JPH0777752A - Photographic sensitive material having transparent magnetic recording layer - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material having on a support, a silver halide emulsion layer and a transparent magnetic recording layer stable in reproduction output and small in read error and superior in abrasion resistance even under high humidity by incorporating a magnetic powder formed in the presence of an organic solvent in the recording layer. CONSTITUTION:The photographic sensitive material has at least one silver halide emulsion layer on one side of the support and the magnetic recording layer containing the magnetic powder, such as that of a metal, iron oxide, iron oxide doped with Co, Cr02, or barium ferrite, formed in the presence of an organic solvent. The form and size of the magnetic powder are not especially limited and many kinds of them may be widely used, but acicular or flat forms are preferable from the viewpoint of electromagnetic conversion characteristics.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION For photographic light-sensitive materials, various information on photographic light-sensitive materials such as type / manufacturing number of photographic light-sensitive material, manufacturer's name, emulsion No., etc. Conditions, filters used, weather, shooting frame size, camera model, various information at the time of camera shooting such as use of anamorphic lens, for example, number of prints, selection of filter, customer's color preference, Various information necessary for printing, such as the size of the trimming frame,
For example, inputting various information obtained at the time of printing such as the number of prints, selection of filters, customer's color preference, size of trimming frame, and other customer information is important for management. It is also necessary to improve print quality and improve the efficiency of printing work.

In a conventional photographic light-sensitive material, it is impossible to input all the information, and
At the time of shooting, I was only optically entering information such as the shooting date / time, aperture, and exposure time. Moreover, at the time of printing, it was impossible to input the above information into the photographic light-sensitive material because there was no means for that.

Since the magnetic recording system is easy to record / reproduce, the use of the magnetic recording system for inputting the above various information to the photographic light-sensitive material has been studied and various techniques have been proposed.

For example, a stripe-shaped magnetic recording layer in which fine particles of a ferromagnetic material are dispersed is provided on the emulsion surface or the back surface next to the image area, and information such as voice and photographing conditions is provided to a silver halide photographic light-sensitive material. The above-mentioned recording is disclosed in JP-A-50-626.
No. 27, No. 49-4503, U.S. Pat.No. 3,243,376, No. 3,220,843, etc., and also on the back surface of the silver halide photographic light-sensitive material, the amount of magnetizable particles, size, etc. Providing a transparent magnetic recording layer having the required transparency by selecting (1) is described in US Pat. Nos. 3,782,947, 4,279,945, and 4,302,523. Also, US Pat. No. 4,947,196 and WO90 / 04254 describe a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material that enables magnetic recording on the back surface of the photographic film. Has been done.

By providing these magnetic recording layers, it becomes possible to record the above-mentioned various kinds of information in the silver halide photographic light-sensitive material, which has been difficult in the past, and also to record voice and image signals in the future. Have sex.

However, in the conventional photographic light-sensitive material having a magnetic recording layer, unlike the tape used for magnetic recording, the magnetic recording layer is an emulsion in which a hydrophilic binder such as gelatin is used. Since it is provided on a photographic light-sensitive material having a layer and a thick base, there is a problem that recording / reproducing of magnetic information cannot be stably performed. Especially in the high humidity state, the magnetic output was not stable and many read errors occurred.

Further, in a photographic light-sensitive material having a magnetic recording layer, the dispersion of the magnetic fine particles is stable in the magnetic coating material in which the magnetic fine particles forming the magnetic recording layer are dispersed, so that the liquid stability is high. It was also required that the magnetic recording layer had high scratch resistance even under high humidity.

[0009]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a photographic light-sensitive material having a magnetic recording layer which is stable in reproduction output even under high humidity, has few reading errors, and has excellent scratch resistance. is there. A second object of the present invention is to provide a photographic light-sensitive material having a magnetic recording layer using magnetic fine particles having excellent dispersibility.

[0010]

The above objects can be achieved by the following photographic light-sensitive materials. (1) In a photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support and a transparent magnetic recording layer on the other side, the magnetic recording layer is formed in the presence of an organic solvent. A photographic light-sensitive material containing the above-mentioned magnetic powder.

The present invention will be described in more detail below. First, the transparent magnetic recording layer will be described. The magnetic substance powder used in the magnetic recording layer of the present invention is a magnetic substance powder formed in the presence of an organic solvent, and includes a metal magnetic substance powder, an iron oxide magnetic substance powder, a Co-doped iron oxide magnetic substance powder, and a dioxide. Examples thereof include chromium magnetic substance powder and barium ferrite magnetic substance powder.

