JP3416824B2 - Silver halide photographic materials - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art For silver halide photographic light-sensitive materials, for example,
Type of photographic light-sensitive material, serial number, manufacturer name, emulsion No.
Various information related to photographic light-sensitive materials, such as shooting date / time, aperture, exposure time, lighting conditions, filter used, weather, size of shooting frame, model of camera, use of anamorphic lens, etc. Various information when shooting with the camera,
For example, various information necessary for printing such as the number of prints, filter selection, customer color preference, trimming frame size, etc., for example, number of prints, filter selection, customer color preference, trimming frame size. It is necessary to enter various information obtained at the time of printing, such as customer information, etc., from the viewpoint of management, improvement of print quality, and efficiency of print 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 ferromagnetic fine particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and photographing conditions. KAISHO 50-62627 publication, JP 49-4503 publication,
U.S. Pat.Nos. 3,243,376 and 3,220,843, etc., and transparent magnetic recording on the back surface of a photographic light-sensitive material to obtain the necessary transparency by selecting the amount and size of magnetizable particles. Providing layers is US license No. 3,782,947
No. 4,279,945, No. 4,302,523, and the like. 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 photographic light-sensitive material, which has been difficult in the past, and it is possible to record voice and image signals. is doing.

However, in the conventional method for preparing the magnetic recording layer, the magnetic powder particles are dispersed in a binder containing an organic solvent and then applied to the support, so that various environmental and safety measures and disaster prevention measures are taken. Due to problems, it was difficult to design a simple production facility. In addition, since magnetic powder particles are basically oxides in surface characteristics and are hydrophilic, it is better than before that hydrophilic medium or water is basically better than lipophilic dispersion medium during dispersion. Are known. Therefore, in order to improve the affinity and wettability of the magnetic powder with the binder and the organic solvent, efforts are being made for surface modification as shown in JP-A-57-111829 and JP-A-60-69819. .

Further, unlike magnetic recording media such as general floppy disks, video tapes and audio tapes, silver halide photographic light-sensitive materials are always subjected to development processing such as wet processing, water-based processing or heat processing, and therefore, they are water resistant and New performance such as alkali resistance is required. Since conventional magnetic recording media do not have these performances, if the developing treatment is carried out as it is, the binder in which the magnetic powder is dispersed dissolves or swells, and the magnetic powder, the dispersant and the lubricant dissociate from the coating film, and the treatment step It often causes fatal defects in the photographic light-sensitive material, such as contamination of the film itself or the film itself, or discoloration or deformation of the binder itself.

Further, the presence of a monomer contained in the binder or a residual monomer due to uncrosslinking of the hardener has an influence on the photographic sensitivity of the photograph, and often causes fog and color development failure.

Therefore, the binder that can be used in the present invention is considerably limited, and in order to put it into practical use, a fairly high level of dispersion technology, crosslinking technology, slipperiness imparting technology, etc. are required, which is very impossible with the prior art. It was a level.

Further, it has been known that a photographic light-sensitive material has conventionally contained a surfactant in JP-A-4-73736 and 4-73735.
No. 4, No. 4-62543, No. 4-96052, No. 4-73744, No. 4-124
No. 635, No. 4-124636, No. 4-124637, etc., but at least one of the surface protective layer, the emulsion layer, the intermediate layer, the undercoat layer, and the back layer which constitute the photographic light-sensitive material. 1
There is no clear description that it is contained in the transparent magnetic material layer other than the description that it is contained in the layer, and its purpose is also shown only as a coating aid, an emulsifying dispersant, a sensitizing agent and other photographic property improving agents.

Further, it is also known that a magnetic recording medium has conventionally contained a surfactant in JP-A-58-159232 and 63-26.
Although described in No. 6630, etc., it is only described that they are used as a coating aid, a polymerization inhibitor, and a polymerization terminator, and it is quite possible to achieve the purpose of the present invention described below. It is impossible.

Further, JP-A-3-109701 and JP-A-2-307202 describe aqueous treatment of the surface of magnetic powder, but both are used for the purpose of improving the dispersibility of magnetic powder in an organic coating. Therefore, it is completely different from the present invention.

Further, in JP-A-55-1632 and JP-A-55-1633, which are used for improving the dispersibility of magnetic powders, the use is a magnetic recording material, so that the transparency required for a photographic light-sensitive material is required. High dispersibility as much as possible, stability of magnetic input and output with a very small amount of magnetic powder, prevention of desorption of additives such as magnetic powder and metal oxide fine particles by developing solution of photographic light-sensitive material, and water-based In order to prevent foaming, which must be paid the most attention in dispersing, the level is extremely impossible, and there is no choice but to carry out post-treatment such as vacuum defoaming and ultrasonic defoaming.

