JPH0777755A - Photographic sensitive material having transparent magnetic recording layer - Google Patents

Abstract

PURPOSE:To obtain the photographic sensitive material having the transparent magnetic recording layer superior in abrasion resistance and free from occurrence of stains and superior in electromagnetic conversion characteristics and small in curling by incorporating a gelatin or a binder mainly comprising a gelatin for the binder of the magnetic recording layer and specifying the surface energy of this layer. CONSTITUTION:The photographic sensitive material has at least one silver halide emulsion layer on one side of a support and the transparent magnetic recording layer, and the gelatin or the binder mainly comprising the gelatin is used for the binder of this layer and the surface energy of this layer is controlled to 23-40dyne/cm<3>. The gelatin to be used may be modified or not, and the binder to be used with the gelatin may be any of those so long as it can be used by mixing it with the gelatin.

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, when a magnetic recording layer is provided on a photographic light-sensitive material, the gelatin on the emulsion layer side absorbs moisture and expands at high humidity, causing a problem of curling. The curl that occurs is stronger in the base of the photographic light-sensitive material than in ordinary magnetic recording materials, and the curl that occurs when the photographic light-sensitive material absorbs moisture is greater than in ordinary magnetic recording materials. The layers don't adhere well,
A magnetic I / O error has occurred.

The present inventors provide a hydrophilic layer on the magnetic recording layer side in order to prevent curling caused by moisture absorption of a photographic light-sensitive material having the magnetic recording layer on the side opposite to the emulsion. However, in these methods, sufficient durability was not obtained, stains were generated, and electromagnetic conversion characteristics were not sufficient, and there was a problem in practical use. Also, gelatin was used as a binder for the magnetic recording layer, but similar to the above, there were problems in terms of scratch resistance, stain generation, and electromagnetic conversion characteristics, and they were insufficient for practical use.

Therefore, as a result of studies by the present inventors, by adjusting the surface energy of the magnetic recording layer within a specific range, the problems in terms of scratch resistance, generation of stains, and electromagnetic conversion characteristics are solved. I found that I can do it.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photographic light-sensitive material having a transparent magnetic recording layer which is excellent in scratch resistance, is free from stains, is excellent in electromagnetic conversion characteristics, and is less likely to curl. .

[0011]

The above objects can be achieved by the following photographic light-sensitive materials.

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 binder of the transparent magnetic recording layer is gelatin or gelatin. The photographic light-sensitive material is characterized in that the transparent magnetic recording layer has a surface energy of 23 to 40 dyne / cm ² while using as a main binder.

The present invention will be described in more detail below.

First, the transparent magnetic recording layer will be described.

The magnetic fine powder used in the magnetic recording layer of the present invention includes metal magnetic powder, iron oxide magnetic powder, and C.
O-doped iron oxide magnetic powder, chromium dioxide magnetic powder,
A barium ferrite magnetic substance powder or the like can be used.

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

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.

The metal magnetic powder has, for example, a metal content of 75% by weight or more, and a metal content of 80% by weight or more 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 the 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 iron oxide can be used without particular limitation.

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.

In the present invention, as the binder of the magnetic recording layer, gelatin or a binder containing gelatin as a main component is used.

The gelatin may be unmodified or modified.

As the binder used with gelatin, any binder can be used so long as it can be mixed with gelatin, and colloidal albumin, casein,
Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, acrylic acid copolymers, polyacrylamide or These derivatives, partial hydrolysates, gelatin derivatives and the like can be mentioned. Further, if it can be used as a mixture with gelatin, a thermoplastic resin, a radiation curable resin, a thermosetting resin, other reactive resins and mixtures thereof can be used.

The above-mentioned thermoplastic resins are preferably used as latex, and as these thermoplastic resins, vinyl chloride-vinyl acetate copolymers, vinyl chloride resins, copolymers of vinyl acetate and vinyl alcohol, vinyl chloride-vinylidene chloride are used. Vinyl-based polymers or copolymers such as copolymers, vinyl chloride-acrylonitrile copolymers, ethylene-vinyl alcohol copolymers, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymers, ethylene-vinyl acetate copolymers. Cellulose derivatives such as coalesce, nitrocellulose, cellulose acetate propionate, cellulose acetate butyrate resin, copolymers of maleic acid and / or acrylic acid, acrylonitrile-styrene copolymers, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene- Suchi Copolymer, methyl methacrylate-butadiene-styrene copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, styrene Examples thereof include rubber-based resins such as butadiene resin and butadiene-acrylonitrile resin, silicone-based resin, and fluorine-based resin.

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.