The shape and size of the magnetic powder can be widely used without any particular limitation. As the shape, needle shape, rice grain,
It may have any shape such as a spherical shape, a cubic shape, or a plate shape, but a needle shape or a plate shape is preferable in terms of electromagnetic conversion characteristics. The crystallite size and specific surface area are not particularly limited. The magnetic powder may be surface-treated. For example, it may be surface-treated with a substance containing an element such as titanium, silicon or aluminum, or may be adsorbed with a nitrogen-containing heterocycle such as carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester or benzotriazole. It may be treated with an organic compound such as a polar compound. The pH of the magnetic powder is not particularly limited, but is preferably in the range of 5-10.

As the metal magnetic powder, for example, the metal content is 75% by weight or more, and 80% by weight or more of the metal content is a ferromagnetic metal or alloy (Fe, Co, Ni, Fe-Co, F).
e-Ni, Co-Ni, Co-Fe-Ni, etc., and other components (Al, Si, S, Sc, etc.) at 20% by weight or less.
Ti, V, Cr, Mn, Cu, Zn, Y, Mo, Rh,
Pd, Ag, Sn, Sb, B, Ba, Ta, W, Re,
Au, Hg, Pb, P, La, Ce, Pr, Nd, T
e, Bi, etc.) are included. Further, the ferromagnetic metal component may contain a small amount of hydroxide or oxide.

Examples of iron oxide of the iron oxide magnetic material and the Co-doped iron oxide magnetic material include γ-iron oxide.
The ratio of divalent iron / trivalent iron in these iron oxides is not particularly limited.

Regarding these magnetic recording layers, Japanese Patent Laid-Open No.
-32812 and 53-109604.

Regarding the size of magnetic particles, it is "television" that there is a correlation between the size and the transparency.
Volume 20, No. 2, "Characteristics of Ultrafine Particle Semitransparent Magnetic Recording Material and Its Application". For example, in the acicular powder of γ-Fe ₂ O ₃ , the light transmittance is improved by reducing the particle size.

US Pat. No. 2,950,971 describes that a magnetic layer consisting of magnetic iron oxide dispersed in a binder is transparent to infrared radiation. US Pat.
No. 9,945 describes that when the particle size is reduced, the wavelength is increased even when the concentration of magnetic particles in the magnetic layer is relatively high.
It is described that the transmittance of 632.8 nm helium / neon laser light is improved.

However, when the magnetic recording layer is provided in the image forming region of the silver halide color photographic light-sensitive material, not only the red region but also the green region and the blue region must have high light transmittance.

In order to increase the light transmittance in the red region, the green region and the blue region, the particle size of the magnetic particles is reduced and the coating amount of the magnetic particles is also limited.

If the particle size of the magnetic particles is reduced to a certain extent or more, the required magnetic characteristics cannot be obtained. Therefore, it is preferable to make the particle size of the magnetic powder small within the range where the required magnetic characteristics are obtained. Further, if the coating amount of the magnetic particles is reduced to a certain extent or more, the required magnetic characteristics cannot be obtained, so it is preferable to reduce the coating amount within the range where the required magnetic characteristics are obtained.

Practically, the coating amount of the magnetic powder is 0.001
A to 3 g / m ^2, more preferably from 0.01 to 1 g / m ^2, particularly preferably 0.2 g / m ² or less.

The magnetic substance powder contained in the magnetic recording layer of the present invention is a magnetic substance powder formed in the presence of an organic solvent.

Methods for producing these magnetic powders are known, and the magnetic powder of the present invention can be produced by referring to these known methods for producing magnetic powders.

The method for producing the magnetic powder of the present invention will be specifically described below, but the magnetic powder of the present invention is not limited to those obtained by these methods.

(Method for producing magnetic powder using alkoxide method) Iron trialkoxide (Fe (OR ₁ ) ₃ ) and cobalt dialkoxide (Co (OR ₂ ) ₃ ) (wherein R ₁ ,
R ₂ represents a methyl group or an ethyl group. 2) in a ratio of 2: 1 in a dry nitrogen atmosphere and an organic solvent to form a homogeneous solution. R _{1 of} the above alkoxide,
When R ₂ is a methyl group, methanol is used as the solvent, and when it is an ethyl group, ethanol is used. Water is gradually added to this solution to first form core particles and then grow crystals to a desired particle size.
After the crystal grows to a desired particle size, it is filtered to obtain a magnetic powder. The obtained magnetic powder had a narrow particle size distribution and was monodisperse.

Other methods for producing magnetic powder include coprecipitation method, high temperature hydrolysis method, chelate method, redox method, compound decomposition and precipitation method, poor solvent dilution method, microemulsion method (emulsion polymerization method). , A phase change method, etc., and these manufacturing methods can also be adopted for manufacturing the magnetic powder of the present invention. In order to produce the magnetic powder of the present invention by these production methods, an organic solvent such as alcohol may be present during production.