[0015]

The first object of the present invention is to provide transparency required for a photographic light-sensitive material, high stability of magnetic input / output with an extremely small amount of magnetic powder, and friction / wear of a magnetic head. Prevents deterioration of durability, prevention of desorption of magnetic powder and metal oxide fine particles by developing solution, prevention of foaming during paint preparation, and elimination of post-treatment such as vacuum defoaming and ultrasonic defoaming. Another object is to provide a silver halide photographic light-sensitive material.

A second object is to provide an excellent silver halide photographic light-sensitive material which is excellent in antistatic property and which is free from dust adhesion after development processing.

The third purpose is to transfer the preparation of the transparent magnetic material layer and the metal oxide fine particle layer to an aqueous system in terms of materials and processes, thereby making it safer and more environmentally friendly in terms of environmental measures, safety and flameproofing. Another object of the present invention is to provide an inexpensive silver halide photographic light-sensitive material.

A fourth object is that by incorporating the ferromagnetic fine particles and the metal oxide fine particles in the same layer, the process load can be reduced and the amount of materials used can be reduced by reducing the number of coatings and the number of dryings during production. It is an object of the present invention to provide a silver halide photographic light-sensitive material whose cost is reduced by reduction or the like.

[0019]

The above object of the present invention can be achieved by any of the following constitutions.

In a photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support,
The photographic light-sensitive material has at least one transparent magnetic layer on at least one side, the binder used for the transparent magnetic layer is an aqueous emulsion resin and / or a water-soluble resin, and the transparent magnetic layer has an HLB. Both a surfactant having a range of 1 to 5 and a HLB having a range of 6 to 10 are used.
A silver halide photographic light-sensitive material characterized by containing both .

At least one transparent magnetic layer is provided on at least one surface of the photographic light-sensitive material, and Zn, Ti, Sn, Al, In, Si, Mg, Ba,
A binder having at least one layer containing Mo, W, V as a main component and containing at least one kind of metal oxide fine particles having an average particle diameter of 1 μm or less, and used for the metal oxide fine particle layer is , An aqueous emulsion resin and / or a water-soluble resin, and HLB is 1 in the metal oxide fine particle layer.
A surfactant in the range of ~ 5 and an HLB in the range of 6 ~ 10
A silver halide photographic light-sensitive material characterized by containing both of the surfactants described in 1 .

[0022]

[0023]   The photographic light-sensitive material is silver halide color
The above, which is a photographic light-sensitive materialorIs Description
Silver halide photographic light-sensitive material.

[0024]   The transparent magnetic layer and / or the metal oxide
The amount of the surfactant contained in the fine particle layer is
/ Or 0.2 to 50 wt% with respect to the metal oxide fine particles
The above characterized by Of any of the above
Silver halide photographic material.

[0025]   The ferromagnetic material used for the transparent magnetic layer is
Ferromagnetic iron oxide fine particles, Co-doped ferromagnetic iron oxide fine particles
Particles, ferromagnetic chromium dioxide fine particles, ferromagnetic metal fine particles
At least one selected from barium ferrite
Above characterized in thatTo any ofDescribed ha
Silver halide photo-sensitive material.

[0026]   Ferromagnetic oxidation on the metal oxide fine particle layer
Iron fine particles, Co-doped ferromagnetic substance Iron oxide fine particles, ferromagnetic substance
Chromium dioxide particles, ferromagnetic metal particles, barium oxide particles
Containing at least one selected from
Characteristic above Silver halide according to any one of
Photographic material.

[0027]   The ferromagnetic material used in the photographic light-sensitive material is
Specific surface area 30m²Characterized by being a fine powder of not less than / g
the above~1. The silver halide photographic light-sensitive material as described in
Fee.

[0028]   The transparent magnetic layer and / or the metal oxide
Fine grain layer through the support and the photosensitive silver halide emulsion layer
And characterized in that they are present on the opposite side. Nozu
The silver halide photographic light-sensitive material described therein.

That is, as a result of intensive studies on a daily basis to solve the problems of the above-mentioned conventional techniques, we have found that HLB contains a surfactant in the range of 1 to 15 so that magnetic powder, metal oxide fine particles, etc. In addition to improving the separability of additives, the transparency required as a photographic light-sensitive material, the stability of magnetic input / output even with an extremely small amount of magnetic powder, and the addition of magnetic powder and metal oxide fine particles by the development processing solution. It has been found that it is possible to prevent desorption of the agent, prevent foaming during the preparation of the coating material, and eliminate the defoaming treatment.