Gelatin or a binder containing gelatin as a main component is 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), and 2-hydroxy-4,6. -Dichloro-1,3,5-triazine, having a reactive halogen described in U.S. Pat.Nos. 3,288,775, 2,732,303, British Patent 974,723, 1,167,207, etc. Compounds, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Patent Nos. 3,635,718, 3,232,763, British Patent 994,869, etc. Compounds having reactive olefins described, N-hydroxymethylphthalimide, U.S. Pat. No. 2,732,316, 2, 586,168
N-methylol compounds described in Japanese Patent No.
Isocyanates described in U.S. Pat.No. 3,103,437, U.S. Pat.No. 3,017,280, 2,9
Aziridine compounds described in 83,611 and the like, U.S. Pat.No. 2,725,294, acid derivatives described in 2,725,295 and the like, U.S. Pat.
Epoxy compounds described in, for example, No. 537,
Examples thereof include halogen carboxaldehydes such as mucochloric acid, and organic silane coupling agents. Further, it is also possible to use an inorganic hardener, the inorganic hardener, such as chrome bright van, zirconium sulfate, JP-B-56-12853, JP 58-32699 JP, Belgian patent No. 825,726, JP-A-60-225148
JP-A-51-126125, JP-B-58-50699, JP-A-52-54427, U.S. Pat. Can 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 magnetic powder is dispersed in the binder 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 based on 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 the 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.

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 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 provide the magnetic recording layer with functions such as imparting lubricity, preventing electrification, preventing adhesion, and improving friction / abrasive properties. 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 the lubricant 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 providing the magnetic recording layer, calendering is performed on the layer to improve smoothness, and S / N of magnetic output is improved.
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, the surface energy of the transparent magnetic recording layer is 23 to 40 dyne / cm ² .

Surface energy of transparent magnetic recording layer (γS)
Can be determined by measuring the contact angle of the liquid with the surface of the transparent magnetic recording layer.

The surface energy is DKOwens "Estimatio
n of the Surface free Energy of Polymers "Journal o
f Based on the literature of Applied Polymer Science 13 (1969), the contact angle between the liquid and the surface of the transparent magnetic recording layer (cos θ)
It is obtained from the following equation (1).

[0048]

[Equation 1] For γL ^d and γL ^h for water and methylene iodide, see J. Panzer "Components of solid Surface free en.
ergy from wetting measurments "Jounal of Colloid a
In nd Interface Science, vol.44 No.1,

[0049]

[Table 1] Therefore, the value of cos θ is calculated for water and methylene iodide, and these cos θ and known γ
Substituting the values of L ^d , γL ^h , and γL ^v into the above equation (1),
γS ^d and γS ^h are obtained.

Then,

[0051]

[Equation 2] Therefore, the surface (energy (γS) of the transparent magnetic recording layer can be obtained from γS ^d and γS ^h obtained above.

The value of the contact angle cos θ can be obtained by dropping water or methylene iodide droplets on the surface of the transparent magnetic recording layer and observing with a microscope.

The surface energy of gelatin or a transparent magnetic recording layer containing gelatin as a main binder varies depending on the water content. The surface energy referred to in the present invention means the surface energy of a photographic light-sensitive material that has been conditioned under an atmosphere of 25 ° C. and 50% RH for 24 hours.

The surface energy of the transparent magnetic recording layer is 23 to 40
The method of setting dyne / cm ² is not particularly limited, but for example,
The surface energy of the transparent magnetic recording layer is adjusted to 23 to 40 dyne / cm ² by using a mixed liquid in which alcohol such as ethyl alcohol and water are mixed at an appropriate ratio as a solvent for the coating liquid for forming the transparent magnetic recording layer. be able to.

The surface energy of the transparent magnetic recording layer is 23 dyne
If it is less than / cm ² , stain generation increases, scratch resistance is insufficient, and electromagnetic conversion characteristics also deteriorate. Also 40dyne / cm ²
Even if it is larger, the generation of dirt increases, scratch resistance cannot be obtained, and electromagnetic conversion characteristics also deteriorate.

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 recovery property 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 polar groups and other substituents.

As the support in the present invention, polyethylene terephthalate and polyethylene naphthalate are preferable.

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 enters 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 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, X-rays. 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 grain contained in the silver halide photographic emulsion to be used may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is 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.

When tabular silver halide grains are used in the present invention, the average ratio of the diameter to the 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 circle-equivalent diameter 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.

Here, 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.

[0074] 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 this invention are:

[0078]

[Equation 3] 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 particles are particles composed of a core that serves as a core and a shell that coats 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, that is, the shell which usually forms 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 grains to be present in a reaction vessel and, if necessary, silver ions, halogen ions or silver halide fine grains. 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 may have a spherical or plate 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 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 completion of the growth of silver halide grains, or may be contained. 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 2 shows the locations.

[0093]

[Table 2] 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 3 shows the relevant locations.

[0094]

[Table 3] 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 4 shows the relevant locations.

[0096]

[Table 4] 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.

In the case of constituting a color photographic light-sensitive material, 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 on the support, and the support may be treated with a chemical agent. , Mechanical treatment, corona discharge treatment, flame treatment,
Surface activation treatment such as ultraviolet ray 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.

[0101]

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] A polyethylene terephthalate film was biaxially stretched, and an antistatic layer and an adhesive layer were sequentially coated on both sides of a film having a thickness of 100 μm, and then an antistatic layer and an adhesive layer were provided on both sides. Film (hereinafter referred to as film base A
Say. ), A magnetic recording layer having the following composition and coating amount was formed by coating to form a photosensitive material base A.