In the present invention, the magnetic powder of the present invention can be used in combination with the magnetic powder produced by another method within a range not impairing the effects of the present invention.

As the binder used in the magnetic recording layer, known thermoplastic resins, radiation curable resins, thermosetting resins and other reactive resins conventionally used as binders for magnetic recording media are used. Mixtures of can be used.

As the above-mentioned thermoplastic resin, vinyl chloride-
Vinyl acetate copolymer, vinyl chloride resin, copolymer of vinyl acetate and vinyl alcohol, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer,
Vinyl-based polymers or copolymers such as ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, nitrocellulose, cellulose acetate propionate, cellulose Cellulose derivatives such as acetate butyrate resin, copolymers of maleic acid and / or acrylic acid, acrylonitrile-styrene copolymers, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene copolymers, methylmethacrylate-butadiene-styrene copolymers Polymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether Fat, polyamide resins, styrene -
Examples thereof include rubber-based resins such as butadiene resin and butadiene-acrylonitrile resin, silicone-based resin, and fluorine-based resin.

The above-mentioned thermoplastic resin has a Tg of -40 ° C to 150 ° C.
C., preferably 60.degree. C. to 120.degree. C., and the weight average molecular weight is preferably 5,000 to 300,000, more preferably 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 phenol resins, amino resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, and silicone-based curable resins.

The binders listed above may have a polar group in the molecule. The polar group is an epoxy group, -C
_{OOM, -OH, -NR 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 a counter ion to form a quaternary ammonium salt, R represents each represent hydrogen, an alkyl group.) And so on.

A hydrophilic binder may also be used as the binder of the magnetic recording layer of the present invention.

The hydrophilic binder usable in the present invention is, for example, Research Disclosure No. 1764.
Examples thereof include water-soluble polymers, cellulose ethers, latex polymers and water-soluble polyesters described on pages 3, 26, and No. 18716, page 651.

As the water-soluble polymer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, acrylic acid type copolymer,
Examples thereof include maleic anhydride copolymers, cellulose ethers such as carboxymethyl cellulose and hydroxyethyl cellulose, and latex polymers such as vinyl chloride copolymers, vinylidene chloride copolymers and acrylic ester copolymers. Examples of the latex include polymers, vinyl acetate-based copolymers and butadiene-based copolymers. Of these, gelatin is the most preferable.

Gelatin may be unmodified or modified. Further, a part thereof is colloidal albumin, casein, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids, for example,
It may be replaced with polyvinyl alcohol, poly N-vinylpyrrolidone, an acrylic acid-based copolymer, polyacrylamide or a derivative thereof, a partial hydrolyzate, a gelatin derivative or the like.

The hydrophilic binder containing gelatin is preferably hardened. Examples of hardeners that can be used include
Aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2
-Hydroxy-4,6-dichloro-1,3,5-triazine, U.S. Pat. Nos. 3,288,775, 2,732,303, British Patent 974,723, 1,167,207, etc. Reactive halogen-containing compounds, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat. Nos. 3,635,718, 3,232,763, and British Patent Compounds having a reactive olefin described in 994,869, etc., N-hydroxymethylphthalimide, US Pat. Nos. 2,732,316, 2,586,1
N-methylol compounds described in 68, etc., isocyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017,280,
2,983,611 and other aziridine compounds, U.S. Pat.No. 2,725,294, and 2,725,295
Acid derivatives described in U.S. Pat.
Examples thereof include epoxy compounds described in 3,091,537 and halogen carboxaldehydes such as mucochloric acid.

Inorganic hardeners may also be used, and examples of the inorganic hardeners include chrome alum, zirconium sulfate, and the like. JP-B-56-12853, 58-3
2699, Belgian Patent No. 825,726, JP 6
0-225148, JP-A-51-126125, JP-B-58-50
699 publication, JP-A-52-54427 publication, U.S. Patent 3,321,313
The carboxyl group-activating type hardeners described in the specification and the like can also be mentioned.

Hardeners are typically 0.
It is used in an amount of 01 to 30% by weight, preferably 0.05 to 20% by weight.

The binder for the magnetic recording layer is preferably one that can be used with an organic solvent.

The magnetic powder is dispersed in the binder using a solvent if necessary to form a coating liquid. A ball mill, homomixer, sand mill, or the like can be used to disperse the magnetic powder. In this case, it is preferable to disperse the magnetic particles one by one as much as possible without damaging the magnetic particles.

