JPH07281352A - Silver halide photographic sensitive material and its production method - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material maintaining transparency necessary for the photosensitive material and to prevent deterioration of color development density during storage and to enhance scratching resistance by regulating an amount of a residual organic solvent caused by forming a magnetic recording layer to a specified value or less. CONSTITUTION:The photosensitive material has one or more silver halide emulsion layers on one side of a support and the transparent recording layer on the other side, and the residual solvent amount is regulated to <=200mul/m<2>, preferably, <=-100mul/m<2>, and the transparent magnetic recording layer contains fine nonmagnetic particles, preferably, in an amount of 20% or 10-300% of a binder in the recording layer, and this recording layer has, preferably, a film thickness of 0.3-2.0mum.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material having an optically transparent magnetic recording layer.

[0002]

2. Description of the Related Art For silver halide photographic light-sensitive materials, for example,
Type of photographic light-sensitive material, serial number, manufacturer name, emulsion No.
Various information related to photographic light-sensitive materials, such as shooting date / time, aperture, exposure time, lighting conditions, filter used, weather, size of shooting frame, model of camera, use of anamorphic lens, etc. Various information when shooting with the camera,
For example, various information necessary for printing such as the number of prints, filter selection, customer color preference, trimming frame size, etc., for example, number of prints, filter selection, customer color preference, trimming frame size. It has been desired to input various kinds of information obtained at the time of printing such as the above and other customer information in terms of management, improvement of print quality, and efficiency of printing work.

Therefore, since the magnetic recording method is easy to record / reproduce, it has been studied to use the magnetic recording method for inputting the above various information to the photographic light-sensitive material.
Various technologies have been proposed. For example, on the back surface of a photographic light-sensitive material, it is necessary to provide a transparent magnetic recording layer having the required transparency by selecting the amount and size of magnetizable particles. US Pat. Nos. 3,782,947 and 4,279,945 Id., 4,302,
No. 523, etc.

By providing these magnetic recording layers, it becomes possible to record the above-mentioned various kinds of information in the photographic light-sensitive material, which has been difficult in the past, and it is possible to record voices and image signals. is doing.

[0005]

However, unlike a general silver halide photographic light-sensitive material, since the transparent magnetic recording layer is provided, the photographic performance may be deteriorated (especially, the color density is lowered) during storage.

Further, since a silver halide photographic light-sensitive material having a transparent magnetic recording layer is rubbed by a magnetic head, it is required to have a strong scratch resistance which has not been found in conventional silver halide photographic light-sensitive materials. Further, since it may be printed or projected through the transparent magnetic recording layer that is rubbed by a magnetic head, it is required to have higher scratch resistance than that required for a conventional magnetic recording medium. However, the conventional transparent magnetic layer has a problem that the scratch resistance is weak.

In particular, the scratch resistance at high temperatures is particularly weak, and the transparent magnetic layer may be damaged to cause a virtual image due to printing or projection, or the transparent magnetic layer may be peeled off to cause a failure of reading a magnetic signal. There were many.

The present inventors have discovered that the cause of the deterioration in photographic performance during storage and the weak scratch resistance is due to the large amount of residual organic solvent due to the provision of the transparent magnetic recording layer. Was achieved. Further, the transparent magnetic recording layer for the above-mentioned purpose has a large ratio of the hydrophobic binder to the ferromagnetic powder unlike the conventional recording layer for movie films such as sound 8 mm, and thus the residual organic solvent amount tends to be large. Was found.

An object of the present invention is to provide a photographic light-sensitive material having a magnetic recording layer which maintains the transparency required for the photographic light-sensitive material, has no decrease in color density during storage, and has excellent scratch resistance. Especially.

[0010]

The above objects of the present invention can be achieved by the configurations described in the claims.

The present invention will be described in detail below.

The transparent magnetic recording layer in the present invention specifically means a magnetic recording layer having a maximum optical density of 1.5 or less. The optical density in the present invention is an optical densitometer PDA-65 (manufactured by Konica Corp.)
It means the optical densities Db, Dg, and Dr measured through G and R. The maximum value among them is Dmax. The maximum optical density Dmax of the magnetic recording layer of the present invention may be 1.5 or less, but it is preferably small in consideration of the influence on photographic images, preferably 0.8 or less, and particularly preferably 0.3 or less.

In the present invention, various supports can be used. Examples of supports that can be used include polyester films such as polyethylene terephthalate and polyethylene naphthalate, cellulose triacetate films, cellulose diacetate films, polycarbonate films, polystyrene films, and polyolefin films.

When the support is a polyester film, the polyester constituting the polyester film is not particularly limited, but is a polyester having a dicarboxylic acid component and a diol component as main components and having film-forming properties. Is preferred.

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2-6 naphthalene dicarboxylic acid, 2-7 naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether diphenyl acid, diphenyl ethane dicarboxylic acid. , Cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketone dicarboxylic acid, phenylindanedicarboxylic acid and the like. Further, as the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-
(Hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol, etc. . Among the polyesters containing these as the main constituents, terephthalic acid and / or 2-6 naphthalenedicarboxylic acid as the dicarboxylic acid component and ethylene glycol and diol as the diol component from the viewpoints of transparency, mechanical strength, dimensional stability, etc. And / or a polyester containing 1-4 cyclohexanedimethanol as a main component is preferred. Among them, polyethylene terephthalate, polyethylene 2-6 naphthalate, terephthalic acid and 2
-6 A polyester composed of naphthalene dicarboxylic acid and ethylene glycol, and a polyester having a mixture of two or more of these polyesters as main constituents are preferable. 70% ethylene terephthalate units and / or 2-6 ethylene naphthalate units for polyester
When it is contained in an amount of not less than wt%, a film having excellent transparency, mechanical strength, dimensional stability and the like can be obtained.

The polyester constituting the polyester film may be further copolymerized with another copolymerization component or may be mixed with another polyester as long as the effect of the present invention is not impaired. Examples of these include the above-mentioned dicarboxylic acid component, diol component, and polyester.

The polyester constituting the polyester film is obtained by copolymerizing at least one compound having at least one hydrophilic group to obtain appropriate water absorption,
At the time of the heat treatment described below, it is easy to allow the film to contain an appropriate amount of water, which is preferable.

