JP3385484B2 - 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, filters used,
Various information at the time of camera shooting such as weather, size of shooting frame, model of shooting machine, use of anamorphic lens, for example, number of prints, selection of filter, customer's color preference, size of trimming frame, etc. Various information necessary for printing, such as the number of prints, filter selection, customer's color preference, trimming frame size, and other information obtained during printing, and other customer information. In terms of management, the print quality
It is also necessary to improve the efficiency of printing work.

In a conventional photographic light-sensitive material, it is impossible to input all the above information, and information such as a shooting date / time, an aperture, an exposure time, etc. is optically input slightly at the time of shooting. It was nothing more. Moreover, at the time of printing, inputting the above information into the photographic light-sensitive material is
It was impossible without that means.

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 shooting conditions. KAISHO 50-62627, 49-4503, U.S. Pat.Nos. 3,243,376, 3,220,843, etc., and the back surface of the photographic light-sensitive material, the amount of magnetizable particles, size It is described in US Pat. Nos. 3,782,947, 4,279,945 and 4,302,523 that a transparent magnetic recording layer having the required transparency is provided by selecting the above. Also, U.S. Pat.No. 4,947,196,
WO 90/04254 describes a photographic camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic substance that enables magnetic recording on the back surface of a photographic film.

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. Further, 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 seen in JP-A-57-111829 and JP-A-60-69819. However, no further improvement has been attempted in the water system.

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.

The conventional material forming the magnetic recording layer does not support the harsh environmental conditions actually used by the user.

Further, no consideration is given to the suitability for production which should be adapted to the production process of the photographic light-sensitive material. Especially, a series of techniques to disperse pigments with high specific gravity such as magnetic powder and high cohesive force at low concentration to form a uniform thin film with no fine defects as a coating solution has never been tried. It can be said that it has not been done.

Even if the coating solution composition of the conventional patent is actually used, none of them can be mass-produced while maintaining stability in the manufacturing process of the photographic light-sensitive material.

In the production of photographic light-sensitive materials, water-based coating with gelatin is the mainstream, but since gelatin as a binder is a natural product, there are large variations in various physical properties, and due to heating during dissolution, etc. , Easily deteriorated due to decay. Moreover, even at low concentration, the viscosity is high, causing gel-like change depending on temperature, foaming during high-speed stirring, etc.
It is too inconvenient for industrial materials. Also, the coating film is brittle, and unless crosslinked, it is difficult to satisfy the required physical properties under aqueous treatment conditions.

Further, as the functions of photographic light-sensitive materials have become higher in recent years,
Although multi-layering such as simultaneous multi-layer coating has been carried out, the invention of the idea based on the fundamental concept of single-layering, such as how to realize various functions as one paint and one coating, has not been made at all. Absent.

[0016]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide photographic light-sensitive material having a transparent magnetic layer which is excellent in optical characteristics required for the photographic light-sensitive material.

The second purpose is to prepare a transparent magnetic layer,
It is an object of the present invention to provide a silver halide photographic light-sensitive material having a transparent magnetic layer which is safer in terms of environment, safety and disaster prevention measures and which has a low environmental cost by transferring the process to an aqueous system.

A third object is to provide a transparent magnetic layer which is excellent in water resistance and developer resistance and has a very small influence on the photographic photosensitive layer in view of fog property, tackiness and the like.

A fourth object is to provide a transparent magnetic layer having excellent dispersion of magnetic powder and good electromagnetic conversion characteristics.

A fifth object is to provide a transparent magnetic layer containing a coating additive capable of preventing sedimentation / aggregation of the coating material for the transparent magnetic layer and maintaining the adhesiveness / optical characteristics at a required level. is there.

A sixth object of the present invention is to provide a silver halide photographic light-sensitive material having a transparent magnetic layer which is excellent in the stability of coating and conveying, reduces the number of man-hours in the production process, and has a low manufacturing cost.

The seventh object is to provide the photosensitive material with sufficient slipperiness and scratch resistance against the contact between the magnetic head and the magnetic recording layer without impairing the transparency, so that the erroneous operation at the time of magnetic recording / reproduction is performed. It is an object of the present invention to provide a photographic light-sensitive material which has a small amount of defects and is free from problems such as deterioration over time or after development processing.