Further, by containing both a surfactant having an HLB in the range of 1 to 5 and a surfactant having an HLB in the range of 6 to 10, further improvement of transparency and improvement of stability of magnetic input / output,
It has been found that the durability can be improved by friction and wear of the magnetic head.

The present invention will be described in detail below.

The term "transparent" as used in the present invention specifically means a case where the maximum optical density of the magnetic recording layer is 1.5 or less. The optical density in the present invention is an optical density measured through filters B, G and R using an optical densitometer PDA-65.
Refers to Db, Dg, and Dr. The maximum value among them is Dmax. The maximum value Dmax of the optical density of the magnetic recording layer of the present invention is 1.
It may be 5 or less, but it is preferably small considering the influence on the photographic image, preferably 0.8 or less, and particularly preferably 0.3 or less.

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

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

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

The shape and size of the ferromagnetic powder can be widely used without particular limitation. The shape is needle-like, rice grain,
It may be spherical, cubic, or plate-like, but needle-like or plate-like is preferable in terms of electromagnetic conversion characteristics. The crystallite size and specific surface area are not particularly limited, but the crystallite size is 400 Å or less, SBET is 20 m ²
/ G or more is preferable, and 30 m ² / g or more is particularly preferable. The pH of the ferromagnetic powder and the surface treatment can be used without particular limitation (the surface treatment may be performed with a substance containing an element such as titanium, silicon or aluminum, carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid). , May be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocycle such as a phosphoric acid ester or benzotriazole). preferable
The pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron. For these magnetic recording layers,
It is described in JP-A-47-32812 and JP-A-53-109604.

The binder used in the magnetic recording layer is a thermoplastic resin, a radiation curable resin, a thermosetting resin, or any other reactive resin, which is dissolved or dispersed in water and is used alone or as a mixture. can do.

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

The thermoplastic resin has a Tg of -40 ° C to 180 ° C.
C., preferably 30.degree. C. to 150.degree. C., with a weight average molecular weight of 5,000 to 300,000, more preferably 10,000 to 200,000.

These can be usually used as an aqueous emulsion or an aqueous colloidal solution. The particle size of these synthetic resin emulsions can be 5 nm to 2 μm.

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

The thermosetting resin and other reactive resins include phenol resin, epoxy resin, polyurethane curable resin, urea resin, alkyd resin, silicone curable resin, etc., which are water-soluble or water-based emulsions. Is mentioned.

The binders listed above may have polar groups in their molecules. Epoxy group as polar group, -CO
_{OM, -OH, -NR 2, -NR} 3 X, -SO 3 M, -OSO 3 M, -PO
₃ M ₂ and —OPO ₃ M (M is hydrogen, an alkali metal, or ammonium, X is an acid that forms an amine salt, and R is hydrogen or an alkyl group).

Other hydrophilic binders that can be used in the present invention include, for example, Research Disclosure.
No.17643, page 26, and No. 18716, page 651 can be mentioned water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters.

Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, acrylic acid-based copolymers, maleic anhydride-based copolymers, etc. in addition to the above-mentioned celluloses. Examples of ethers include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

When using a water-soluble polymer, it is preferable to use a hardener. 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,
U.S. Pat.No. 3,288,775, 2,732,303,
British Patent No. 974,723, compounds having a reactive halogen described in 1,167,207 and the like,
Divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat.Nos. 3,635,718, 3,232,763 and British Patent 994,869 Compounds with reactive olefins, N-hydroxymethylphthalimide, US Patent
2,732,316, N-methylol compounds described in 2,586,168 and the like, isocyanates described in U.S. Pat.No. 3,103,437, U.S. Pat.No. 3,017,280, No. 2,983,611 Compounds described in U.S. Pat. No. 2,725,29
4, acid derivatives described in 2,725,295 and the like, epoxy compounds described in U.S. Pat.No. 3,091,537, halogen carboxaldehydes such as mucochloric acid. it can.
Further, it is also possible to use an inorganic hardener, as the inorganic hardener, chrome bright vane, zirconium sulfate, and JP-B-56-12853, 58-32699. , 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.

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

Examples of the lubricant include silicone oils such as polysiloxane, plastic fine 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. Those which can be dissolved or diffused in water are preferable.

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., Chromium oxide (Cr ₂ O ₃ ), Iron oxide (α-
Fe ₂ O ₃ ), oxides such as silicon dioxide and titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond. Their average particle size is 0.
01 ~ 1.0 μm is preferable, 0.5 ~ 30 per 100 magnetic powder
It can be added in the range of parts by weight.