When forming an optically transparent magnetic recording layer, the binder is preferably used in an amount of 1 to 50 parts by weight per 1 part by weight of the magnetic powder. More preferably, magnetic powder
It is 2 to 30 parts by weight with respect to 1 part by weight. Further, the solvent is used in such an amount that the coating can be easily performed.

As a method for providing the magnetic recording layer on the support, air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, A spray coat can be used. In order to perform multi-stripe coating, these coating heads may be arranged in multiple rows. Specific methods of stripe coating include, for example, JP-A-48-25503, JP-A-48-25504, JP-A-48-98803, and JP-A-50-13803.
7, gazette 52-15533 gazette, gazette 51-3208 gazette, gazette 51-6
No. 239, No. 51-65606, No. 51-140703, Japanese Patent Publication No. 29-4221, U.S. Pat.No. 3,062,181, the same.
The description in the specification of 3,227,165 can be referred to.

A support having a magnetic recording layer may be prepared by co-casting a solution of a binder in which magnetic particles are dispersed and a solution of a polymer for forming a support. in this case,
The binder that disperses the magnetic particles is preferably substantially the same as the polymer for forming the support. The support on which the magnetic recording layer is formed by co-casting may be stretched in order to satisfy mechanical strength, dimensional stability and the like.

In order to firmly adhere these magnetic recording layers to the support, the support may be provided with an undercoat layer, 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 thickness of the magnetic recording layer is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1.
It is 5 to 3 μm.

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to impart functions to the magnetic recording layer such as imparting lubricity, preventing electrification, preventing adhesion, and improving friction and abrasion characteristics. Various additives such as agents can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and for preventing clogging of the magnetic head. An abrasive can be added to the. Functions such as lubrication, antistatic, adhesion prevention, friction / abrasive property improvement, and magnetic head clogging prevention may be provided by providing these functional layers separately from the magnetic recording layer. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance. When the magnetic recording layer is provided in a stripe shape, a transparent polymer layer containing no magnetic material may be provided thereon to eliminate the step due to the magnetic recording layer.
In this case, the transparent polymer layer may have various functions described above.

Examples of lubricants include silicone oils such as polysiloxane, fine plastic powders such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, and fluorocarbons.
These may be used alone or in combination.
These may be added in an amount of 0.2 to 20 parts by weight with respect to 100 parts by weight of the binder.

Examples of the abrasive 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.), Examples thereof include 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 powder such as diamond. The average particle size of these is preferably 0.05 to 1.0 μm, and can be added in the range of 0.5 to 200 parts by weight with respect to 100 parts by weight of the magnetic powder.

After the magnetic recording layer is provided, the surface of the layer is subjected to calendering to improve the smoothness, and the S / N ratio of the magnetic output is increased.
It is also possible to improve the ratio. In this case, it is preferable to apply the silver halide photographic light-sensitive layer after the calendering treatment.

In the present invention, various supports can be used. As the support that can be used, a film of polyester such as polyethylene terephthalate or polyethylene naphthalate, a cellulose triacetate film, a cellulose diacetate film, a polycarbonate film, a polystyrene film, a polyolefin film, a reaction of pyromellitic acid or its anhydride with a diamine, etc. The obtained polyimide film, polyethylene laminated paper, etc. can be mentioned.

The polyester support is not particularly limited, but aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol, 1,4-
Examples thereof include condensation polymers with alkylene glycols such as butanediol, such as polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and copolymers thereof.

In particular, from the curl and curl recovery after development processing, JP-A 1-244446, 1-291248, 1-298350, 2-89045, 2-93641, Ibid 2-181749
It is preferable to use a polyester having a high water content as shown in JP-A Nos. 2-214852 and 2-291135.

These polyesters may have a polar group and other substituents.

The support in the present invention is preferably triacetyl cellulose, polyethylene terephthalate or polyethylene naphthalate.

The above polyester has an area ratio in order to satisfy the mechanical strength and dimensional stability of the film support.
Stretching is preferably performed in the range of 4 to 16 times.

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 support is used for the purpose of neutralizing the tint of the minimum density portion, preventing the light piping phenomenon (fogging) that occurs when light is incident on the film coated with the photographic emulsion layer from the edge, and preventing halation. Dyes can be included.

The type of dye used is not particularly limited, but when a polyester film is used as a support,
In the film forming process, those having excellent heat resistance are preferable, for example,
Examples include anthraquinone-based chemical dyes. Also, as the color tone, if the purpose is to prevent light piping,
Gray dyeing is preferable as seen in general light-sensitive materials. As the dye, one kind or a mixture of two or more kinds may be used. The target can be achieved by using dyes such as Diaresin manufactured by Mitsubishi Kasei Co., Ltd. and MACROLEX manufactured by Bayer Co. alone or in an appropriate mixture.