[0023]

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

A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support, wherein the average major axis length is 0.8 μm or less on at least one surface of the silver halide photographic light-sensitive material. A silver halide photographic light-sensitive material comprising a transparent magnetic layer containing magnetic particles and non-magnetic conductive oxide particles having a volume fraction of the dry coating film of 8% or more and 50% or less.

The silver halide photographic light-sensitive material as described above, characterized in that the transparent magnetic layer contains a lubricant having a melting point of 50 ° C. or higher in a weight fraction of 0.5% to 20% with respect to the dry coating film.

The silver halide photographic light-sensitive material as described above or above, wherein the transparent magnetic layer contains non-magnetic particles having a Mohs hardness of 6 or more and an average particle diameter of 0.01 μm or more and 2 μm or less.

The silver halide photographic light-sensitive material as described above or above, wherein the binder used in the transparent magnetic layer is an aqueous latex resin.

The silver halide photographic light-sensitive material as described above, wherein the binder used in the transparent magnetic layer is a polyester-based aqueous latex resin.

The silver halide photographic light-sensitive material as described above, wherein the binder used in the transparent magnetic layer is an acrylic water-based latex resin.

The present invention will be described in detail below.

The volume fraction referred to in this patent is the proportion of a certain substance in the coating film in terms of volume.
To calculate the volume fraction of a certain composition, the weight of each component is divided by the specific gravity of the component to calculate the volume, and the volume of the entire coating film can be determined as 100%.

When the composition is not known, a large number of electron micrographs of the cross section of the coating film are taken, the atoms and molecules of each particle are identified by X-ray analysis, and estimated from the area ratio occupied in the photographic image.

Even if the coating film of which composition is unknown
It is also possible to separate the components by various analytical chemistry methods after drying at%, scraping off with a sharp edged tool, calculating the volume.

The pigment powder including the magnetic material is dispersed together with a binder dissolved in water or a binder emulsified in water to form a coating solution. The method for dispersing the pigment powder including the magnetic material is not particularly limited, and the order of adding the components and the like can be set appropriately. For the preparation of the magnetic paint, a conventional kneading machine, for example, a two-roll mill, a three-roll mill, a ball mill, a pebble mill, a tron mill,
Sand grinder, Szegvari attritor, high-speed impeller, disperser, high-speed stone mill, high-speed impact mill, disper, kneader, high-speed mixer, revo-siplender, co-kneader, intensive mixer,
A tumbler, a blender, a disperser, a homogenizer, a single screw extruder, a twin screw extruder, an ultrasonic disperser, etc. can be used. 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 1 to 200 parts by weight with respect to 1 part by weight of the magnetic powder.
It is preferable to use parts by weight. More preferably, it is 2 to 50 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, pH
A regulator and a surfactant may be added.

As a method for providing a magnetic recording layer on a support, an extrusion coater air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, Cast coat, spray coat, etc. can be used. In order to perform multi-stripe coating, these coating heads may be arranged in series. Specific methods of stripe coating include, for example, JP-A-48-25503, JP-A-48-25504, and JP-A-48-25504.
-98803 publication, 50-138037 publication, 52-15533 publication, 51-3208 publication, 51-6239 publication, 51-65606 publication, 51-140703 publication, JP-B-29 -4221 publication, U.S. Pat. Nos. 3,062,181, and 3,227,165 can be referred to.

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

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, 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. The above-mentioned functions such as imparting lubricity, preventing electrification, preventing adhesion, improving friction / abrasive properties, and preventing clogging of the magnetic head may be imparted 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 substance 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.

After providing the magnetic recording layer, calendering is performed on this layer to improve smoothness, and S of magnetic output is obtained.
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.

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

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

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

The shape of the ferromagnetic powder can be widely used without particular limitation. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like, but needle shape and plate shape are preferable in terms of electromagnetic conversion characteristics. The crystallite size and non-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 magnetic substance particles having an average major axis length of 0.8 μ in the present invention have a value of 0.8 when a particle size value which is the largest value of the particles of each magnetic powder is integrated and a simple average is taken. It is a group of magnetic particles having μ. Particles having a small average major axis length have small scattering of transmitted light when dispersed in a resin, and are advantageous when formed as a coating film on a photographic film. or,
If the average major axis length becomes too small, the magnetic performance as a magnetic material will deteriorate, and it will be difficult to make it into a paint.
If the average major axis length is large, the sharpness of the image as a photographic film deteriorates. As a result of examination by the inventors,
It was confirmed that the preferable range is that the average major axis length is 0.8 μm or less and 0.1 μm or less can be used.