As the antistatic agent, fine particles of metal oxide are preferable.

Examples of metal oxides include oxygen-rich oxides such as Nb ₂ O _{5 + X} , oxygen-deficient oxides such as RhO _2-X and Ir ₂ O _3-X , or Ni (OH) _X. Non-stoichiometric hydride, such as Hf
O ₂ , ThO ₂ , ZrO ₂ , CeO ₂ , ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O
₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable.
As an example containing a heteroatom, for example, Zn, Al, In
Etc., addition of Nb, Ta, etc. to TiO ₂ and addition of Sb, Nb, halogen element, etc. to SnO ₂ are effective.
The added amount of these heteroatoms is preferably in the range of 0.01 mol% to 25 mol%, and particularly preferably in the range of 0.1 mol% to 15 mol%.

The volume resistivity of these electrically conductive metal oxide powders is preferably 10 ⁷ Ωcm or less, particularly 10 ⁵ Ωcm or less. Further, it may be a sol in which fine particles of the metal oxide are mixed in an aqueous solution.

Besides, conductive fine powder such as carbon black or carbon black graft polymer may be used.

As the surfactant, any one of an anionic surfactant, a cationic surfactant, a nonionic surfactant and an amphoteric surfactant may be used alone, or 2
You may use together more than one kind. The HLB of the surfactant is preferably in the range of 1 to 15, and it is more preferable to use a surfactant having an HLB of 1 to 5 in combination with a surfactant having an HLB of 6 to 10.

Specific examples of the surfactant will be given below, but the surfactant usable in the present invention is not limited to the following.

Examples of anionic surfactants include alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines. , Sulfosuccinates, sulfoalkyl polyoxyethylene-alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., such as carboxy, sulfo, phospho, sulfate, phosphate, etc. Those containing a group are preferred.

Specific examples preferably used in the present invention are shown below.

Anionic surfactant

[0059]

[Chemical 1]

[0060]

[Chemical 2]

Examples of the cationic surfactant include alkylamine salts, fatty acid or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing a fatty acid or a heterocycle. Is preferred.

Specific examples preferably used in the present invention are shown below.

Cationic surfactant

[0064]

[Chemical 3]

[0065]

[Chemical 4]

As nonionic surfactants, saponins (steroidal), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol /
Polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicones), glycidol derivatives ( For example, alkenyl succinic acid polyglyceride, alkylphenol polyglycide), polyhydric alcohol fatty acid esters, and sugar alkyl ester sugars are preferable.

Specific examples preferably used in the present invention are shown below.

Nonionic surfactant

[0069]

[Chemical 5]

As the amphoteric surfactant, amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides and the like are preferable.

Specific examples preferably used in the present invention are shown below.

Amphoteric surfactant

[0073]

[Chemical 6]

The HLB of the above-mentioned surfactants is described in "Surfactant Handbook" edited by Ichiro Nishi, Tomoaki Imai, Masatake Kasai, Sangyo Tosho Co., Ltd. (Showa 38.6.10), 3rd edition, 316-317.
It is a value calculated by the method described on the page.

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

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

As a method for providing the magnetic recording layer on the support, slide hopper coating, air doctor coating,
Blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat, and extrusion 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 undercoat layer is preferably an aqueous latex type.

The thickness of the magnetic recording layer is preferably 0.01 to 20 μm, more preferably 0.05 to 15 μm, and further preferably
0.1 to 10 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, antistatic property, antiadhesive property, 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.

These surfactants may be contained as a substituent of the polymer.

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

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.

The magnetic powder is dispersed together with a binder dissolved in water or a binder emulsified in water to form a coating liquid. A ball mill, homomixer, sand mill, or the like can be used to disperse the magnetic powder. That is, the dispersion method is not particularly limited, and the addition order of each component can be appropriately set. For the preparation of magnetic paints, conventional kneading machines such as two-roll mill, three-roll mill, ball mill, pebble mill, tron mill, sand grinder, Szegvari attritor, high speed impeller, disperser, high speed stone mill, high speed impact mill. , Disperser, kneader, high speed mixer, revosiblender, cokneader, intensip mixer, tumbler, blender, disperser, homogenizer, single-screw extruder, twin-screw extruder and ultrasonic disperser can be used. 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 20 parts by weight based on 1 part by weight of the magnetic powder. More preferably, it is 2 to 15 parts by weight with respect to 1 part by weight of the magnetic powder. Further, the solvent is used in such an amount that the coating can be easily performed.