The hydrophilic group of the compound having at least one hydrophilic group is sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, polyoxyalkylene group, sulfamoyl group, carbamoyl group, acylamino group, sulfonamide. Group, disulfonamide group, ureido group, urethane group, alkylsulfonyl group, alkoxysulfonyl group, and the like, among them, sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, a polyoxyalkylene group, A disulfonamide group is preferred.

Examples of the compound having a hydrophilic group include an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof, a dicarboxylic acid having a polyoxyalkylene group or an ester-forming derivative thereof, and a diol having a polyoxyalkylene group. Is mentioned. Above all, in terms of polymerization reactivity of polyester and transparency of the film,
5-sodium sulfoisophthalic acid, 2-sodium sulphoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and their sodium to other metals (eg potassium, lithium, etc.) A compound substituted with an ammonium salt, a phosphonium salt, or the like, or an ester-forming derivative thereof, polyethylene glycol, polytetramethylene glycol, a polyethylene glycol-polypropylene glycol copolymer, or a hydroxy group at both ends thereof is oxidized to a carboxyl group. Compounds and the like are preferable.

These compounds having a hydrophilic group may be used alone or in combination of two or more. In particular, it is preferable that both the aromatic dicarboxylic acid component having a sulfonate group and the compound component having a polyoxyalkylene group are copolymerized with the polyester because the water absorption of the film is further improved.

The copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group is preferably 0.5 to 10 mol% based on the difunctional dicarboxylic acid constituting the polyester.

The number average molecular weight of the compound component having a polyoxyalkylene group is preferably 300 to 20000, more preferably 600
It is preferably in the range of up to 10,000, especially in the range of 1000 to 5000. The copolymerization ratio is preferably 0.5 to 15% by weight based on the polyester of the reaction product.

If the copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group, the number average molecular weight of the compound component having a polyoxyalkylene group, and the copolymerization ratio are within these ranges, the transparency and mechanical strength of the film will be impaired. It is possible to improve the water absorption.

For the purpose of improving the heat resistance of the film, a bisphenol compound, a compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio of these is 3 to 20 mol% based on the difunctional dicarboxylic acid constituting the polyester.
Is preferred.

The polyester used in the present invention may contain an antioxidant. In particular, the effect becomes remarkable when the polyester contains a compound having a polyoxyalkylene group. The antioxidant to be contained is not particularly limited as to its type, and various antioxidants can be used, for example, hindered phenol compounds,
Antioxidants such as phosphite compounds and thioether compounds can be mentioned. Among them, antioxidants of hindered phenolic compounds are preferable in terms of transparency.

The content of the antioxidant is usually 0.01 to 2% by weight, preferably 0.1 to 1.5% by weight, based on the polyester.
Is. When the content of the antioxidant is small, a so-called fog phenomenon in which the density of the unexposed portion of the photographic light-sensitive material becomes high is likely to occur, and when it is too large, haze of the film becomes high and transparency may be deteriorated. In addition, these antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type.

The polyester used in the present invention preferably contains a dye for the purpose of preventing the light piping phenomenon. The dye to be blended for such a purpose is not particularly limited in its type, but in the production of the film, it is necessary that it has excellent heat resistance, and examples thereof include anthraquinone-based and perylene-based dyes. To be Further, as the color tone, gray dyeing is preferable as seen in general photographic light-sensitive materials. These dyes include Bayer's MACROLEX series, Sumitomo Chemical's SUMIPLAST series, Mitsubishi Kasei's Dlaresl.
From the n series and the like, one kind may be used alone, or two or more kinds of dyes may be mixed and used so as to obtain a necessary color tone. At this time, the dye has a spectral transmittance of 60% to 85% in the wavelength range of 400 to 700 nm and a difference between the maximum and the minimum of the spectral transmittance of 10% in the wavelength range of 600 to 700 nm. Is preferable in order to prevent the light piping phenomenon and to obtain a good photographic print.

If necessary, the polyester film of the present invention may be provided with slipperiness. The slipperiness imparting means is not particularly limited, but an external particle addition method of adding inert inorganic particles to polyester, an internal particle precipitation method of precipitating a catalyst to be added during the synthesis of polyester,
Alternatively, a method of applying a surfactant or the like on the back surface of the film is common. Among these, the internal particle deposition method that can control the deposited particles relatively small,
It is preferable because slipperiness can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but Ca and Mn are particularly preferable because high transparency can be obtained. These catalysts may be used alone or in combination of two kinds.

The polyester film of the present invention may have a multilayer structure composed of different polyesters. For example,
When the above-mentioned polyester layer is the A layer and the above-mentioned other polyester layer is the B layer or the C layer, a two-layer structure consisting of the A layer and the B layer may be used.
A three-layer structure such as B layer / A layer, A layer / B layer / C layer, B layer / A layer / B layer or B layer / A layer / C layer may be used. Further, a structure having four or more layers is of course possible, but it is not preferable in practice because the manufacturing equipment becomes complicated. The thickness of the layer A is preferably 20% or more, and more preferably 30 to 70% of the total thickness of the polyester film. In this case, the thickness of the A layer is the thickness of the layer when the A layer has only one layer, and is the sum of the thicknesses when the A layer has two or more layers. The thickness of the B layer or C layer is preferably 5 to 60 μm, more preferably 10 to 50 μm. When the thickness of each layer is within the above range, transparency, mechanical strength, and dimensional stability are excellent, and further, water absorbability is provided, and thus a polyester film having excellent curl recovery property can be obtained.

The polyester constituting the B layer or the C layer is formed by laminating a polyester or copolymerized polyester layer such as polyethylene terephthalate, which is excellent in transparency, mechanical strength and dimensional stability, to obtain the transparency of the entire film, Mechanical strength, dimensional stability, etc. can be improved.

Further, when the polyester film of the present invention has a layer structure, the above-mentioned functions such as anti-oxidation, light-piping prevention, slipperiness, etc., or addition of various additives other than those mentioned above is applied only to the surface layer. Since it can be performed, the transparency of the film can be maintained high.

The method for synthesizing the polyester as the raw material of the polyester film of the present invention is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, a dialkyl ester is first used as a dicarboxylic acid component, and an ester exchange reaction is performed between this and the diol component, and this is heated under reduced pressure. It is possible to use a transesterification method in which polymerization is carried out by removing excess diol component. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. In addition, in each process during synthesis, coloring agent, antioxidant,
A crystal nucleating agent, a slip agent, a stabilizer, an antiblocking agent, an ultraviolet absorber, a viscosity adjusting agent, a defoaming agent, a clarifying agent, an antistatic agent, a pH adjusting agent, a dye, a pigment and the like may be added.