The pH and surface treatment of the ferromagnetic powder can be used without particular limitation (the surface may be treated with a substance containing an element such as titanium, silicon, aluminum, carboxylic acid, sulfonic acid, sulfuric acid ester, It may be treated with an organic compound such as a phononic acid, a phosphoric acid ester, an adsorptive compound having a nitrogen-containing heterocyclic ring such as benzotriazole). The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron.

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

In the case of the present invention, the preferred amount of magnetic powder used is
4 × 10 ^-4 g or more is preferable per 1 m ^{2 of the} photographic light-sensitive material. If it is less than this, input / output of magnetic recording will be hindered. The upper limit may be any number as long as the optical density of light having a wavelength of 436 nm is 1.5 or less, but the limit is about 4 g per 1 m ² , and if it is more than this, a problem occurs in practical use as a photograph.

The term "transparent" in the present invention means that the optical density of the magnetic recording layer is 1.5 or less. The optical density is measured using a Konica Sakura Densitometer PDA-65, a filter transmitting blue light is used, and light having a wavelength of 436 nm is vertically incident on the coating film to absorb the light. It depends on the method of calculating. The optical density is preferably small considering the influence on the photographic image, and is 0.2 or less, particularly preferably 0.1 or less.

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 may be used alone or in combination.

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

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

These are usually solvent-based or water-based latex,
Alternatively, it can be used as an aqueous emulsion or an aqueous colloidal solution. In the case of these synthetic resin latexes and synthetic resin emulsions, those having a particle size of 5 nm to 2 μm can be used.

The term "aqueous latex resin" as used in this patent refers to a resin obtained by emulsifying and suspending a resin as a solid phase in a liquid phase containing water as a main solvent. Chemistry of Polymer Latex "(Souichi Muroi, Polymer Publishing Association).

In this patent, water-based latex, water-based emulsion, water-based emulsion, water-based colloid, etc. that can be dried to form a film are treated as synonymous.

The resin emulsified and suspended in water may be crystalline, amorphous, or rubber-like. A surfactant or the like may be used during emulsification, or a hydrophilic group may be introduced into the molecule of the resin to swell in the liquid phase and emulsify. As the water-based latex resin, polyester and acrylic resins are particularly preferable.

The radiation-curable resin is a resin which is cured by radiation such as electron beam and ultraviolet rays, and is a maleic anhydride type, urethane acryl type, ether acryl type, epoxy acryl type solvent-based or water-based latex or water-based emulsion. The following are listed.

The thermosetting resin and other reactive resins include phenol resin, epoxy resin, polyurethane-based curable resin, urea resin, alkyd resin, silicone-based curable resin, etc., which are solvent-based or water-soluble or water-based. Examples include latex and aqueous emulsion.

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 usable 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,
Compounds having a reactive halogen described in British Patent No. 974,723 and 1,167,207, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5- Triazine, U.S. Pat.Nos. 3,635,718, 3,232,763, and compounds having reactive olefins described in British Patent 994,869, N-hydroxymethylphthalimide, U.S. Pat.
No. 2,316, 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. 7,280, 2,983,611, etc., aziridine compounds, U.S. Pat.Nos. 2,725,294, 2,725,295, etc., acid derivatives, U.S. Pat. No. 3,091,537 And halogen carboxaldehydes such as mucochloric acid. 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-5
The carboxyl group-activating type hardeners described in 2-54427, U.S. Pat. No. 3,321,313 and the like can also be mentioned.

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

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. Condensation polymers with alkylene glycols such as polyethylene terephthalate, polyethylene-2,6
-Dinaphthalate, polypropylene terephthalate, polybutylene terephthalate and the like, or 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 No. 2-214852, JP-A No. 2-291135 and the like.

Further, it is more preferable to use a support as shown in Japanese Patent Application No. 5-99649 in which two or more layers of copolyester having different water contents are laminated.

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 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. Diaresin manufactured by Mitsubishi Kasei Corporation and MACROLE manufactured by Bayer
The target can be achieved by using dyes such as X 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 and the like may be used.