To prevent aggregation of the water-based emulsion,
A regulator and a surfactant may be added.

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

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-butanediol, etc. Examples thereof include condensation polymers with alkylene glycols 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 No. 2-214852 and JP-A No. 2-291135.

These polyesters may have polar groups and other substituents.

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

The polyester is preferably stretched at an area ratio of 4 to 16 times in order to satisfy the mechanical strength and dimensional stability of the film support.

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 (flickering) 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 is not particularly limited, but when a polyester film is used as the support, it is preferable that it has excellent heat resistance in the film forming process, and examples thereof include anthraquinone chemical dyes. Further, as the color tone, when it is intended 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. Mitsubishi Kasei Co., Ltd. Diaresin, Bayer MACROLEX
It is possible to achieve the target by using such dyes 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.

[0098]

EXAMPLES Specific examples of the present invention will be described below.
The embodiments of the present invention are not limited to these.

Example 1 <Preparation of Support A> As a polyester resin for the support, S-1: commercially available polyethylene terephthalate (intrinsic viscosity
0.65) S-2: To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, 0.1 part by weight of hydrate of calcium acetate as an ester exchange catalyst was added, and transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: S
IP) ethylene glycol solution (concentration 35% by weight) 28 parts by weight (5 mol% / total ester bond), polyethylene glycol (abbreviation: PEG) (number average molecular weight: 4,000) 11 parts by weight (8.5% by weight / reaction product) Total weight), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.13 part by weight, Irganox 1010 (CIBA-GEIGY as an antioxidant
(Made by the company) was added so that it might be 1 weight% with respect to the product polymer. Then gradually raise the temperature and reduce the pressure to 280 ° C, 0.5 mm
Polymerization was carried out with Hg to obtain a copolyester. (Intrinsic viscosity 0.55) A: After vacuum drying S-1 and S-2 at 150 ° C. respectively,
Two of the three extruders were used for S-2, melt-extruded at 285 ° C., and the film thickness ratio of three layers was S-2: S-1: S-2 =
The layers were joined in a T-die so as to have a ratio of 1: 1: 1, and rapidly solidified on a cooling drum to obtain a laminated unstretched film.
At this time, the thickness of each layer was controlled by adjusting the extrusion amount of each material. Then, after longitudinal stretching (3.4 times) at 85 ℃, the temperature is further increased to 9
After transverse stretching (3.4 times) at 5 ° C., heat setting was performed at 210 ° C. to obtain a biaxially stretched film A having a film thickness of 90 μm.

<Preparation of Film Base> Both sides of the biaxially stretched film A obtained above were subjected to a corona discharge treatment of 8 W / (m ² · min), and one surface was coated with a subbing coating solution B-1 to form a dry film. Thickness
The undercoat layer B-1 is formed by coating so as to have a thickness of 0.8 μm, and the following undercoat coating solution B-2 is coated on the other surface of the support A so as to have a dry film thickness of 0.8 μm. The undercoat layer B-2 was formed.

<Undercoating Coating Liquid B-1> Copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content). 30%) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating liquid B-2> 40 wt% butyl acrylate, 20 wt% styrene And 40% by weight glycidyl acrylate copolymer latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml Further subbing 8 W / on layer B-1 and subbing layer B-2
A corona discharge of (m ² · min) is applied, and the following coating solution B-3 is applied on the undercoat layer B-1 to a dry film thickness of 0.1 μm to form an undercoat layer B-3. Then, on the undercoat layer B-2,
The metal oxide fine particle layer coating composition 2 shown in Table 4 was dried to a film thickness of 1.
The metal oxide fine particle layer 2 having an antistatic function was formed by coating so as to have a thickness of 0 μm.

[0102] <Coating liquid B-3>   Gelatin 10g   Compound (UL-1) 0.2 g   Compound (UL-2) 0.2 g   Compound (UL-3) 0.1 g   Silica particles (average particle size: 3 μm) 0.1 g   Finish with water 1000 ml

[0103]

[Chemical 7]

On the metal oxide fine particle layer 2, 8 W / (m
After applying a corona discharge treatment for ² min), the coating composition 1 for the transparent magnetic layer shown in Table 3 is applied so that the amount of the magnetic powder is 40 mg / m ² , and then 8 W / (m ² · min) corona discharge treatment, and then the lubricant layer coating composition 1 described below is applied, and Table 1
And the film base 1 was produced by the structure as shown in Table 2.

