is performed under constant drying conditions from the beginning to the end, and various characteristics such as film quality, charging, and fog are improved, so drying is not possible for some reason. It is common to pass through zones having different conditions one after another to dry. When such a drying method is adopted, the constant rate drying in the drying period and the separation in the decreasing rate drying period cannot be determined by the evaporation rate. Therefore, since most solvents in the photographic industry are mostly water, the film surface temperature is measured and considered as the constant rate period for the same period as the wet bulb temperature, and after that, until the film surface temperature becomes the same as the dry bulb temperature. Is the rate-reduction dry period.

The conditions of these drying processes: drying temperature, humidity,
It is well known that the physical properties of the coating film are significantly affected by the speed and the like. As an example thereof, JP-A-53-70426 can be cited as an example focusing on the point that the drying conditions during this rate-decreasing drying period significantly change the physical properties of the film.

However, contrary to the patent, the present inventor has found that the adhesion between the support and the gelatin layer can be remarkably improved by performing the constant rate drying rapidly. This object was satisfied when the evaporation rate of the solvent during the constant rate drying period was 35 g / m ² · min or more on average over the constant rate period. Therefore, a coating material with a large coating amount takes a long time, and a coating material with a small coating amount finishes constant rate drying in a short time, but it is not the constant rate drying time that can achieve this object, but rather , I knew that it was decided by the evaporation rate. The evaporation rate of the solvent during the constant rate drying period is effective at 35 g / m ² · min or more, but is preferably 39 g / m ² · min, particularly preferably 44 g / m ² · min or more. The upper limit of this evaporation rate is rather limited by the method and mechanical structure of the drying process, and although the preferable region is not attached, it is not an abnormal condition.
200g / m ² · min or less is recommended.

Following the constant rate drying shown in the present invention, the rate reduction period,
And there is a humidity control period, but these may be any conditions as long as they are generally known, for example, wet-bulb temperature of 5 ° C to 25 ° C, relative humidity of 30 to 80%, reduced rate drying, dry-bulb temperature. 20
It is good to adjust the humidity at -40 ℃ and relative humidity of 50-70%.

Such drying is performed by a conventional method of blowing air. As a method of conveying the photographic light-sensitive material in the drying step, any of a straight method, an arch method, an air conveying method and the like can be used.

The photographic light-sensitive material produced according to the present invention can be used in any photographic light-sensitive material which is subjected to ordinary development processing. For example, it is used for X-ray photographic light-sensitive materials, lith type photographic light-sensitive materials, black and white negative photographic light-sensitive materials, color negative light-sensitive materials, color reversal light-sensitive materials, color paper light-sensitive materials, black-and-white paper light-sensitive materials.

When used as a photographic material for X-rays, RE
SEARCH DISCLOSURE Item18431 (August 1979 P.433 ~ P.44
1) Technology related to stabilizers, antifoggants and anti-knitting agents (P.433 to P.436), technology related to protective layer (P.436, IV), crossover control technology (P.436V) ) And the like are preferably used.

To obtain an X-ray photographic image, the exposure may be carried out by using a usual method. That is, it is a method of directly irradiating X-rays or exposing a light-sensitive material having a light-sensitive layer on both sides to X-rays by using two lead foil intensifying screens or fluorescent intensifying screens.

Alternatively, in the case of a photosensitive material having a photosensitive layer on one side, a method of irradiating a fluorescent intensifying screen with X-rays and recording the emitted light on the photosensitive material is used. Of course, the photosensitive material may be brought into contact with the fluorescent intensifying screen to perform X-ray irradiation.

Here, as the phosphor, a blue-emitting calcium tungstate, a barium sulfate or other fluorescent material, and a green-emitting rare earth fluorescent material are used. After the X-ray exposure is accumulated in the fluorescent material, the cathode ray tube flying spot, the emitting diode, the laser light (for example, gas laser, YAG laser,
It is also possible to expose with various light sources including infrared light such as a dye laser and a semiconductor laser).

