JPH0926639A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form a transparent magnetic recording layer excellent in resistance to water and a developer and very slightly affecting a photographic sensitive layer from the viewpoint of fogging property, adhesiveness, etc. SOLUTION: This silver halide photographic sensitive material with at least one silver halide emulsion layer on at least one side of the substrate has at least one transparent magnetic recording layer contg. magnetic powder having <=0.6μm average major axis size and 700-1,0000e coercive force Hc and polyurethane having a wt. average mol.wt. of >=50,000 on at least one face of the sensitive material.

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 N
o. 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, such as the number of prints, filter selection, customer's color preference, trimming frame size, and other information necessary for printing, such as the number of prints, filter selection, customer color Entering various information obtained at the time of printing, such as the user's preference and the size of the trimming frame, and other customer information, in order to improve print quality from the viewpoint of management.
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, 49-45
03, U.S. Pat. No. 3,243,376,
No. 3,220,843, etc. Further, a transparent magnetic recording layer having the required transparency is provided on the back surface of a photographic light-sensitive material by selecting the amount and size of magnetizing particles. However, U.S. Pat. No. 3,782,947, 4,
No. 279,945 and No. 4,302,523. Also, U.S. Pat. No. 4,947,
No. 196, WO 90/04254 describes 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 a photographic film.

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

However, in the conventional method for preparing a coating material for a magnetic recording layer, magnetic particles are dispersed in a binder (also referred to as a binder) containing an organic solvent and then coated on a support, so that dust or organic particles are dispersed. It has been difficult to design a simple production facility because of various environmental safety measures for solvents and various disaster prevention problems. In addition, since the magnetic powder particles are basically oxide in surface characteristics and are hydrophilic, when dispersed,
A hydrophilic dispersion medium or water is basically known rather than a lipophilic dispersion medium. However, a water-soluble paint binder is advantageous because it can increase the viscosity and suppress aggregation of the magnetic powder, but it is difficult to improve water resistance in a dry coating film. Further, it is difficult to stably disperse the magnetic powder in a coating material called a latex or emulsion having a low viscosity and a high solid content.

Further, in order to improve the affinity and wettability between the magnetic powder and the binder or the organic solvent, JP-A-57-11182.
No. 9, JP-A-60-69819, JP-A-63-839.
Although efforts are being made to improve the surface, improve the binder and improve the dispersion method as shown in No. 22, almost no improvement has been attempted in an aqueous 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, so that the water resistance 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.

In addition, the presence of a monomer contained in the binder or a residual monomer due to uncrosslinking of the film hardener often influences the photosensitivity of the photograph and causes fog and poor color development.

Therefore, the binder which can be used in the present invention is considerably limited, and in order to put it into practical use, a considerably advanced dispersion technique, crosslinking technique, slipperiness imparting technique and the like are required.
It was a level that was impossible with conventional technology.

The conventional material for 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 a pigment with high specific gravity such as magnetic powder with high cohesive force at a low concentration to form a uniform thin film without 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 for which a patent has been applied or patented has been 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. It is liable to be altered due to decay. In addition, even at low concentration, the viscosity is high, causing gel change due to 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, in recent years, with the higher functionality of photographic light-sensitive materials, multi-layering such as simultaneous multi-layer coating has been carried out. However, it is fundamental to see how various functions can be realized as one coating material and one coating film. No invention has been made based on the concept of simple layering.

[0017]

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

A second object is to prepare a transparent magnetic recording layer, and transfer the material and the process to an aqueous system. The silver halide having a transparent magnetic recording layer which is safer in terms of environment, safety and disaster prevention measures and has a low environmental cost. Third in providing photographic light-sensitive material
It is an object of the present invention to provide a transparent magnetic recording 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 fogging property, tackiness and the like.

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

A fifth object is to have sufficient slipperiness for contact between the magnetic head and the magnetic recording layer without impairing transparency,
It is an object of the present invention to provide a photographic light-sensitive material which is provided with scratch resistance to a light-sensitive material, has few malfunctions during magnetic recording and reproduction, and has no trouble such as deterioration over time or after development processing.

[0021]

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

In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on at least one side of a support, at least one surface of the silver halide photographic light-sensitive material has an average major axis length of 0. 6 μm or less,
A silver halide photographic light-sensitive material comprising at least one transparent magnetic recording layer containing magnetic powder particles having an Hc of 700 to 1000 oersteds and a polyurethane having a weight average molecular weight of 50,000 or more.

The silver halide photographic light-sensitive material as described above, wherein the transparent magnetic recording layer is dispersed in an aqueous solvent.

The aqueous solvent is a hydrophilic organic solvent 30
The silver halide photographic light-sensitive material as described above or above, characterized in that the silver halide photographic light-sensitive material is contained in an amount of not more than wt%.