The photographic light-sensitive material having the magnetic recording layer of the present invention is a black-and-white light-sensitive material, a color negative light-sensitive material, a color paper light-sensitive material, a color reversal light-sensitive material, a movie light-sensitive material, an X-ray. Any photosensitive material such as a photosensitive material, a photosensitive material for printing, a photosensitive material for microphotography, etc. may be used.

Any silver halide can be used in the silver halide emulsion, for example, silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide. , Silver chloroiodobromide, which is appropriately selected depending on the required performance, but silver bromide and silver iodobromide are preferred from the viewpoint of obtaining high sensitivity.

The silver halide grains contained in the silver halide photographic emulsion to be used may be grains in which a latent image is mainly formed on the surface, or may be grains mainly formed inside the grain. .

The silver halide grains may have a regular crystal form such as a cube, octahedron or tetradecahedron,
It may have an irregular crystal shape such as a sphere or a plate. In these particles, (100) plane and (111) plane
Any surface ratio can be used. Further, it may have a composite form of these crystal forms, and grains of various crystal forms may be mixed, but twin silver halide grains having two parallel twin planes facing each other are preferable. .

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the article Photographiesche Correspondents. (Photographishe Korrespondenz)
Volume 99, page 99, volume 100, page 57.

In the present invention, when tabular silver halide grains are used, the average value of the ratio of diameter to thickness of tabular grains (also referred to as aspect ratio) is preferably less than 5, more preferably 1.1 or more. Less than 4.5, particularly preferably
It is 1.2 or more and less than 4. This average value is obtained by averaging the ratio of diameter to thickness of all tabular grains.

The diameter of the silver halide grain is indicated by the diameter corresponding to the circle of the projected area of the silver halide grain (the diameter of the circle having the same projected area as the silver halide grain),
The thickness is preferably 5.0 μm, more preferably 0.2 to 4.0 μm, and particularly preferably 0.3 to 3.0 μm.

As the silver halide photographic emulsion, any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used, but a monodisperse emulsion is preferable.

As the monodisperse silver halide emulsion,
It is preferable that the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more, more preferably 70% or more, and still more preferably the weight of all silver halide grains. 80% or more.

[0070] Here, the average particle diameter r is the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum.

Particle size r here i is a silver halide grain
Convert the projected image of the silver halide grains of the child into a circular image of the same area.
It is the diameter when

Particle size r i is, for example, an electron microscope of the particles.
The image is magnified 10,000 to 70,000 times, and the particles are printed directly on the print.
It can be obtained by measuring the diameter or the area at the time of projection.
Yes (the number of particles measured must be 1,000 or more indiscriminately)
And ).

Particularly preferred highly monodisperse emulsions of the present invention are:

[0074]

[Equation 1] When the breadth of distribution is defined by, the breadth of the distribution is 20%
It is the following, and more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

In the present invention, when silver iodobromide is used as the silver halide, the content of the silver iodide is 4 mol% or more and 15 mol or more as an average silver iodide content in the entire silver halide grains. % Or less, more preferably 5 mol% or more and 12 mol% or less, and particularly preferably 6 mol% or more and 10 mol% or less.

The silver halide grains contained in the silver halide photographic emulsion are preferably so-called core / shell type grains in which silver iodide is concentrated.

The core / shell type particle is a particle composed of a core serving as a core and a shell covering the core, and the shell is formed by one layer or more layers. The silver iodide contents of the core and the shell are preferably different from each other, and it is particularly preferable that the silver iodide contents of the core portions are maximized.

The silver iodide content of the above core is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 25 mol% or more. The silver iodide content of the outermost shell of the above shells, that is, the shell usually forming the outermost surface layer is preferably 5 mol% or less, more preferably 0 to 2 mol%. The proportion of the core is preferably 2 to 60% of the total volume of the particles, and more preferably 5 to 50%.

The silver halide grains contained in the silver halide photographic emulsion are prepared by preliminarily allowing an aqueous solution containing a protective colloid such as gelatin and seed particles to be present in a reaction vessel and, if necessary, silver ions, halogen ions or silver halide fine particles. Can be obtained by growing the seed particles to grow crystals. Here, the seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed grains is arbitrary and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred.

When seed grains are used for preparing a silver halide emulsion, the seed grains may have a regular crystal form such as a cube, octahedron or tetradecahedron, or have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, any ratio of (100) plane to (111) plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed,
It is preferable to use the monodisperse spherical seed particles described in Japanese Patent Application No. 2-408178.