The thickness of the polyester film of the present invention is not particularly limited. It may be set so as to have a required strength according to the purpose of use. Particularly when the polyester film is used for a photographic light-sensitive material for color negative, it is preferably 20 μm or more, and particularly preferably 40 μm or more.
In addition, when it is used for medical and printing photographic light-sensitive materials,
It is preferably 50 μm or more, and particularly preferably 60 μm or more.

In the method of laminating the same or different polyesters having different intrinsic viscosities, the difference in the intrinsic viscosities is 0.02 to
0.5 (dl / g) is preferable, and in the method of changing the thickness of both outer layers, the thickness of both outer layers is d.
_{If 1} and d ₂ , then 1.1 ≦ d ₁ / d ₂ ≦ 10, and further 2 ≦ d ₁
/ D ₂ ≦ 5 is preferable from the viewpoint of production such as stretching of the film.

The intrinsic viscosity is determined as follows. Film or pellet with phenol 1,1,2,
It was dissolved in a mixed solvent of 2-tetrachloroethane (weight ratio 60/40) to prepare solutions having concentrations of 0.2 g / dl, 0.6 g / dl and 1.0 g / dl, and each was measured at 20 ° C. with an Ubbelohde viscometer. Relative viscosity increment η _{SP at} concentration (C) (ratio η of increment η-η _S to η _S of solvent viscosity η _S of polymer solution viscosity η η
_SP : η _SP = (η-η _S ) / η _S ) is calculated. Then η _SP
/ C is plotted against C, and the straight line obtained by the method of least squares is extrapolated to the concentration C = 0 to obtain η at the concentration C = 0.
_{Calculate SP} / C. The intrinsic viscosity [η] is η _SP / C (C =
0). The unit is indicated by dl / g.

The Tg of the polyester film is preferably 60 ° C. or higher, more preferably 70 ° C. or higher and 150 ° C. or lower. Tg is determined by measuring with a differential scanning calorimeter. Tg
Within this range, the film is not deformed in the drying step of the development processor, and a photosensitive material with a small curl after development is obtained.

Further, for the purpose of reducing the curling of the polyester photographic support, the methods described in JP-A-51-16358 and JP-A-6-35118 can be preferably used.

That is, it is a method of heat-treating at a temperature of 50 ° C. or higher and a glass transition point or lower for 0.1 to 1500 hours.

Since this heat treatment is carried out at a high temperature of 50 ° C. or higher, if it is carried out after coating the emulsion, it tends to cause deterioration of the performance of the emulsion layer. Therefore, it is desirable to do it before coating the emulsion layer.

The support of the present invention includes a matting agent, an antistatic agent, a lubricant, a surfactant, a stabilizer, a dispersant, a plasticizer, an ultraviolet absorber, a conductive substance, a tackifier, a softening agent and a fluidity. Additives, thickeners, antioxidants and the like can be added.

The silver halide photographic light-sensitive material of the present invention is a light-sensitive material for black and white, a light-sensitive material for color negative, a light-sensitive material for color paper, a light-sensitive material for color reversal, a light-sensitive material for movies, an X-ray light-sensitive material. , A photosensitive material for printing, a photosensitive material for microphotography, and the like.

The present invention is characterized in that the residual solvent amount is 200 μl / m ² or less, more preferably 100 μl / m ² or less,
Most preferred is 50 μl / m ² or less.

There is no limitation on the means, but the following embodiments are preferable.

First, it is preferable that the thickness of the transparent magnetic recording layer is thin (2.0 μm or less (particularly 1.5 μm or less)), but if it is too thin, scratch resistance deteriorates. Therefore, it is preferably 0.3 μm or more. It is preferably 0.5 μm or more.

The second solvent used preferably contains 35 wt% or more, more preferably 50 wt% or more of the solvents having a boiling point of 100 ° C. or less in the solvent ratio. Examples of preferable solvents include ethyl acetate, methyl ethyl ketone, and acetone.

Thirdly, a high drying temperature (80 ° C. or higher (particularly 100 ° C. or higher (further 120 ° C. or higher)) is preferable, but 170 ° C. or lower is preferable and 150 ° C. or lower because the base is deformed if it is too high. Is more preferable, and 140 ° C. or lower is most preferable. Further, the support is preferably used in combination with polyethylene-2,6-naphthalenedicarboxylate (PEN base), which has a high Tg and is hardly deformed, and can improve the flatness. When used in combination with the PEN base, the drying temperature is preferably 90 ° C or higher, and preferably 120 ° C or lower.

Fourth, it is preferable to contain non-magnetic fine particles such as a matting agent, an abrasive and an antistatic agent. This non-magnetic fine particle means the particle size of the primary particle that is not ferromagnetic 10 μm
The following solid particles are referred to. The fine particles to be contained have a refractive index of 1.
It is preferably 8 or less, more preferably 1.6 or less, most preferably 1.5 or less. The content is preferably 5 wt% or more, more preferably 10 wt% or more, most preferably 20 wt% or more from the viewpoint of reducing the amount of residual solvent with respect to the binder containing fine particles, and from the viewpoint of scratch resistance, It is preferably 400 wt% or less (particularly 300 wt% or less). The fine particles to be contained preferably have an average particle diameter of 3.0 μm or less, more preferably 1.0 μm or less, most preferably 0.3 μm or less. In addition, this average particle diameter is an area average particle diameter of cross-sectional area circle conversion particle diameter of a primary particle.

Fifth, it is preferable to use a binder that reduces residual solvent.

As a result of our study, it was confirmed that the amount of residual solvent changes depending on the binder used, although the cause is not clear.

The representative binders are listed below in order.

[0051]

[Table 1]

Sixth, by using the first to fifth combinations in combination, the residual solvent is further reduced, which is more preferable.

The hydrophobic binder used in the magnetic recording layer may be a thermoplastic resin, a radiation curable resin, a thermosetting resin, or any other reactive resin, which may be used alone or in combination.

As the above-mentioned thermoplastic resin, vinyl chloride-
Vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, copolymer of vinyl acetate and vinyl alcohol, partially hydrolyzed vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile Copolymer, ethylene-vinyl alcohol copolymer,
Vinyl-based polymers or copolymers such as chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, and cellulose derivatives such as nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate resin. , Maleic acid and / or acrylic acid copolymer, acrylic acid ester copolymer, acrylonitrile-styrene copolymer, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer Coalesce, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, Examples thereof include rubber resins such as amino resins, styrene-butadiene resins, butadiene-acrylonitrile resins, silicone resins, and fluorine resins.