The transparent magnetic recording layer has a grain size of 0.05 to 3
(5) The silver halide photographic light-sensitive material as described in any one of (1) to (4) above, wherein the magnetic recording layer contains nonmagnetic particles having a Mohs hardness of 6 or more in an amount of 0.5 to 15% by weight based on polyurethane in the magnetic recording layer.

The silver halide photographic light-sensitive material as described in any one of 1 to 3, wherein the main chain of the polyurethane is an aliphatic isocyanate and an aliphatic polyester polyol or an aliphatic polycarbonate polyol.

The silver halide photographic light-sensitive material as described in any one of the above 1 to 3, wherein the Tg of the polyurethane is 90 ° C. or higher.

[0028]

DETAILED DESCRIPTION OF THE INVENTION The present invention is described in detail below.

In the following description, the volume fraction is the volume ratio of a certain substance in the coating film. In order 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 composition is unknown,
It is also possible to dry at 40% and then scrape off with a sharp edged tool, calculate the volume, and then separate the components by various analytical chemical methods.

(Magnetic Recording Layer) The magnetic recording layer used in the present invention will be described below.

The pigment powder including the magnetic substance is dispersed 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, cokneader, intensive mixer, tumbler, blender, disperser,
A homogenizer, a single screw extruder, a twin screw extruder, an ultrasonic disperser, etc. can be used. In this case, it is preferable that the magnetic particles are dispersed and dispersed as much as possible without damaging the magnetic particles.

When forming an optically transparent magnetic recording layer, the binder is 1 to 20 parts by weight with respect to 1 part by weight of the magnetic powder.
It is preferable to use 0 part by weight. More preferably, it is 2 to 50 parts by weight with respect to 1 part by weight of the magnetic powder. Also,
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 of providing the magnetic recording layer on the 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 multiple stripe coating, these coating heads may be formed in multiples. As a specific method of stripe coating,
For example, JP-A-48-25503 and 48-25.
No. 504, No. 48-98803, No. 50-1.
No. 38087, No. 52-15533, No. 51
-3208 gazette, the same 51-6239 gazette, the same 51-
No. 65606, No. 51-140703, Japanese Patent Publication No. 29-4221, and U.S. Pat. No. 3,062,18.
The description in the No. 1 specification and the No. 3,227,165 specification can be referred to.

The thickness of the magnetic recording layer is 0.01 to 20 μm.
Is more preferable, 0.05 to 15 μm is more preferable, and 0.1 to 10 μm is still more preferable.

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to impart functions to the magnetic recording layer such as lubricity, antistatic property, antiadhesive property and friction / wear property improvement. Various additives such as can be added. In addition, in addition to the coating liquid, for example, a plasticizer to give flexibility to the magnetic recording layer, a dispersant to help disperse the magnetic material in the coating liquid, to prevent clogging of the magnetic head Can be added to the polishing agent. The above-mentioned functions such as lubricity, antistatic, adhesion prevention, friction / wear 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 the 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 the 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 a 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 7
5 wt% or more, and 80 wt% or more of the metal content is at least one kind of ferromagnetic metal or alloy (Fe, Co, N
i, Fe-Co, Fe-Ni, Co-Ni, Co-Fe
-Ni, etc.) and other components (Al, Si, S, Sc, Ti, V, Cr, Mn, C at 20 wt% or less of the metal content.
u, Zn, Y, Mo, Rh, Pd, Ag, Sn, Sb,
B, Ba, Ta, W, Re, Au, Hg, Pb, P, L
a, 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 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 of the ferromagnetic powder can be widely used without particular limitation. The shape may be any of a needle shape, a rice grain shape, a spherical shape, a cubic shape, a plate shape and the like, but a needle shape and a 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, and the SBET is 2
0 m ² / g or more is preferable, and 30 m ² / g or more is particularly preferable.

In the present invention, the magnetic substance particles having an average major axis length of 0.8 μm are the values obtained by integrating the particle size values which are the largest values of the particles of each magnetic powder and taking a simple average. 0.
It is a group of magnetic particles having a size of 8 μm. 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. On the other hand, if the average major axis length is too small, the magnetic performance of the magnetic material deteriorates, and it becomes difficult to form a coating material. When the average major axis length is large, the sharpness of the image as a photographic film deteriorates. As a result of examination by the present inventors, the preferable range is that the average major axis length is 0.6 μm.
It was confirmed below that even the one having a thickness of 0.1 μm 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 or aluminum, carboxylic acid, sulfonic acid, sulfuric ester, It may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocyclic ring such as phononic acid, phosphoric acid ester and benzotriazole). The preferred pH range is 5-10. In the case of a 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 as long as it is in the range of 700 to 1000 oersteds. Preferably 730 to 950 Oe
It is.