[0105] <Lubricant layer coating composition 1>   Carnauba wax (Kato Yoko Co., Ltd.) 1g   Pure water 700g   710 g of methanol

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

Binder type A ... Byronal MD-1220 B manufactured by Toyobo Co., Ltd. Plus Coat Z-446 C manufactured by Kyoyo Chemical Industry Co., Ltd. JSR 0693 D manufactured by Nippon Synthetic Rubber Co., Ltd. Japan Synthetic Rubber Co., Ltd. ) SX 808 (B) -01 E ... Shin-Etsu Chemical Co., Ltd. Poval PA-05 GP F ... Ocein gelatin cross-linking agent type a ... Dai-ichi Kogyo Seiyaku Co., Ltd. Elastron BN-69 b ... Nagase Kasei Co., Ltd. ) Denacol EX-512 metal oxide type A ... SnO ₂ powder SN-100P (average particle size 0.1 μm) manufactured by Ishihara Sangyo Co., Ltd. B ... TiO ₂ ET-300W (average particle size 0.3 μm) manufactured by Ishihara Sangyo Co., Ltd. C ... BaSO ₄ powder Pastran TYPE-IV (average particle size: 0.2 μm) manufactured by Mitsui Mining & Smelting Co., Ltd. Further, a corona discharge of 25 W / (m ² · min) was applied on the undercoat layer B-5. Later, a multilayer color light-sensitive material having the emulsion layer constitution of Example 1 described in Japanese Patent Application No. 4-267697. Then, a photographic light-sensitive material 1 was prepared.

Gelatin per m ² in the multilayer emulsion layer
The silver halide grains of 13.7 g, 0.3 to 0.4 μm and 0.7 to 0.8 μm each have 2.3 g, the amount of oil droplets is 2.8 g, and the film thickness is 27 μm.

The produced film base and photographic light-sensitive material were subjected to development processing with the processing steps shown below and the processing solutions having the compositions shown below.

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Wash with water 2 minutes 10 seconds Fixed arrival 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stable 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N-Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 mg Sodium bisulfite 4.6 g Water added 1.0 l pH 6.6 Stabilizer Formalin (40%) 2.0mg Polyoxyethylene-p-monononylphenyl ether Le on both sides of the support A obtained in (average polymerization degree: 10) was added to 0.3g water 1.0l Example 1 wherein, 8W / (m ² · mi
n) is subjected to a corona discharge treatment, and the undercoating coating solution B-1 is applied on one surface so as to have a dry film thickness of 0.8 μm.
-1, and a metal oxide fine particle layer coating composition 2 shown in Table 4 is applied to the other surface of the support A so as to have a dry film thickness of 0.8 μm and has an antistatic function. Layer 2 was formed.

Further, a corona discharge treatment of 8 W / (m ² · min) was applied on the undercoat layer B-1 and the metal oxide fine particle layer 2.
On the undercoat layer B-1, the coating solution B-3 was dried to a film thickness of 0.
The undercoat layer B-3 is formed by coating so as to have a thickness of 1 μm, and the transparent magnetic layer coating composition 1 shown in Table 3 is coated on the metal oxide fine particle layer 2 at a magnetic powder coating amount of 40 mg / m ² . And then apply a corona discharge treatment of 8 W / (m ² · min) on it, and then apply the lubricant layer coating composition 1 described above and apply the composition as shown in Table 1 and Table 2. A film base 2 was produced.

Further, on the undercoat layer B-3, Example 1 was formed.
A multilayer color light-sensitive material was prepared in exactly the same manner as described above to prepare a photographic light-sensitive material 2.

The film base and the photographic light-sensitive material thus produced were processed in the same manner as described in Example 1 with a processing step and a processing solution.

Examples 3 to 31 Film bases 3 to 3 were prepared in the same manner as in Example 2 except that the constitutions shown in Tables 1 to 4 were changed.
1 and photographic light-sensitive materials 3 to 31 were prepared and developed.

Example 32 A film base 32 and a photographic light-sensitive material 32 were prepared in the same manner as in Example 3 except that the layer structure 2 shown in Table 2 was changed to 3, and the development treatment was carried out. went.

Example 33 On both sides of the support A obtained in Example 1, 8 W / (m ² · mi
n) is subjected to a corona discharge treatment, and the undercoating coating solution B-1 is applied on one surface so as to have a dry film thickness of 0.8 μm.
-1, and the metal oxide fine particle layer coating composition 6 shown in Table 4 is applied to the other surface of the support A so as to have a dry film thickness of 0.8 μm and has an antistatic function. Layer 6 was formed.