The above-mentioned thermoplastic resin has Tg of -40 to 180 ° C,
It is preferably 30 to 150 ° C., the weight average molecular weight is preferably 5,000 to 300,000, and more preferably the weight average molecular weight is 10,000 to 200,000.

The radiation-curable resin is a resin which is cured by radiation such as electron beam and ultraviolet rays, and examples thereof include maleic anhydride type, urethane acryl type, ether acryl type and epoxy acryl type.

Examples of thermosetting resins and other reactive resins include phenolic resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, and silicone-based curable resins.

The hydrophobic binders listed above may have a polar group in the molecule. The polar group epoxy group, -COOM, -OH, -N (R 1) R 2, -NR 3 X, -SO 3 M, -OSO
_{3 M, -PO 3 M 2,} -OPO 3 M (M each hydrogen, an alkali metal, an ammonium, X is an acid which forms an amine salt, R
Represent hydrogen and an alkyl group, respectively. ) Is mentioned.

The hardener is usually added in an amount of 0.01 to the resin solid content.
-60% by weight, preferably 0.05-50% by weight.

The magnetic recording medium of the present invention can be obtained by dispersing and kneading the above components in an organic solvent, coating the mixture on a non-magnetic support, orienting it if necessary, and then drying. After drying, planar treatment may be performed if necessary.

As the solvent used in the dispersion, kneading and coating of the present invention, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone and tetrahydrofuran in any ratio; methanol, ethanol, propanol, butanol, Alcohol such as isobutyl alcohol, isopropyl alcohol, methylcyclohexanol; ester such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isopropyl acetate, ethyl lactate, glycol acetate, monoethyl ether; ether, glycol dimethyl ether, glycol Glycol ethers such as monoethyl ether and dioxane; benzenetoluene, xylene,
Tar-based compounds (aromatic hydrocarbons) such as cresol, chlorobenzene and styrene; chlorinated hydrocarbons such as methylene chloride, ethylene chloride, carbon tetrachloride, chloroform, ethylene chlorohydrin and dichlorobenzene, N, N-
Dimethyl formaldehyde, hexane, etc. can be used.

The method of dispersion is not particularly limited, and the order of addition of each component can be set appropriately. For the preparation of the magnetic paint, a conventional kneading machine such as a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a tron mill,
Sand grinder, Szegvari attritor, high speed impeller, disperser, high speed stone mill, high speed impact mill, disper, kneader, high speed mixer, reciprocating blender, cokneader, intensive mixer,
A tumbler, a blender, a disperser, a homogenizer, a single screw extruder, a twin screw extruder, an ultrasonic disperser, etc. can be used.

The magnetic recording layer may be provided on the support by using a coater such as an extrusion coater, an air doctor coater, a blade coater, an air knife coater or a squeeze coater, an impregnation coat method, a reverse roll coat method, Transfer roll coating method, gravure coating method, kiss coating method, cast coating method, spray coating method and the like can be used. In order to perform multi-stripe coating, these coating coaters may be arranged in series. As a specific method of stripe coating, for example,
JP-A-48-25503, JP-A-48-25504, and JP-A-48-98803
No. 50-138037, No. 52-15533, No. 51-
3208, 51-6239, 51-65606, 5
1-140703 publication, Japanese Patent Publication No. 29-4221 publication, U.S. Patent 3,06
The descriptions in the Nos. 2,181 and 3,227,165 can be referred to.

In order to firmly adhere these magnetic recording layers to the support, an undercoat layer may be provided on the support, and the support may be subjected to chemical treatment, mechanical treatment, corona discharge treatment,
Flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment,
Surface activation treatment such as active plasma treatment, laser treatment, concentrated acid treatment, or ozone oxidation treatment may be performed. Furthermore, an undercoat layer may be provided after the surface activation treatment. The undercoat layer is preferably an aqueous latex type.

The ferromagnetic fine powder used in the transparent magnetic layer of the present invention includes ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder, and strong metal powder. Magnetic alloy powder, barium ferrite, etc. can be used.

As an example of the ferromagnetic alloy powder, the metal content is 75
wt% or more, and 80 wt% or more of the metal content is at least one kind of ferromagnetic metal or alloy (Fe, Co, Ni, Fe-Co, Fe-
Ni, Co-Ni, Co-Fe-Ni, etc.) and 20 wt% of the metal content
Other components (Al, Si, S, Sc, Ti, V, Cr, Mn, C
u, Zn, Y, Mo, Rh, Pd, Ag, Sn, Sb, B, Ba, Ta,
W, Re, Au, Hg, Pb, P, La, Ce, Pr, Nd, Te, Bi, etc.) can be included. In addition, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide.

The method for producing these ferromagnetic powders is known,
The ferromagnetic powder used in the present invention can also be manufactured according to a known method.

The shape and size of the ferromagnetic powder can be widely used without particular limitation. As the shape, needle shape, rice grain,
It may be spherical, cubic, or plate-like, but needle-like or plate-like is preferable in terms of electromagnetic conversion characteristics. The crystallite size and specific surface area are not particularly limited, but the crystallite size is 400 Å or less, and the BET value is 2
0 m ² / g or more is preferable, and 30 m ² / g or more is particularly preferable. The pH of the ferromagnetic powder and the surface treatment can be used without particular limitation (the surface treatment may be performed with a substance containing an element such as titanium, silicon, aluminum, carboxylic acid,
It may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocyclic ring such as sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester, and benzotriazole).
The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron. These magnetic recording layers are described in JP-A-47-32812 and 53-109604.

Hc of the ferromagnetic powder can be used without any particular limitation. It is preferably 400 to 2000 Oe.

In the case of forming an optically transparent magnetic recording layer, the binder is preferably used in an amount of 1 to 20 parts by weight with respect to 1 part by weight of the ferromagnetic powder. More preferably, it is 2 to 15 parts by weight with respect to 1 part by weight of the magnetic powder. Further, the solvent is used in such an amount that the coating can be easily performed.

After providing the magnetic recording layer, calendering is performed on this layer to improve smoothness, and S of magnetic output is improved.
It is also possible to improve the / N ratio. In this case, it is preferable to apply a silver halide photographic light-sensitive layer on the side opposite to the support after calendering.