The silver halide photographic emulsion can be produced by any of the acidic method, the neutral method and the ammonia method.

In the production of silver halide photographic emulsion,
The halide ion and the silver ion may be mixed at the same time, or the other may be mixed in the presence of either one. Also,
It may be grown by adding halide ions and silver ions successively or simultaneously while controlling the pH and pAg in the mixing vessel while taking into consideration the critical growth rate of silver halide crystals. The conversion method may be used to change the silver halide composition of the grains at any step of the silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel.

In the production of silver halide photographic emulsion,
Known silver halide solvents such as ammonia, thioether, thiourea and the like can be present.

The silver halide grains contained in the silver halide photographic emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), in the process of forming grains and / or in the process of growing grains. Rhodium salt (including complex salt)
And at least one selected from iron salts (including complex salts) can be used to add a metal ion so that these metal elements can be contained inside and / or on the surface of the particles, and the particles are placed in a suitable reducing atmosphere. By this, reduction sensitization nuclei can be imparted to the inside of the grain and / or the surface of the grain.

In the silver halide photographic emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained therein. When removing the salts, Research Disclosure (Research D
isclosure, hereinafter abbreviated as RD. ) It can be carried out based on the method described in No. 17643, Section II.

Conditions other than those mentioned above in the production of the silver halide photographic emulsion according to the present invention are described in JP-A-61-6643.
No. 61, No. 61-14630, No. 61-112142, No. 62-
No. 157024, No. 62-18556, No. 63-92942,
63-151618, 63-l63451, 63-220238.
The optimum conditions can be selected with reference to known methods such as Japanese Patent Publication No. 63-311244 and Japanese Patent Publication No. 63-311244.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are RD No.17643, RD No. 18716 and RD No.
No. 308119 (Respectively RDl7643, RDl8716 and RD308
Abbreviated as 119. )It is described in. Table 1 shows the locations.

[0089]

[Table 1] When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, photographic additives that can be used are described in the above RD. Table 2 shows the relevant locations.

[0090]

[Table 2] The hardener is used in an amount of 1 to 20% by weight, preferably 2 to 10% by weight, based on dry-processed gelatin.

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used, specific examples of which are described in RDl7643 and RD308119 below. Table 3 shows the related description.

[0092]

[Table 3] Further, these additives can be added to the photographic photosensitive layer by the dispersion method described in RD308119, page 1007, item XIV.

For the color photographic light-sensitive material, the above-mentioned RD308119 is used.
An auxiliary layer such as a filter layer or an intermediate layer described in the section VII-K can be provided.

When the color photographic light-sensitive material is constituted, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned RD308119 VII-K can be adopted.

An undercoat layer may be provided on the support in order to firmly adhere the photosensitive silver halide emulsion layer, the filter layer and the conductive layer to the support, and the support may be treated with a chemical agent. Surface activation treatment such as mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment and ozone oxidation treatment may be performed. Further, an undercoat layer may be provided after the surface activation treatment, and a photographic emulsion layer or the like may be coated thereon.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James, Theory of the Photographic Process 4th Edition (Th
e Theory of The Photografic Process Forth Editio
n) Pages 291-334 and the Journal of the American Chemical Society (JournaI of the Ame
rican Chemical Society) Volume 73 to 3,100 (195
The developers known per se described in 1) can be used. The color photographic light-sensitive material is
17643 pp. 28-29, RDl 8716 pp. 615 and RD308119 XIX can be processed by a conventional method.

[0097]

EXAMPLES Specific examples of the present invention will be described below.
The embodiments of the present invention are not limited to these. Example 1 [Sample 1] On one surface of a triacetylcellulose film (TAC) having a base thickness of 110 μm, the following coating solution for conductive layer was applied.
It was coated so as to have a volume of milliliter / m ² and dried at 80 ° C. for 5 minutes to form a conductive layer (first layer). <Coating liquid for conductive layer>

[0098]

[Chemical 1] 35 g SiO ₂ fine particles (average particle size 3.0 μm) 0.1 g ethylene glycol 270 ml methanol 600 ml acetone 4000 ml Further, the following magnetic recording layer coating liquid is applied to the first layer to give a magnetic recording layer thickness of 0.2 μm. As described above, a magnetic recording layer (second layer) was formed.

<Coating Liquid for Magnetic Recording Layer> γ-F e₂O₃ 10 parts Dicetyl cellulose 30 parts Acetone 600 parts Methanol 400 parts (γ-F e₂O₃) Γ-F e₂O₃Is a solvent
Manufactured by the methyl alkoxide method using
Of.