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, paraffin wax and fluorocarbons. Specifically, these can be used alone or in combination. The addition amount of these is 100
It can be used in the range of 0.5 to 20 parts by weight with respect to parts by weight. The melting point is preferably 50 ° C or higher.

Specifically, C _n H _{2n + 2} n = 24 or more, and C ₁₁ H ₂₃ COOC ₃₀ H ₆₁ C ₁₃ H ₂₇ COOC ₃₀ H ₆₁ C ₁₅ H ₃₁ COOC ₃₀ H ₆₁ C ₁₇ H ₃₅ COOC ₃₀ H ₆₁ C ₂₁ H ₄₃ COOC ₃₀ H ₆₁ C ₂₇ H ₅₅ COOC ₃₀ H ₆₁ C ₁₁ H ₂₃ COOC ₄₀ H ₈₁ C ₁₃ H ₂₇ COOC ₄₀ H ₈₁ C ₁₅ H ₃₁ COOC ₄₀ H ₈₁ C ₁₇ H ₃₅ COOC ₄₀ H ₈₁ C ₂₇ H ₅₅ COOC ₄₀ H ₈₁ C ₁₁ H ₂₃ COOC ₅₀ H ₁₀₁ C ₁₃ H ₂₇ COOC ₅₀ H ₁₀₁ C ₁₅ H ₃₁ COOC ₅₀ H ₁₀₁ C ₁₇ H ₃₅ COOC ₅₀ H ₁₀₁ C ₂₇ H ₅₅ COOC ₂₈ H ₅₇ etc. To be

Examples of the abrasive include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specifically, aluminum oxide (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 0.01-2.0
μm is preferable, and it can be added in the range of 0.5 to 500 parts by weight relative to 100 of the magnetic powder.

The non-magnetic powder of the present invention has a magnetization of 5 emu or less per gram.

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. Such non-stoichiometric hydrides, HfO ₂ , ThO ₂ , ZrO ₂ , CeO ₂ , ZnO, TiO ₂ , SnO ₂ , Al _{2
O 3, In 2 O 3,} SiO 2, MgO, BaO, MoO 2, V 2 O 5 , etc., or preferably composite oxides thereof, in particular ZnO, TiO ₂ and SnO ₂ are preferred. Examples of containing different kinds of atoms include, for example, addition of Al, In or the like to ZnO, addition of Nb or Ta to TiO ₂ , or
The addition of Sb, Nb, halogen elements, etc. is effective for SnO ₂ . Addition amount of these hetero atoms is 0.01 mol% to 25 mol%
Is preferable, but the range of 0.1 mol% to 15 mol% is particularly preferable.

From the viewpoint of electrical resistance, physical strength of the coating film, and abrasion resistance, it is preferable that these conductive oxidants have a volume fraction of the dry coating film of 8% or more and 50% or less. A particularly preferred range is 15% or more and 40% or less in terms of the volume fraction.

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.

In addition, conductive fine powders such as carbon black and carbon black graft polymer, nonionic surfactants such as alkylene oxide, glycerin and glycidol, higher alkylamines, quaternary ammonium salts, pyridine and others. A salt of a heterocyclic compound, a cation-type surfactant such as phosphonium or sulfonium; an anion-type surfactant containing an acidic group such as carvone, phosphorus, sulfate ester group and phosphate ester group;
Examples thereof include amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphoric acid esters of amino alcohols.

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

[0084]

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

Example 1 1-1) Preparation of Undercoat Treatment Base As a polyester resin for a support, P-1: commercially available polyethylene terephthalate (intrinsic viscosity)
0.65) P-2: 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added to 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, and transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: 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) P-1 and P-2 were vacuum-dried at 150 ° C, respectively, and two of the three extruders were used for P-2 and melt-extruded at 285 ° C to obtain a film thickness ratio of three layers. However, P-2: P-1: P-2 = 1:
The layers were joined in a T-die so as to be 2: 3, and were rapidly solidified on a cooling drum to obtain a laminated unstretched film. Then, after longitudinal stretching (3.4 times) at 85 ° C., transverse stretching (3.4 times) at a temperature of 95 ° C., and heat setting at 210 ° C., a biaxially stretched film having a thickness of 90 μ was obtained.