Examples of the polishing agent include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specifically, aluminum oxides (α-alumina, γ-alumina,
Corundum, etc., Chromium oxide (Cr ₂ O ₃ ), Iron oxide (α-
Fe ₂ O ₃ ), oxides such as silicon dioxide and titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond. Their average particle size is 0.
01-1.0 μm is preferable, the binder of the layer to which the abrasive is added
It can be added in the range of 0.5 to 400 parts by weight with respect to 100 parts by weight.

As the antistatic agent, fine particles of metal oxide are preferable. Examples of metal oxides include oxygen-rich oxides such as Nb ₂ O _{5 + X} , oxygen-deficient oxides such as RhO _2-X and Ir ₂ O _3-X , or Ni (OH) _X. Nonstoichiometric hydride, HfO
₂ , ThO ₂ , ZrO ₂ , CeO ₂ , ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In
₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _5, etc., or a composite oxide thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of containing a heteroatom include, for example, ZnO with A
Addition of l, In, etc., addition of Nb, Ta, etc. for TiO ₂ , and S
The addition of Sb, Nb, halogen elements, etc. is effective for nO ₂ . Addition amount of these hetero atoms is 0.01 mol% to 25 mol%
Is preferable, but the range of 0.1 mol% to 15 mol% is particularly preferable. The volume resistivity of these electrically conductive metal oxide powders is preferably 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less. Further, it may be a sol in which fine particles of the metal oxide are mixed in an aqueous solution.

Besides these, nonionic fine particles, but nonionic surfactants such as alkylene oxides, glycerin and glycidols; higher alkyl amines, quaternary ammonium salts, salts of pyridine and other heterocyclic compounds, Cationic surfactants such as phosphonium or sulfonium compounds; anionic surfactants containing an acidic group such as carboxylic acids, phosphorus compounds, sulfate ester groups, and phosphate ester groups; amino acids, aminosulfonic acids, sulfuric acid of amino alcohols or Examples thereof include amphoteric surfactants such as phosphoric acid esters. These surfactants may be contained as a substituent of the polymer.

In the present invention, a general matting agent may be used. 1 to 100 of binder in the layer to which the matting agent is added
It can be added in the range of up to 400 parts by weight. Specific examples of the matting agent are shown below, but the matting agent is not limited thereto.

[0076]

[Chemical 1]

[0077]

[Chemical 2]

A wax having an average particle size of 0.01 μm to 3.0 μm may be included in the binder in the uppermost layer. To see the size of wax particles, the sample coated on the support was embedded in a room temperature curable resin, and then a microtome was used to make an ultrathin section of about 150 nm thickness. It can be held on a copper mesh and observed with a scanning transmission electron image by an electron microscope. When viewed by this observation method, the shape of the wax particles is generally spindle-shaped or needle-shaped, and some of the waxes having a high melting point are spherical. The diameter or major axis length of 100 or more wax particles observed by the above electron microscope was averaged to obtain the average particle diameter. In the present invention, the average particle size is preferably 0.01 to 3.0 μm, and when 0.01 μm or more, sufficient slipperiness is obtained, and when 3.0 μm or less, scratch resistance is good. And, among these, 0.05-1.0 μm is more preferable, and 0.1-
Most preferred is 0.5 μm.

In the present invention, the layer containing wax having an average particle size of 0.01 to 3.0 μm is the uppermost layer on the side where the transparent magnetic recording layer is provided, and wax may be added to a layer other than the uppermost layer. . The wax at this time can be used without any limitation on the average particle size, but it is more preferable to use a wax that can be added to the uppermost layer.

The uppermost layer may be a protective layer or a magnetic layer, but the uppermost layer is preferably a magnetic layer from the viewpoint of cost. If the top layer is a protective layer, the protective layer thickness is 0.1
It is preferably at least μm, more preferably at least 0.5 μm, and preferably at most 3 μm.

The amount of wax to be added can be used without any particular limitation, but if it is too small, the scratch resistance tends to deteriorate, and if it is too large, the turbidity tends to increase, so that it is relative to the total weight of the binder in the layer containing the wax. 0.1 to 50 wt% is preferable, 1.0 to 20 wt%
Is more preferable and 5.0-10 wt% is the most preferable.

If the wax used for the uppermost layer is present as a liquid at the time of dispersion, it is easily incorporated into the binder and it is difficult to obtain a sufficient effect. Further, if it becomes a liquid during the development processing, it flows out into the development processing solution. Since it is easy, the melting point is preferably 38 ° C or higher, and more preferably 50 ° C or higher in view of storage characteristics such as sticking. Further, it is preferably 150 ° C. or lower for easy handling.

The type of wax used in the present invention can be used without any particular limitation. Specific examples include carnauba wax, candelilla wax, rice wax, wood wax, beeswax, montan wax, ozokerite, ceresin, paraffin wax, and fisher wax.
Examples thereof include troche wax, polyethylene wax, silicone oil such as polysiloxane, fluorine-based lubricant, higher fatty acid, higher fatty acid ester and the like.

[0084]

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

Example 1 [Samples 1-1 to 1-3] 1-1) Preparation of undercoating base <Preparation of support 1> As a polyester resin for the support, P-1: commercially available polyethylene terephthalate ( Intrinsic viscosity
0.65) P-2: 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added to 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SI
P) ethylene glycol solution (concentration 35% by weight) 28 parts by weight (5 mol% / total ester bond), polyethylene glycol (abbreviation: PEG) (number average molecular weight: 4,000) 11 parts by weight (8.5% by weight / reaction product) Total weight), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.13 part by weight, Irganox 1010 (CIBA-GEIGY as an antioxidant
(Made by the company) was added so that it might be 1 weight% with respect to the product polymer. Then gradually raise the temperature and reduce the pressure to 280 ° C, 0.5 mm
Polymerization was carried out with Hg to obtain a copolyester (intrinsic viscosity
0.55).

After vacuum drying each of P-1 and P-2 at 150 ° C., two of the three extruders were used for P-2.
Melt extruded at ℃, the film thickness ratio of the three layers is P-2: P-1: P
-2 = 1: 2: 3, the layers were joined in a T-die in a layered form, and rapidly solidified on a cooling drum to obtain a laminated unstretched film. Then, after longitudinal stretching (3.4 times) at 85 ℃, the temperature is further 95
After transverse stretching (3.4 times) at ℃, heat set at 210 ℃,
A biaxially stretched film having a thickness of 90 μm was obtained.