Then, on the surface of the support opposite to the surface on which the conductive layer and the magnetic recording layer were provided, after the corona discharge treatment,
The following photographic constituent layers were sequentially formed to prepare a multilayer color photographic light-sensitive material (Sample 1).

Unless otherwise specified, the quantities shown in the photographic constituent layers shown below are expressed in quantities per 1 m ² . Also, silver halide and colloidal silver are shown in terms of silver.

<Photographic Constituent Layer> First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.15 g Ultraviolet Absorber (UV-1) 0.20 g Colored Cyan Coupler (CC-1) 0.02 g High Boiling Solvent (Oil-1) ) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average grain size 0.3 μm) (Average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (Average grain size 0.4 μm) (Average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) ) Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR Compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g

Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) (average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / silver 1 mol) ) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL -2) Gelatin 0.8 g Sixth layer; low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) (Average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion ( Average particle size 0.3 μm) (Average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ⁻⁴ (Mol / silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0g

Seventh layer: high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm) (average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) ) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g 8th layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) ) 0.15 g Gelatin 1.0 g 9th layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm) De content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average particle size 0.4 .mu.m) (average iodide content of 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 -4 ( mol / silver Mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling solvent (Oil-2) 0.18 g Gelatin 1.3 g

Tenth layer: high-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm) (average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High Boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorption Agent (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling point solvent (Oil-1) 0.07 g High boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g 12 layers; second protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethylmethacrylate (average particle size 3 μm) 0.02 g Copolymer of tylmethacrylate: ethylmethacrylate: methacrylic acid = 3: 3: 4 (weight ratio) 0.13 g gelatin 1.0 g-Preparation of silver iodobromide emulsion-Used for the 10th layer The prepared silver iodobromide emulsion was prepared by the following method.

A silver iodobromide emulsion was prepared by the double jet method using monodispersed silver iodobromide grains having an average grain size of 0.33 μm (silver iodobromide content of 2 mol%) as seed crystals.

A solution (G-1) having the following composition was treated at a temperature of 70 ° C. and pA.
While maintaining g7.8 and pH 7.0, 0.34 mol of seed emulsion was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase) After that, a solution (H-1) having the following composition and a solution (S-
1) and were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External High Iodine Phase-Shell Phase-) Subsequently, while maintaining pAg10.1 and pH 6.0, (H-2) and (S-
2) and were added at a flow rate accelerated at a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added and redispersed, and pH and pAg were adjusted to 5.8 and 8.0 at 40 ° C., respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Solution Ocein gelatin 100.0 g 10% by weight solution of -1 of the following compound in ethanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml Compound-1: polyiso Propyleneoxy / polyethyleneoxy / sodium disuccinate

<H-1> Solution Ocein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml

<S-1> solution Silver nitrate 309.2 g 28% aqueous ammonia solution Equivalent Finish with water 1030.5 ml

<H-2> Solution Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml

<S-2> Solution Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent Finish with water 3776.8 ml Silver iodobromide emulsions used in layers other than the 10th layer were also treated in the same manner as described above with the average grain size of seed crystals, The above emulsions having different average grain sizes and silver iodobromide contents were prepared by changing the temperature, pAg, pH, flow rate, addition time and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimal chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, sensitizing dye, 4-hydroxy-6.
-Methyl-1,3,3a, 7-tetrazaindene, 1-
Phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material further comprises the compound SU.
-1, SU-2, viscosity modifier, hardener H-1, H-2,
Stabilizer ST-1, antifoggant AF-1, AF-2 (heavy
Weight average molecular weight of 10,000 and 1,100,000), dyeing
AI-1 and AI-2 and compound DI-1 (9.4 mg /
m² ) Is included.

[0119]

[Chemical 2]

[0120]

[Chemical 3]

[0121]

[Chemical 4]

[0122]

[Chemical 5]

[0123]

[Chemical 6]

[0124]

[Chemical 7]

[0125]

[Chemical 8]

[0126]

[Chemical 9]

[0127]

[Chemical 10]

[Sample 2] For the magnetic recording layer in Sample 1
Γ-F of coating liquid e₂O₃The following Co-doped γ-F e₂O₃To
Sample 2 was prepared exactly like sample 1 except that
It was (Co-doped γ-F e₂O₃) The above Co-doped γ-F e₂
O₃Is methanol using methanol as a solvent.
Made from lucoxide and cobalt dimethyl alkoxide
It is a thing.