8 W / on both sides of the support of this polyethylene terephthalate (laminated type of materials having different moisture absorption)
(M ² · / min) corona discharge treatment is applied, and the following subbing coating solutions U-1 and U-2 are applied to the outside of the thin side of the copolyester.
To a dry film thickness of 0.8 μm and 0.1 μm, respectively, and to the other surface, apply the undercoating coating solution U-3 below to a dry film thickness of 0.8 μm. A layered support was prepared.

[0087] [Undercoat layer coating liquid U-1]   Butyl acrylate / t-butyl acrylate / styrene 270g   / 2-hydroxy acrylate copolymer latex liquid   (Weight composition ratio: 30: 20: 25: 25, solid content 30%)   Compound (A-1) 0.6 g   Hexamethylene-1,6-bis (ethylene urea) 0.8 g These were mixed and diluted with water to make 1 liter.

[0088] [Undercoat layer coating liquid U-2]   Gelatin 10g   Compound (A-1) 0.2 g   Compound (A-2) 0.2 g   Compound (A-3) 0.1 g   Silica particles (average particle size: 3 μm) 0.1 g These were mixed and diluted with water to make 1 liter.

[Undercoat Layer Coating Liquid U-3] Polyester latex liquid (solid content 30%) 223 g Tin oxide fine powder (average particle size 0.1 μm) 107 g “SN100P” manufactured by Ishihara Sangyo Co., Ltd. 1000 g of a 3/1 mixture of water / isopropanol was added.

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

[0091]

[Chemical 1]

1-2) Coating of magnetic recording layer On the coating of the undercoating layer U-3 of the above-mentioned undercoating base, a magnetic coating material having the following composition is used to form a dry film thickness of 0.8 μm using a precision extrusion coater. The magnetic material was orientated in the application direction in an orientation magnetic field while the coating film was not dried, and the output was increased during magnetic recording and reproduction.

[Magnetic Paint M-1] Cobalt-containing gamma iron oxide 5 parts by weight Average major axis length 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc 600 Oe Tin oxide fine powder (average particle size 0.1 μm) 60 parts by weight Part (SN100P made by Ishihara Sangyo Co., Ltd.) α-alumina (average particle size 0.5 μm) 7 parts by weight paraffin wax (melting point approx. 64 ° C.) 3 parts by weight polyester latex liquid 135 parts by weight (Tg = 70 ° C., number average molecular weight 20,000) , Solid content 30%) These were kneaded and dispersed to obtain a magnetic paint.

The original film after coating the magnetic recording layer was passed through a heat treatment zone at 150 ° C. to sufficiently form a latex.

1-3) Coating of the photosensitive material layer The surface opposite to the surface having the magnetic recording layer, that is, the undercoat layer U-
After applying a corona discharge of 25 W / (m ² · min) on top of 2,
A multilayer color light-sensitive material having the emulsion layer structure of Example 1 described in Japanese Patent Application No. 4-267697 was prepared, and a photographic light-sensitive material was prepared.
This is designated as Sample No. 1.

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

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

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds 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 150.0g Ammonium nitrate 10.0g Water added 1.0l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium 1.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0mg Sodium bisulfite 4.6g Water added 1.0l pH 6.6 Stabilizer Formalin (40%) 2.0mg Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree 10) 0.3 g Water to make 1.0l Examples 2-5 in Table 1 the composition of the magnetic coating material M-1 in 1-2) of Comparative Example 1-6 Example 1
A photographic light-sensitive material was prepared in exactly the same manner as in Example 1 except that the above was changed.

[0100]

[Table 1]

(1) Tin oxide (SnO ₂ ) average particle size 0.1 μm (2) SiO ₂ fine particles average particle size 0.3 μm (3) Paraffin wax melting point about 64 ° C. (4) Polyester latex Tg = 70 ° C., solid content concentration 30
% Examples 6 to 8 and Comparative Examples 7 to 26 The composition of the magnetic paint M-1 in 1-2) of Example 1 is shown in Table 2.
A photographic light-sensitive material was prepared in exactly the same manner as in Example 1 except that the above was changed.