When used for purposes other than X-ray photography, ordinary exposure methods can be used.

The light-sensitive material of the present invention may be exposed using a light wavelength conversion element.

Photographic processing of the light-sensitive material of the present invention includes, for example, RESEARCH DISCLOSURE No. 176-28.
Any known method and known processing solution as described on page 30 (RD-17643) can be applied.

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, a black and white photographic processing developer can include known developing agents. Examples of developing agents include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-).
Aminophenol) and the like can be used alone or in combination. For photographic processing of the light-sensitive material of the present invention,
Processing with a developing solution containing imidazoles as a silver halide solvent described in JP-A-57-78535 can also be used. Further, it can be processed with a developer containing a silver halide solvent described in JP-A-58-37643 and an additive such as indazole or triazole. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, dissolution aids, color tones, development accelerators, surfactants, defoamers, A water softener, a hardener (eg, glutaraldehyde), a viscosity imparting agent, etc. may be included.

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 present invention will be further described with reference to examples.

(Example 1) 0.35 µ of nearly cubic silver iodobromide was prepared by the control double jet method.

1-phenyl-5-mercapto-tetrazole was added to this emulsion for chemical sensitization using gold / sulfur sensitization in combination, and 4-hydroxy-6-methyl-1,3,3 as a stabilizer.
a, 7-Tetrazaindene was added, and the compounds of the present patent application were added as shown in Table 1, and 2,4-dichloro- was added as a hardening agent.
An emulsion coating solution was prepared by adding 6-hydroxy-s-triazine.

Further, a coating solution for a surface protective layer containing gelatin as a binder, a matting agent, an anionic surfactant, a fluorine-containing compound organopolysiloxane and a polyethylene oxide nonionic surfactant was prepared separately.

These coating solutions were applied at the same time and dried through a drying zone blown by dry air. The coating water content (including trace amounts of other organic solvents) was 117 g / m ² . Further, the temperature, humidity and air flow in the drying zone were added so that the time of the constant rate drying period was as shown in Table 1. After that, these samples were subjected to the same conditions (temperature: 27 ° C, humidity: 60%), and then reduced rate drying and humidity conditioning. Thus, samples (1) to (10) were prepared.

These samples were tested for adhesion as shown below,
The results are also shown in Table 1.

Adhesive strength, test method The sample is developed as shown below. Apply a load of 500 g to a spherical rubber having a diameter of 5 mm, and rub it about 3 mm from the edge of the wet sample to the center, and repeat this 5 times.

The length of the emulsion layer peeled off by the work of 1. is measured, and this is taken as a measure of the goodness of adhesion. Table 1 shows the peeled length.

Of course, the smaller the value, the better.

The following points can be seen from Table 1.

(1) The system to which the compound (1) or dextran is added is
Poor adhesion, but if constant rate drying is quickly dried, it will improve.

(2) The improvement is seen at the evaporation rate of 35 CC / m ² · min or more.

(Example 2) A silver nitrate aqueous solution and a potassium bromide aqueous solution were added to a gelatin aqueous solution to prepare silver bromide particles having an average particle diameter of 0.55 µm. An aqueous silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were further added to this emulsion to form silver iodobromide containing 2 mol% of silver iodide on the outside of the previous grains.

After desilvering this emulsion by a usual method, gelatin was added and 1-phenyl-5-mercapto-tetrazole was added for gold / sulfur sensitization. Each emulsion was chemically ripened for its optimum time and then 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene and 3- (5-
It was stabilized by adding sodium mercaptotetrazolyl) -benzenesulfonate. Furthermore, a compound as shown in Table 2 and resorcinol were added, and the development swelling ratio was about
A hardening agent was added so that the thickness would be 230% (total film thickness when swollen / dry film thickness), and the mixture was coated on a polyethylene terephthalate support.
At this time, at the same time, the matting agent, inorganic salt, fluorine-containing compound, anionic surfactant, organopolysiloxane, DV-759 described in Japanese Patent Application No. 62-335570, and polyethylene oxide nonionic surfactant as shown in Table 2 A surface protection layer containing the agent was applied.