Further, a corona discharge treatment of 8 W / (m ² · min) was performed on the undercoat layer B-1 and the metal oxide fine particle layer 6,
On the undercoat layer B-1, the coating solution B-3 was dried to a film thickness of 0.
1 μm is applied to form an undercoat layer B-3, and the lubricant layer coating composition 1 described above is applied on the metal oxide fine particle layer 6, and as shown in Tables 1 and 2. The film base 33 was produced with the configuration.

Furthermore, on the above-mentioned undercoat layer B-3, Example 1
A multilayer color light-sensitive material was produced in exactly the same manner as described to produce a photographic light-sensitive material 33. The produced film base and photographic light-sensitive material were developed in the same manner as in Example 1 with the processing steps and processing solutions.

Examples 34 and 35 Film bases 35, 36 and photographic light-sensitive materials 35, 36 were prepared in the same manner as in Example 2 except that the constitutions shown in Tables 1 to 4 were changed. , Development processing was performed.

Example 36 On both sides of the support A obtained in Example 1, 8 W / (m ² · mi
n) is subjected to corona discharge treatment, and one surface is coated with the metal oxide fine particle layer coating composition 2 shown in Table 4 so as to have a dry film thickness of 0.8 μm to form the metal oxide fine particle layer 2. The metal oxide fine particle layer coating composition 6 shown in Table 4 was applied on the other surface of the support A to a dry film thickness of 0.8 μm to form a metal oxide fine particle layer 2 having an antistatic function.

Further, a corona discharge treatment of 8 W / (m ² · min) was performed on the metal oxide fine particle layer 2 and the metal oxide fine particle layer 6, and the coating solution was formed on the metal oxide fine particle layer 2. B
-1 is applied to a dry film thickness of 0.8 μm to form an undercoat layer B-
1 is formed on the metal oxide fine particle layer 6 and the lubricating layer coating composition 1 is applied on the metal oxide fine particle layer 6, and further 8 W / (m ² · min) of corona discharge is formed on the undercoat layer B-1. The undercoat layer B-3 is subjected to a treatment and applied so as to have a dry film thickness of 0.1 μm to form an undercoat layer B-3, and a film base 34 having the structure shown in Tables 1 and 2 is prepared. did.

Further, on the undercoat layer B-3, Example 1 was formed.
A multilayer color light-sensitive material was produced in exactly the same manner as described to produce a photographic light-sensitive material 34.

The produced film base 34, photographic light-sensitive material
No. 34 was processed in the same manner as described in Example 1 with a processing process and a processing solution.

Comparative Examples-Comparative Example 2 with the transparent magnetic material layer coating composition 1 shown in Tables 1 to 4.
A film base and a photographic light-sensitive material were produced and processed in the same manner as in Example 2 except that the composition and the coating composition described were changed.

Comparative Examples-Comparative Example 19 with the same composition and coating composition as those shown in Tables 1 to 4 for the metal oxide fine particle layer coating composition, but in the same manner as in Example 19 except for changing the film base and the photograph. A light-sensitive material was prepared and developed.

Further, the following evaluations were carried out, and the results are shown in Tables 5 and 6.

Evaluation Method (1) Optical Density Using a Sakura Densitometer PDA-65 manufactured by Konica Corporation, an interference filter that transmits blue light was used to vertically inject light of a specific wavelength into the coating film. The absorption of light by the coating film was calculated.

(2) Turbidity Turbidity was measured using SEP-PT-501D type manufactured by Mitsubishi Kasei Co., Ltd.

(3) Evaluation of magnetic recording output error With the signal input method disclosed in World Publication No. 90-04205, a photographic film magnetically input once from the back layer before development is output 500 times with a magnetic head after development. The operation was performed and the number of times the error occurred was shown. The error is the first output value
It is 100% and is less than 70%.

(4) Surface specific resistance The specific resistance was measured using a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd. under the conditions of an applied voltage of 100 V, 23 ° C. and 20% RH.

(5) Durability A magnetic recording / reproducing apparatus of the format disclosed in US Pat. No. 5,021,820 was used for magnetic recording / reproducing on the side coated with the transparent magnetic material layer of the photographic light-sensitive material packed in a cartridge. Repeated 1000 times. After the test, the surface of the photographic light-sensitive material coated with the transparent magnetic material layer was observed under a microscope magnification of 100 times to check for scratches, and the following evaluations were performed.

A: No flaws B: 2-3 flaws C: Magnetic head contact area on the entire surface The flaws are dents or scrapes on the surface that can be confirmed in the running direction of the magnetic head, and a magnification of 100 times. Can be confirmed at.