Magnetic recording layer Gelatin 5 g / m² l, 2-bis (vinylsulfonylamide) ethane (A)
0.5 g / m² C o Adhesion γ-F e₂O₃(Needle-shaped particles, BET42m²/ G, HC = 7
00 Oe) 0.1 g / m² As a solvent for the magnetic recording layer, use a mixture of water and ethyl alcohol.
Using a combined solvent (water: ethyl alcohol = 7: 3),
The minutes were dispersed by a sand mill. In addition, the river for application
A slur coater was used.

Then, after corona discharge treatment, the following photographic constituent layers were sequentially formed on the surface of the support opposite to the magnetic recording layer 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 UV 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 monodisperse silver iodobromide grains (silver iodobromide content 2 mol%) having an average grain size of 0.33 μm 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 1) were added over 86 minutes at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) while maintaining a flow rate ratio of 1: 1.

(Formation of External High Iodity 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 ethanol solution of -1 of the following compound 25.0 ml 28% ammonia solution 440.0 ml 56% acetic acid solution 660.0 ml Finish with water 5000.0 ml Compound-1: polyisopropyleneoxy Polyethyleneoxy sodium succinate

<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 to 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 to obtain 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.

The structure of each compound used for forming the silver halide photographic light-sensitive material according to the present invention is shown below.

[0122]

[Chemical 1]

[0123]

[Chemical 2]

[0124]

[Chemical 3]

[0125]

[Chemical 4]

[0126]

[Chemical 5]

[0127]

[Chemical 6]

[0128]

[Chemical 7]

[0129]

[Chemical 8]

[0130]

[Chemical 9]

[Sample 2] Water was used as a solvent for the magnetic recording layer.
Mixed solvent of ethyl alcohol (water: ethyl alcohol =
A multilayer color photographic light-sensitive material (Sample 2) was prepared in exactly the same manner as Sample 1 except that 5: 5) was used.

[Sample 3] Water was used as a solvent for the magnetic recording layer.
Mixed solvent of ethyl alcohol (water: ethyl alcohol =
A multilayer color photographic light-sensitive material (Sample 3) was prepared in exactly the same manner as Sample 1 except that 6: 4) was used.

[Sample 4] The composition and coating amount of the magnetic recording layer
Instead of the following, as the solvent of the magnetic recording layer,
Mixed solvent of water and ethyl alcohol (water: ethyl alcohol
The same as sample 1 except that
A layer color photographic light-sensitive material (Sample 4) was prepared. Magnetic recording layer Gelatin 5g / m² Hardener (Dimethyl-dioctyloxysilane) 0.5g / m² C o Adhesion γ-F e₂O₃(Needle-shaped particles, BET42m²/ G, HC = 700 Oe) 0.1 g / m²

[Sample 5] A multilayer color photographic light-sensitive material (Sample 5) was prepared in the same manner as in Sample 1 except that water was used as the solvent for the magnetic recording layer.

[Sample 6] A multilayer color photographic light-sensitive material (Sample 6) was prepared in exactly the same manner as Sample 1 except that ethyl alcohol was used as the solvent for the magnetic recording layer.

With respect to the obtained sample, the surface energy of the magnetic recording layer was measured, and the stain, scratch resistance and output reduction after development processing were evaluated according to the following. The results are shown in Table 5.
Shown in

<Dirt> The obtained sample was developed by an automatic developing machine, and after the developing treatment, the roll which was in contact with the magnetic recording layer was visually observed during the developing treatment. Was determined.

<Scratch resistance> A magnetic head was brought into contact with the magnetic recording layer of the obtained sample under a load of 150 g, and the generation of scratches when reciprocating 50 times was visually observed and evaluated by the following. ◯: No scratches or the like are generated. Δ: Shallow scratches occurred. X: Deep scratches occurred.

<Decrease in output after development processing> A signal was input to the magnetic recording layer of the obtained sample from a magnetic head obtained by modifying a writing / reading device of a magnetic card. The input signal was reproduced and the reproduction output was obtained. Further, the samples to which these signals were input were subjected to development processing, the input signals were reproduced again, the reproduction output was obtained, and the ratio of the decrease in reproduction output after the development processing was calculated.

[0140]

[Table 5] As can be seen from Table 5, the photographic light-sensitive material of the present invention has excellent scratch resistance, does not cause stains, and does not decrease the reproduction output after development processing.

[0141]

The photographic light-sensitive material of the present invention is excellent in scratch resistance, is free from stains, is excellent in electromagnetic conversion characteristics, and is less likely to curl.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kimio Ozawa 1st Sakura-cho, Hino City, Tokyo Konica Stock Company

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, wherein the binder of the transparent magnetic recording layer is gelatin or A photographic light-sensitive material characterized by using gelatin as a main binder and having a surface energy of a transparent magnetic recording layer of 23 to 40 dyne / cm ² .