[0102]

[Table 2]

(5) Tin oxide (SnO ₂ ) average particle size 0.1 μm (6) SiO ₂ fine particles average particle size 0.7 μm (7) α-Al ₂ O ₃ average particle size 0.5 μm (8) CaCO ₃ average particle size 0.5μm (9) Talc fine powder Average particle size 0.5μm (10) Polyester latex Tg = 70 ℃, solid content concentration 30
% (Same as that of Sample 1) Examples 9 to 12, Comparative Examples 27 to 33 In the composition of the magnetic coating material M-1 in 1-2) of Example 1, α
-A photographic light-sensitive material was prepared in exactly the same manner as in Example 1 except that the alumina and polyester latex liquids were replaced as shown in Table 3.

[0104]

[Table 3]

(11) SiO ₂ fine particles (12) Polyester latex Tg = 65 ° C., number average molecular weight
24,000, solid content 30% (13) Acrylic ester latex Tg = 70 ℃, solid content
30% (14) Gelatin aqueous solution Solid content 10% Examples 13 to 17 The composition of the magnetic paint M-1 in 1-2) of Example 1 is shown in Table 4.
A photographic light-sensitive material was prepared in exactly the same manner as in Example 1 except that the binder latex solution was changed as described above.

[0106]

[Table 4]

Evaluation of photographic light-sensitive material Each sample of the photographic light-sensitive material prepared as described above was evaluated as follows.

[1] Turbidity (Haze Value) The turbidity meter SEP-PT-501D manufactured by Mitsubishi Kasei Co., Ltd. was used to measure each sample immediately before coating the photosensitive material layer.

[2] Surface resistivity sample was cut into a width of 35 mm and a length of 70 mm, and the temperature was 25 ° C. and the humidity (RH).
After storing at 10% for 10 hours, using a teraohm meter VE-30 manufactured by Kawaguchi Electric Co., Ltd., applied voltage 100 V, 23 ° C., 20
% (RH) was measured. The side fixed surface is the magnetic recording layer coated surface immediately before the coating of the photosensitive material.

[3] Scratch test Tip of a 0.025mmR diamond needle is vertically placed at 25 ° C, 60% (R
Under the environment of (H), the load was continuously increased and the scratch was performed at a constant speed.

The sample was observed under transmitted light under a microscope, and the load at the point where continuous streaks changed to discontinuous scratches was defined as the number of scratches. The larger the value, the better. The side not having the emulsion layer before the development processing was tested.

[4] Durability Test A sample was fixed with the measuring surface of the sample on a loading platform that horizontally reciprocates at a distance of 15 cm, and the stainless steel ball (5
mmφ) was applied with a load of 50 g. The platform was slid at a speed of 10 cm / sec and repeated 1000 times. The degree of subsequent scratching was measured by the rank shown below.

A: No scratches B: Sliding marks, but no reduction in output in the magnetic recording / reproducing apparatus C ... Scratches, 50% reduction in output in the magnetic recording / reproducing apparatus D ... The film peeling measurement surface is the surface without the emulsion layer before development, and the measurement environment was room temperature (25 ° C., 55% RH).

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

[6] Sticking test Each sample is cut into four pieces each having a width of 35 mm and a length of 70 mm and stored for one day (24 hours) in an atmosphere of 23 ° C. and 80% RH so that they do not contact each other. After that, stack four sheets with the emulsion layer on top, sandwich them with cardboard of the same size,
Apply a load of 800 g to the entire surface and store in an atmosphere of 40 ° C and 80% RH for 3 days (72 hours). This sample was taken out and peeled off into each section, and the areas of the three front and back bonded portions were measured, and the average value was taken as the adhesion resistance.

Rank Area of bonded portion A 0 to 10% B 10 to 30% C 30 to 50% D 50 to 80% E 80 to 100% [7] Blocking 5 kg per 10 cm coating width on a resin core with a diameter of 20 cm After being wound up for 200 m under the tension of 1, and allowed to stand at room temperature for a whole day and night, the sample was unwound to check the variation of the tension on the feeding side when the photographic light-sensitive material was applied.

○: Tension fluctuation is within the range of machine accuracy and stable production is possible △: Peeling noise is generated when unwinding, tension fluctuation is about 10%, but trial production of sample is possible, Things that are judged to be difficult to stabilize during mass production × ・ ・ ・ Unwinding tension is unstable and workers can barely make trial samples [8] Guide dirt heat treatment zone exit side The metal guide rolls in contact with the surface coated with the magnetic coating of No. 1 were marked with X when the metal guide rolls were continuously conveyed for 100 m and caused fogging due to dirt, and those with no change were marked with O. From the experience, the X level has a high possibility of causing coating failure in the process.