[Sample 3] Sample 1 was used for the magnetic recording layer.
Γ-F of coating liquid e₂O₃Is replaced with the following metal magnetic powder
Sample 3 was prepared in the same manner as sample 1 except for the above. (Metallic Magnetic Powder) The above metallic magnetic powder is used in Sample 1.
Γ-F e₂O₃Is hydrogen-reduced according to the usual method
It

[Sample 4] Sample 1 was used for the magnetic recording layer.
Γ-F of coating liquid e₂O₃To the barium ferrite powder below
Sample 4 was prepared in exactly the same way as sample 1 except that
It was (Barium ferrite powder) The above barium ferrite powder
The end uses methylalkoxy as a solvent and methylalkoxy
It is manufactured by the de method.

[Sample 5] For the magnetic recording layer in Sample 1
Γ-F of coating liquid e₂O₃Was replaced with the following chromium dioxide powder
Sample 5 was prepared in exactly the same manner as Sample 1 except for the above. (Chromium dioxide powder) The chromium dioxide powder is a solvent
Produced by the methyl alkoxide method using methanol
It was made.

[Sample 6] Sample 1 was used for the magnetic recording layer.
Γ-F of coating liquid e₂O₃Is the following γ-F e₂O₃Other than
Sample 6 was prepared in the same manner as Sample 1. (Γ-F e₂O₃) Γ-F e₂O₃Is manufactured according to the usual method
It was done.

[Sample 7] Sample 1 was used for the magnetic recording layer.
Γ-F of coating liquid e₂O₃The following Co-doped γ-F e₂O₃To
Sample 7 was prepared in exactly the same way as sample 1 except that
It was (Co-doped γ-F e₂O₃) The above Co-doped γ-F e₂
O₃Is manufactured according to a conventional method.

[Sample 8] Sample 1 was used for the magnetic recording layer.
Γ-F of coating liquid e₂O₃Is replaced with the following metal magnetic powder
Sample 8 was prepared in the same manner as Sample 1 except for the above. (Metallic Magnetic Powder) The above metallic magnetic powder is prepared according to a conventional method.
It is manufactured.

[Sample 9] Sample 1 was used for the magnetic recording layer.
Γ-F of coating liquid e₂O₃To the barium ferrite powder below
Sample 9 was prepared in exactly the same way as sample 1 except that
It was (Barium ferrite powder) The above barium ferrite powder
The powder is manufactured according to a conventional method.

[Sample 10] The magnetic recording layer in Sample 1
Coating liquid γ-F e₂O₃Instead of the following chromium dioxide powder
Sample 10 was prepared in exactly the same manner as Sample 1 except for the above. (Chromium dioxide powder)
It was manufactured accordingly.

The obtained samples 1 to 10 were evaluated as follows. The results are shown in Table 4. <Roll scratch resistance> The magnetic recording layer of the obtained sample was conveyed 50 times so as to hit the roll, and the occurrence of scratches was visually observed and evaluated by the following. 1; No scratches were generated. 3; Shallow scratches occurred. (There is not much influence on the print.) 5; Deep, sharp scratches occurred. (The obvious effect appears on the print.)

<Magnetic Head Scratch Resistance> A sample processed into a card shape was passed through a magnetic card writer / reader 50 times with a magnetic head load of 150 g, and the generation of scratches was visually observed and evaluated by the following. 1; No scratches were generated. 3; Shallow scratches occurred. (There is not much influence on the print.) 5; Deep, sharp scratches occurred. (The obvious effect appears on the print.)

<Dispersibility> Magnetic paint is applied with an applicator.
After casting on a glass plate with a film thickness of 60 μm and drying, the reflected light was compared with a reference plate by a gloss meter.

<Stability of coating liquid> Magnetic coating immediately after production and
The magnetic paint stored for 12 hours was cast on a glass plate with a film thickness of 60 μm by an applicator and dried, and the reflected light on the surface of the magnetic recording layer was obtained by a gloss meter and evaluated by the following. ◯: There is not much difference in glossiness. X: The difference in glossiness is large.

<Decrease in Output> A signal was input to the magnetic recording layer of the obtained sample from a magnetic head obtained by modifying the writing / reading device of the magnetic card. The input signal is 40 ℃,
Reproduced repeatedly in an environment of 80% RH. The reproduction output after 50 times was calculated, and the rate of decrease from the initial reproduction output was calculated as a percentage.

[0142]

[Table 4]

[0143]

INDUSTRIAL APPLICABILITY The photographic light-sensitive material having the transparent magnetic recording layer of the present invention has stable reproduction output even under high humidity, has few reading errors, and has excellent scratch resistance, and the magnetic recording of the present invention. The coating solution for forming the layer has excellent stability.

Claims (1)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support and a transparent magnetic recording layer on the other side in the presence of an organic solvent in the magnetic recording layer. A photographic light-sensitive material containing the magnetic powder formed in step 1.