8 W / (m) on both sides of the support of this polyethylene terephthalate (laminated type of materials having different moisture absorption)
² min. Of corona discharge treatment, and the following subbing coating solutions U-1 and U-2 are applied to the outer side of the thin side of the copolyester.
Coating to a dry film thickness of 0.8 μm and 0.1 μm, and to the other surface, apply the undercoating coating solution U-3 below to a dry film thickness of 0.8 μm to obtain an undercoating layer having an antistatic function. A formed support was prepared.

(Undercoating Coating Liquid U-1) Copolymer Latex Liquid of Butyl Acrylate / t-Butyl Acrylate / Styrene / 2-Hydroxy Acrylate (Superposed Composition Ratio; 30: 20: 25: 25, Solid Content 30%) 270 g Compound (A-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g These were mixed and diluted with water to make 1 liter.

(Undercoating Coating Solution U-2) Gelatin 10 g Compound (A-1) 0.2 g Compound (A-2) 0.2 g Compound (A-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Was mixed and diluted with water to make 1 liter.

(Undercoating coating liquid U-3) Polyester latex liquid (solid content 30%) 223 g Tin oxide fine powder (average particle size 0.05 μm) “SN100P” made by Ishihara Sangyo Co., Ltd. 107 g These are mixed and dispersed to prepare water / isopropanol. 1000 g of the 3/1 mixture was added.

The structures of the compounds A-1 to A-3 used are shown below.

[0092]

[Chemical 3]

1-2) Coating of magnetic recording layer On the coating of the undercoating layer U-3 of the undercoating base, the magnetic coating material M-1 having the following composition was dried as shown in Table 2 using a precision extrusion coater. Apply to achieve the film thickness and at 90 ° C
It was dried for 10 minutes.

(Magnetic paint M-1) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Vinyl chloride / vinyl acetate copolymer resin 70 parts by weight VAGH (manufactured by Union Carbide Co., Ltd.) Carnauba wax No. 1 7 parts by weight Refractive index 1.46 Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight These were kneaded and dispersed to obtain a magnetic paint.

[Samples 1-4 to 1-5] Samples 1-2 were prepared in the same manner except that the solvent composition was changed to the solvent composition shown in Table 2 without changing the amount of solvent.

[Samples 1-6 to 1-8] Samples 1-2 were prepared in the same manner except that the drying temperature shown in Table 2 was changed.

[Sample 1-9] Magnetic Paint M- of Sample 1-2
It was made in the same manner except that 1 was changed to M-2 below.

(Magnetic paint M-2) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Vinyl chloride / vinyl acetate copolymer resin 70 parts by weight VAGH (Union Carbide Co., Ltd.) Tin oxide fine powder 7 parts by weight SN-100P (Ishihara Sangyo Co., Ltd.) Average particle size 0.05 μm Refractive index 1.98 Carnauba wax No. 1 7 parts by weight Solvent 375 parts by weight The solvent composition is shown in Table 2. [Sample 1-10] Sample 1-9 was prepared in the same manner except that the amount of tin oxide fine powder was changed to 56 parts by weight.

[Sample 1-11] A sample was prepared in the same manner as in Sample 1-9 except that the amount of tin oxide fine powder was changed to 105 parts by weight.

[Sample 1-12] A tin oxide fine powder of Sample 1-9 was prepared in the same manner except that the following matting agent was used.

Matting agent Average particle size 0.012 μm, refractive index
1.45 Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd.) [Sample 1-1
3] Sample 1-12 was manufactured in the same manner except that the amount of matting agent was changed to 56 parts by weight.

[Sample 1-14] The amount of the matting agent of Sample 1-12 was changed to
The same procedure was performed except that the amount was changed to 105 parts by weight.

[Sample 1-15] Magnetic Paint M- of Sample 1-2
It was made in the same manner except that 1 was changed to M-3 below.

(Magnetic Paint M-3) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Butyl acetate / vinyl chloride copolymer (molar ratio 1 1) 20 parts by weight Polyurethane resin 10 parts by weight Toluene diisocyanate 40 parts by weight Carnauba wax No.1 7 parts by weight Solvent 150 parts by weight Solvent composition is shown in Table 2 [Sample 1-16] Magnetic properties of sample 1-2 Paint M-1 below M-
It was made in the same manner except that it was changed to 4.

(Magnetic paint M-4) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Polyurethane resin 70 parts by weight UR-8200 (Toyobo Co., Ltd. )) Carnauba wax No. 1 7 parts by weight Solvent 300 parts by weight The solvent composition is shown in Table 2 [Sample 1-17] The magnetic paint M-1 of Sample 1-2 was used as M-
It was made in the same manner except that it was changed to 5.

(Magnetic coating M-5) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Polyurethane resin 70 parts by weight CA-239 (Toyo Morton ( Carnauba wax No.1 7 parts by weight Solvent 300 parts by weight Solvent composition is shown in Table 2 [Sample 1-18]
It was made in the same manner except that it was changed to 6.

(Magnetic paint M-6) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Vinyl acetate / vinyl chloride copolymer 70 parts by weight MR -110 (manufactured by Nippon Zeon Co., Ltd.) Carnauba wax No. 1 7 parts by weight Solvent 300 parts by weight Solvent composition is shown in Table 2 [Sample 1-19]
It was made in the same manner except that the number was changed to 7.

(Magnetic paint M-7) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe 100 parts by weight BTH-1 / 2 ( (Asahi Kasei Co., Ltd.) (Solid content 70 wt%) Carnauba wax No. 1 7 parts by weight Solvent 500 parts by weight Solvent composition is shown in Table 2 [Sample 1-20] Sample 1-2 magnetic paint M-1 M-
It was made in the same manner except that it was changed to 8.

(Magnetic paint M-8) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Diacetylcellulose resin 70 parts by weight Carnauba wax No. 1 7 parts by weight Solvent 500 parts by weight The solvent composition is shown in Table 2 [Sample 1-21] The magnetic paint M-1 of Sample 1-2 was used as M-
It was made in the same manner except that it was changed to 9.