The results of evaluating the samples of the photographic light-sensitive materials thus obtained are shown in Tables 5 to 8 below.

[0119]

[Table 5]

[0120]

[Table 6]

[0121]

[Table 7]

[0122]

[Table 8]

The results of Tables 5 to 8 show that the use of the magnetic powder of the specific size and the specific amount of the conductive powder according to the present invention greatly improves the optical transparency and the surface resistivity of the transparent magnetic material. It can be seen that the layer can be provided, the scratch strength and durability are significantly improved over the conventional one, and the output error after development is extremely small.

Further, it is understood that by using the inorganic filler having the hardness limited by the present invention and the paraffin wax in combination, the optical characteristics are lowered and the durability is improved and the productivity is also improved. In particular, it can be seen that the effect of the water-based latex binder is great.

According to the present invention, a halogen having a transparent magnetic recording layer which has a magnetic recording layer superposed on the image area and which is excellent in optical characteristics and durability, has no malfunction of magnetic input and output, and has good productivity. It was found that a silver halide photographic light-sensitive material was obtained.

Further, it was found that the photographic light-sensitive material of the present invention has equivalent or higher performance in terms of image quality such as sharpness of an image after development and suitability for a developing machine is equal to that of a commercially available product of our company.

[0127]

According to the present invention, firstly, it is possible to provide a silver halide photographic light-sensitive material having a transparent magnetic layer excellent in optical characteristics required for the photographic light-sensitive material.

Secondly, the silver halide photographic light-sensitive material having a transparent magnetic layer which is safer in terms of environment, safety and disaster prevention measures by transferring the preparation of the transparent magnetic layer to an aqueous system in terms of both environment and safety. Can be provided.

Thirdly, it is possible to provide a transparent magnetic layer which is excellent in water resistance and developer resistance and has a very small influence on the photographic photosensitive layer from the viewpoint of fog property, tackiness and the like.

Fourthly, it is possible to provide a transparent magnetic layer excellent in dispersion of magnetic powder and excellent in electromagnetic conversion characteristics.

Fifth, it is possible to provide a transparent magnetic layer containing a coating additive capable of preventing sedimentation / aggregation of the coating material for the transparent magnetic layer and maintaining the adhesion / optical characteristics at a required level. .

Sixthly, it is possible to provide a silver halide photographic light-sensitive material having a transparent magnetic layer which is excellent in the stability of coating and transporting, the number of working steps in the production process is reduced and the manufacturing cost is low.

Seventh, the photosensitive material is provided with sufficient slipperiness and scratch resistance against the contact between the magnetic head and the magnetic recording layer without impairing the transparency, and erroneous operation during magnetic recording / reproduction is prevented. It is possible to provide a photographic light-sensitive material that is less in number and is free from problems such as deterioration over time or after development processing.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-4-62543 (JP, A) JP-A-4-124635 (JP, A) JP-A-4-125553 (JP, A) JP-A-4- 328741 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/00 G03C 1/04 501 G03C 1/38 G03C 1/85

Claims (6)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support, wherein the average major axis length is 0.8 μm on at least one surface of the silver halide photographic light-sensitive material. A silver halide photographic light-sensitive material comprising a transparent magnetic layer containing the following magnetic particles and non-magnetic conductive oxide particles having a volume fraction with respect to a dry coating film of 8% or more and 50% or less. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the transparent magnetic layer contains a lubricant having a melting point of 50 ° C. or higher in a weight fraction of 0.5% to 20% with respect to the dry coating film. . 3. The silver halide photograph according to claim 1, wherein the transparent magnetic layer contains non-magnetic particles having a Mohs hardness of 6 or more and an average particle diameter of 0.01 μm or more and 2 μm or less. Photosensitive material. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the binder used in the transparent magnetic layer is an aqueous latex resin. 5. The silver halide photographic light-sensitive material according to claim 4, wherein the binder used in the transparent magnetic layer is a polyester-based water-based latex resin. 6. The silver halide photographic light-sensitive material according to claim 4, wherein the binder used in the transparent magnetic layer is an acrylic water-based latex resin.