The amounts of these solutions were changed so that the amount of coating water was as shown in Table 2.

After coating as described above, the drying conditions were set so that the constant rate drying time was as shown in Table 2, and the subsequent rate-reducing drying to humidity control was performed under the same constant conditions as in Example 1 to obtain Samples 11 to 19. Was prepared and the same adhesive strength test as in Example 1 was performed. The results are shown in Table 2.

As can be seen from Table 2, the quality of adhesion is uniquely determined by the evaporation rate, not by the time of constant rate drying or the amount of applied water, and as shown in this patent, it is faster than 35 g / m ² · min. It turns out that it is effective if dried.

(Example 3) 30 g of gelatin, 5 g of potassium bromide and 0.05 g of potassium iodide were added to 1 water, and an aqueous solution of silver nitrate (5 g as silver nitrate) and 0.73 g of potassium iodide were added to a container kept at 75 ° C with stirring. The aqueous potassium bromide solution was added by the double jet method over 1 minute. Further, an aqueous silver nitrate solution (145 g as silver nitrate) and an aqueous potassium bromide solution were added by the double jet method. The addition flow rate at this time is
The flow rate was accelerated so that the flow rate at the end of the addition was 8 times that at the start of the addition. After this, 0.37 g of potassium iodide aqueous solution
Was added.

After the addition was completed, the soluble salts were removed at 35 ° C by the precipitation method, the temperature was raised to 40 ° C, and 60 g of gelatin etc. was added to adjust the pH to 6.5.
Adjusted to. The temperature is raised again to 56 ° C., and 650 mg of sensitizing dye anhydro-5,5′-di-chloro-9-ethyl-3,3′-di (3-sulfopropyl) oxacarbocyanine hydroxide sodium salt is added. After that, chemical sensitization using gold and sulfur sensitization was applied. The resulting emulsion has a hexagonal tabular shape with a projected area diameter of 0.85 μm and an average thickness of 0.158 μm.
It was m.

4-Hydroxy-6-methyl- was added to this emulsion as a stabilizer.
1,3,3a, 7-tetrazaindene and 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine,
Trimethylolpropane as a dry antifoggant and a compound as shown in Table 3 were added to prepare a coating solution.

As a surface protective layer, in addition to gelatin, prepare an aqueous gelatin solution containing polymethylmethacrylate fine particles, a fluorine-containing compound, sodium polyacrylate, an anionic surfactant, a polyethylene oxide nonionic surfactant, and the compound shown in Table 3. did.

As a hardener in the surface protective layer solution and the emulsion coating solution 1,
2-Bis (vinylsulfonylacetamide) ethane was added and simultaneously coated on a blue-colored PET support, and then constant rate drying and rate reduction drying were carried out so that the evaporation rates shown in Table 3 were obtained. After that, all the samples were conditioned at 25 ° C. and 65% for 3 minutes and wound into samples 20 to 25.

The results of the adhesion test for these samples are shown in Table 3.

It can be seen from Table 3 that if the evaporation rate in constant rate drying is high, the adhesion is good, but the evaporation rate in reduced rate drying has no significant effect.

On the contrary, it seems that the evaporation rate should be slower in the reduction rate drying.

This was a new finding that was the opposite of the previously known result.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer or a non-light-sensitive layer in the vicinity thereof has the following general formula (I). In the method for producing a photographic light-sensitive material containing a polymer and / or dextran containing repeating units represented by the formula, the average evaporation rate in the constant rate drying step of the coating and drying steps is 35 g / m ² · min or more. A method for producing a characteristic silver halide photographic light-sensitive material. General formula (I) In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ² and R ³ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, an aryl group or an aralkyl group. , The same or different. Also R ² , R ³
May be bonded to each other to form a nitrogen-containing heterocycle with the nitrogen atom. L is a divalent linking group. n is 0 or 1, and m is 1 or 2.