(Magnetic paint M-9) Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 Oe Phenoxy resin 70 parts by weight PKHH (Union Carbide ( Carnauba Wax No. 1 7 parts by weight Solvent 300 parts by weight The solvent composition is shown in Table 3 [Sample 1-22] The magnetic coating material M-1 of Sample 1-2 was used as the following M-
The film was manufactured in the same manner except that the film thickness was changed to 10 and the film thickness was changed to the film thickness shown in Table 3.

(Magnetic paint M-10) Cobalt-containing gamma iron oxide specific surface area 45 m ² / g 1 part by weight Cobalt-containing gamma iron oxide specific surface area 80 m ² / g 1 part by weight Barium ferrite fine powder specific surface area 15 m ² / g 2 parts by weight Part Barium ferrite fine powder Specific surface area 40 m ² / g 2 parts by weight Butyl acetate / vinyl chloride copolymer (molar ratio 1: 1) 20 parts by weight Polyurethane resin 10 parts by weight Toluene diisocyanate 40 parts by weight Carnauba wax No. 1 7 parts by weight Solvent 150 parts by weight Solvent composition is shown in Table 3 [Sample 1-23] Sample 1-22 was prepared in the same manner except that the solvent composition shown in Table 3 was changed.

[Sample 1-24] A sample was prepared in the same manner except that the solvent composition of sample 1-20 was changed to the solvent composition shown in Table 3.

[Sample 1-25] The sample was prepared in the same manner except that the solvent composition of sample 1-2 was changed to the solvent composition shown in Table 3.

[Sample 1-26] The same procedure as in Example 1-2 was repeated except that the support 1 of sample 1-2 was changed to the following support 2 and the following heat treatment was performed.

2-6 To 100 parts by weight of dimethyl naphthalenedicarboxylate and 60 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added, and transesterification reaction was carried out according to a conventional method. Antimony trioxide (0.05 parts by weight) and phosphoric acid trimethyl ester (0.03 parts by weight) were added to the obtained product. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 290 ° C. and 0.5 mmHg to obtain polyethylene 2-6 naphthalate having an intrinsic viscosity of 0.60.

Using this, it was vacuum dried at 150 ° C. for 8 hours, melt-extruded in layers from a T die at 300 ° C., adhered onto a cooling drum at 50 ° C. while electrostatically applied, cooled to solidify, and unstretched. Got the sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total lateral stretching ratio using a tenter type lateral stretching machine, and further at a second stretching zone at 155 ° C. in a total lateral stretching ratio of 3.3 times. Was stretched. Then, it was heat-treated at 100 ° C. for 2 seconds, further fixed at a first heat setting zone of 200 ° C. for 5 seconds, and heat fixed at a second heat setting zone of 240 ° C. for 15 seconds. Then, while being relaxed in the transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

<Heat Treatment> After the magnetic recording layer was coated and dried, the magnetic recording layer was wound inside a stainless steel core having a diameter of 30 cm, and heat treatment was performed at 110 ° C. for 6 hours.

[Samples 1-27 to 1-29] The samples 1-26 were manufactured in the same manner except that the drying temperature shown in Table 3 was changed.

[Samples 1-30 to 1-31] Samples 1-2 were prepared in the same manner except that the film thicknesses in Table 1-2 were changed to those shown in Table 3.

[Sample 1-32] A sample was prepared in the same manner as in Sample 1-9 except that the amount of fine tin oxide powder was changed to 3.5 parts by weight.

[Sample 1-33] A sample was prepared in the same manner as sample 1-9 except that the amount of tin oxide fine powder was changed to 210 parts by weight.

[Sample 1-34] A sample was prepared in the same manner as in Sample 1-9 except that the amount of the tin oxide fine powder was changed to 245 parts by weight.

[Sample 1-35] The amount of the matting agent of Sample 1-12 was changed to
It was made in the same manner except that the amount was changed to 3.5 parts by weight.

[Sample 1-36] The amount of the matting agent of Sample 1-12 was changed to
It was made in the same manner except that the amount was changed to 210 parts by weight.

[Sample 1-37] The amount of the matting agent of Sample 1-12 was changed to
The same production was performed except that the amount was changed to 245 parts by weight.

[Sample 1-38] The sample was prepared in the same manner except that the matting agent of Sample 1-13 was changed to the following matting agent.

Matting agent Seahost KE-P100 (manufactured by Nippon Shokubai Co., Ltd.) Average particle size 1.0 μm Refractive index 1.43 [Sample 1-39] The same as the matting agent of Sample 1-13 except that the following matting agent was used. It was made.

Matting agent Seahoster KE-P150 (manufactured by Nippon Shokubai Co., Ltd.) Average particle diameter 1.5 μm Refractive index 1.44 1-3) Coating of photosensitive material layer Layer U-2
After applying a corona discharge treatment of 25 W / (m ² · min) on the
A multilayer color light-sensitive material having the emulsion layer structure of Example 1 described in Japanese Patent Application No. 4-267697 was prepared to prepare a photographic light-sensitive material.

In the multilayer emulsion layer, 13.7 g of gelatin, 2.3 g of silver halide grains having an average grain size of 0.3 to 0.4 μm and 0.7 to 0.8 μm, and an oil drop amount of 2.8 g per m ² , respectively, a film thickness of 27 μm Is.

<Development Treatment> The produced film base and photographic light-sensitive material were subjected to development treatment with the treatment process shown below and the treatment liquid having the composition shown below.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was on the street.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N-Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 liter pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water was added to 1.0 liter pH 6.0 Fixer Disodium ethylenediamine tetraacetate 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 mg Sodium bisulfite 4.6 g Water was added 1.0 liter pH 6.6 Stabilizer Formalin (40%) 2.0mg Polyoxyethylene-p-mono Nonylphenyl ether (average degree of polymerization: 10) 0.3 g Water was added to 1.0 liter The sample obtained as described above was evaluated as follows.

[Amount of Residual Solvent] 1 cm of 7 cm ² sample before development processing
The mixture was placed in a 0 ml vial and sealed, heated at 170 ° C. for 20 minutes, and then quantified by headspace gas chromatography.

(Headspace Gas Chromatography Apparatus) HP5890 Gas Chromatography (manufactured by Hewlett Packard) HP7694 Headspace Sampler (manufactured by Hewlett Packard) DB-WAX column (manufactured by J & W Scientific) Length 30 m, inner diameter 0.53 mm [ Decrease in color density] Samples before development were processed at 25 ℃ and 60% RH for 3
After humidity conditioning for a period of time, the product was placed in a polyethylene resin-coated bag, sealed, and heated at 50 ° C. for 1 week.