[0137]

[Table 5]

[0138]

[Table 6]

From Tables 5 and 6, the photographic light-sensitive materials 1 to 36 obtained in the present invention are photographically transparent due to their excellent dispersibility, excellent in sharpness and graininess, magnetic input / output characteristics and antistatic properties. It can be seen that it is excellent, and deterioration in durability due to friction and wear by the magnetic head is prevented, and there is no deterioration or adhesion of dust even after development processing, and there is no problem photographically.

[0140]

According to the present invention, firstly, the transparency required for a photographic light-sensitive material, high stability of magnetic input / output even with an extremely small amount of magnetic powder, and deterioration of durability due to friction and wear of a magnetic head. Excellent halogenation that can prevent the desorption of magnetic powder and metal oxide fine particles by the development processing solution, the prevention of foaming during paint preparation and the elimination of post-treatments such as vacuum defoaming and ultrasonic defoaming. A silver photographic light-sensitive material can be provided.

Secondly, it is possible to provide an excellent silver halide photographic light-sensitive material which is excellent in antistatic property and is free from adhesion of dust after development processing.

Thirdly, the preparation of the transparent magnetic material layer and the metal oxide fine particle layer is moved to an aqueous system in terms of materials and processes so that it is safer and more environmentally friendly in terms of environmental measures, safety and flameproofing. An inexpensive silver halide photographic light-sensitive material can be provided.

Fourthly, by incorporating the ferromagnetic fine particles and the metal oxide fine particles in the same layer, the process load and the amount of materials used can be reduced by reducing the number of coatings and the number of dryings during production. It is possible to provide a silver halide photographic light-sensitive material whose cost has been reduced by the above.

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Claims (8)

(57) [Claims] 1. A photographic light-sensitive material having a photosensitive silver halide emulsion layer on at least one side of a support, and at least one transparent magnetic layer on at least one side of the photographic light-sensitive material, and the transparent material. The binder used in the magnetic layer is an aqueous emulsion resin and / or a water-soluble resin, and the transparent magnetic layer has a surfactant having an HLB of 1 to 5 and an interface having an HLB of 6 to 10. Activator with both
A silver halide photographic light-sensitive material characterized by containing also . 2. A photographic light-sensitive material having at least one transparent magnetic layer on at least one side thereof, and Zn, Ti, Sn, Al, In, Si, Mg, Ba, M on at least one side of the photographic light-sensitive material.
There is at least one layer containing o, W, V as a main component and at least one kind selected from metal oxide fine particles having an average particle size of 1 μm or less, and the binder used for the metal oxide fine particle layer is , An aqueous emulsion resin and / or a water-soluble resin, and HLB is 1 to 1 in the metal oxide fine particle layer.
Surfactant and HLB in the range of 5 to 6 to 10
A silver halide photographic light-sensitive material characterized by containing both a certain surfactant . 3. The photographic light-sensitive material is a silver halide color image.
A true light-sensitive material according to claim 1 or 2.
The described silver halide photographic light-sensitive material. 4. The transparent magnetic layer and / or the metal oxide.
The amount of the surfactant contained in the fine particle layer depends on the ferromagnetic material and / or
Or 0.2 to 50 wt% of the metal oxide fine particles.
The halogen according to any one of claims 1 to 3, characterized in that
Silver halide photographic material. 5. The ferromagnetic material used in the transparent magnetic layer is strong.
Magnetic iron oxide fine particles, Co-doped ferromagnetic iron oxide fine particles
Particles, ferromagnetic chromium dioxide fine particles, ferromagnetic metal fine particles
At least one selected from barium ferrite
It exists, It is characterized by the above-mentioned.
Silver halide photographic light-sensitive material. 6. Ferromagnetic iron oxide in the metal oxide fine particle layer
Fine particles, Co-doped ferromagnetic iron oxide fine particles, ferromagnetic material
Chromium oxide particles, ferromagnetic metal particles, barium oxide particles
Specially contains at least one selected from lights
Silver halide according to any one of claims 2 to 5
Photographic material. 7. A ferromagnetic material used in the photographic light-sensitive material has a ratio of
A contract characterized by being a fine powder with a surface area of 30 m ² / g or more
7. A silver halide photographic light-sensitive material according to any one of claims 1 to 6.
Fee. 8. The transparent magnetic layer and / or the metal oxide.
The fine grain layer is provided between the photosensitive silver halide emulsion layer and the support.
It exists on the opposite side, and either of Claims 1-7 characterized by the above-mentioned.
The silver halide photographic light-sensitive material described therein.