After that, the sample taken out from the bag was exposed to white light with a step wedge for sensitometry, and then,
The color development processing was performed.

Then, the maximum green density of color development was measured, and the storage photographic performance represented by the following formula was determined. The closer the value is to 100%, the better.

[0138]

[Equation 1]

[Flatness] A sample before development treatment was performed at 23 ° C. and 55%.
After conditioning the humidity for 12 hours under the condition of RH, it was spread on a flat board, the degree of the waviness was visually evaluated, and ranked according to the following criteria. The practicality in this ranking is determined based on the tolerance of the quality of the photographic light-sensitive material, and it is necessary that the rank is ◯ or higher.

Rank Waviness ◎ Good ○ Rubbing is visible when viewed closely × Waviness is large [Scratch resistance] A sample before development processing was put on a stainless steel ball (10 mmφ) using HEIDON Trigear Type 14DR
A load of 50 g was applied, and sliding was repeated 100 times at a speed of 10 cm / sec. The degree of subsequent scratching was determined as shown below.

5: No scratches 4: There was a slight sliding trace 3: There was a sliding trace 2: There was a sliding trace, which had an effect on image quality when printing or projecting.

1: There is a scratch 0: There is film peeling If it is 3 or more, there is no problem in practical use such as printing or projection.

[0143]

[Table 2]

[0144]

[Table 3]

From the examples, it can be seen that when the residual solvent amount is 200 μl / m ² or less, the color density reduction and the scratch resistance are improved. It can be seen that the high temperature scratch resistance is further improved by setting the residual solvent amount to 100 μl / m ² or less, and the high temperature scratch resistance is most excellent when the residual solvent amount is 50 μl / m ² or less. Further, the dry film thickness of the transparent magnetic layer is 0.3 to 2.0 μm, the residual solvent amount is small,
It can be seen that it is also excellent in scratch resistance. In addition, non-magnetic fine particles are contained in the transparent magnetic recording layer in an amount of 10 wt% or more (particularly
It can be seen that the content of the residual solvent is small and the scratch resistance is excellent by containing 20 wt% or more). Even if it contains 5wt%,
It can be seen that there is no effect of reducing the amount of residual solvent, and if the content exceeds 300 wt%, the scratch resistance is slightly reduced. Further, it is found that nitrocellulose, diacetyl cellulose and phenoxy resin are more excellent as the binder used. Further, it is found that when the polyethylene-2,6-naphthalenedicarboxylate support is used and the drying temperature is 90 ° C. or higher and 120 ° C. or lower, the residual solvent amount is small and the flatness is excellent.

[0146]

When the amount of residual organic solvent is small, the decrease in color density during storage is small and the scratch resistance is excellent.

When the non-magnetic fine particles are contained in the binder in an amount of 20 wt% or more, the amount of residual organic solvent can be reduced, the reduction in color density during storage can be reduced, and the scratch resistance can be improved.

When a transparent magnetic recording layer coating liquid containing a solvent having a boiling point of 100 ° C. or lower at a solvent ratio of 35 wt% or higher is applied and dried at 100 ° C. or higher, and then a silver halide emulsion layer is formed,
The amount of residual organic solvent can be made small, the color density at the time of storage can be made small, and the scratch resistance can be improved, while the adverse effects of high temperature drying on the silver halide emulsion layer can be prevented.

Claims (10)

[Claims] 1. A silver halide photographic light-sensitive material having one or more silver halide emulsion layers on one side and a transparent magnetic recording layer on the other side on a support, wherein the silver halide photographic light-sensitive material is used. A silver halide photographic light-sensitive material characterized in that the amount of organic solvent remaining therein is 200 μl / m ² or less. 2. A silver halide photographic light-sensitive material having one or more silver halide emulsion layers on one side and a transparent magnetic recording layer on the other side of a support, wherein the silver halide photographic light-sensitive material is used. A silver halide photographic light-sensitive material, characterized in that the amount of organic solvent remaining in the solution is 100 μl / m ² or less. 3. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side and a transparent magnetic recording layer on the other side of a support, wherein the transparent magnetic recording layer is provided. However, the silver halide photographic light-sensitive material is characterized by containing 20 wt% or more of non-magnetic fine particles with respect to the binder in the transparent magnetic recording layer. 4. The silver halide photographic light-sensitive material according to claim 1, wherein the transparent magnetic recording layer contains non-magnetic fine particles in an amount of 10 wt% to 300 wt% with respect to the binder of the transparent magnetic recording layer. material. 5. The thickness of the transparent magnetic recording layer is 0.3 μm to 2.0 μm.
5. The silver halide photographic light-sensitive material according to claim 1, 2, 3 or 4. 6. The transparent magnetic recording layer comprises nitrocellulose,
6. The silver halide photographic light-sensitive material according to claim 1, comprising at least one binder selected from diacetyl cellulose and phenoxy resin. 7. The halogenated product according to claim 1, wherein the support used for the transparent magnetic recording layer is polyethylene-2,6-naphthalenedicarboxylate. Silver photographic light-sensitive material. 8. A method for producing a silver halide photographic light-sensitive material having one or more silver halide emulsion layers on one side of a support and a transparent magnetic recording layer on the other side of the support. Characterized by coating a transparent magnetic recording layer coating liquid containing a solvent having a boiling point of 100 ° C or lower in a solvent ratio of 35 wt% or higher, followed by drying at a drying temperature of 100 ° C or higher, and then forming a silver halide emulsion layer And a method for producing a silver halide photographic light-sensitive material. 9. The transparent magnetic recording layer contains 1 part by weight or more of a hydrophobic binder with respect to 1 part by weight of ferromagnetic powder in the transparent magnetic recording layer. ,
3, 4, 5, 6 or 7 silver halide photographic light-sensitive material. 10. A support containing one or more silver halide emulsion layers on one side, and one or more parts by weight of a hydrophobic binder on the other side with respect to 1 part by weight of a ferromagnetic powder. In a method for producing a silver halide photographic light-sensitive material having a transparent magnetic recording layer, a transparent magnetic recording layer coating solution containing a solvent having a boiling point of 100 ° C. or less in a solvent ratio of 35 wt% or more is applied on a support, and then 100 A method for producing a silver halide photographic light-sensitive material, which comprises drying at a drying temperature of ℃ or more and then forming a silver halide emulsion layer.