In the case of the present invention, the preferred amount of magnetic powder used is
It is preferably 4 × 10 ⁻⁴ g or more per 1 m ^{2 of the} photographic light-sensitive material. If it is less than this, the input / output of the magnetic recording is hindered. The upper limit may be any number as long as the optical density of the 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, practically a problem occurs as a photograph.

The transparency of the transparent magnetic recording layer in the present invention means that the optical density of the magnetic recording layer is 1.5 or less. The optical density measurement method is Konica (made by) Sakura Densitometer PD
A-65 is used, a light having a wavelength of 436 nm is vertically incident on the coating film using a filter that transmits blue light, and the absorption of light by the coating film is calculated. 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.

(Polyurethane) Next, polyurethane will be described. It results from the reaction of polyols with polyisocyanates. As the polyol, a polyester polyol obtained by reacting a polyol with a polybasic acid is generally used. Therefore, if a polyester polyol having a polar group is used as a raw material, a polyurethane having a polar group can be synthesized.

A polyester (polyol) having a polar group can be synthesized from a polyol and a polybasic acid partially having a polar group. A polar group may be introduced into a part of the polyol.

Examples of polybasic acids having polar groups include 5
-Sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-
Examples thereof include sulfoisophthalic acid, dialkyl 5-sulfoisophthalate, dialkyl 2-sulfoisophthalate, dialkyl 4-sulfoisophthalate, and their sodium salts and potassium salts. These are all aromatic polybasic acids, but those in which the benzene ring portion of these compounds is changed to a cyclohexane ring by hydrogenation can also be mentioned as an example of the polybasic acid having a polar group.

Examples of polyols include trimethylolpropane, hexanetriol, glycerin, trimethylolethane, neopentyl glycol, pentaerythritol, ethylene glycol, propylene glycol, 1.3-butanediol, 1.4-butanediol, 1 6-hexanediol, diethylene glycol, cyclohexanedimethanol and the like can be mentioned. Further, an aliphatic carboxylic acid containing two or more methylol groups such as dimethylolpropionic acid can be used as a polyol having a polar group. In this case, the carboxyl group may be a metal salt such as sodium salt or potassium salt, or may be in the form of a salt by reacting with an amine or the like.

Examples of polyisocyanates include diphenylmethane-4-4'-diisocyanate (MDI),
Hexamethylene diisocyanate (HMDI), tolylene diisocyanate (TDI), 1.5-naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), lysine isocyanate methyl ester (LDI) and the like can be mentioned.

As another method for synthesizing a polyurethane having a polar group, an addition reaction between a polyurethane having a hydroxyl group and the following compound having a polar group and a chlorine atom is also effective. _{Cl-CH 2 CH 2 SO 3} M, Cl-CH 2 CH 2 OS
_{O 2 M, Cl-CH 2} COOM, Cl-CH 2 -P (=
0) (OM ¹ ) _{2 As} a technique for introducing a polar group into polyurethane, JP-B-58-41565 and JP-A-57-9242 are known.
No. 2, No. 57-92423, No. 59-8127, No. 59-5423, No. 59-5424, No. 62-12.
It is described in the publications such as 1923, and these can be used in the present invention. In the present invention, both the polyester polyol and the polyisocyanate are preferably aliphatic, that is, those containing no aromatic ring.

(Other Binder) Polyurethane having a weight average molecular weight of 50,000 or more is used as a binder (binder) used in the magnetic recording layer, but it is a thermoplastic resin, a radiation curable resin or other reactive resin. Then, those which are stably suspended in water or a hydrophilic solvent can be mixed and used. These are used within a range that does not impair the effects of the present invention.

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 Vinyl-based polymers or copolymers such as copolymers, ethylene-vinyl alcohol copolymers, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymers, ethylene-vinyl acetate copolymers, nitrocellulose, cellulose acetate pro Cellulose derivatives such as pionate and cellulose acetate butyrate resin, copolymers of maleic acid and / or acrylic acid, acrylic acid ester copolymers, acrylonitrile-styrene copolymers, chlorinated polyethylene, acrylonitrile-chlorinated polyethylene-styrene. Copolymer, meth 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-butadiene resin, butadiene-acrylonitrile Examples thereof include rubber-based resins such as resins, silicone-based resins, and fluorine-based resins.

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

These can be usually used as solvent-based or water-based latex, or water-based emulsion or water-based 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 the present invention 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 the present invention, those capable of being dried to form a film, such as an aqueous latex, an aqueous emulsion, an aqueous emulsion, and an aqueous colloid, 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 or ultraviolet ray, 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 phenolic resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, silicone-based curable resins and the like, which are solvent-based or water-soluble or water-based. Examples include latex and aqueous emulsion.

The binder listed above may have a polar group in its molecule. As the polar group, an epoxy group, -C
_{OOM, -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.). To be

Other hydrophilic binders that can be used in the present invention include, for example, Research Disclosure No. 17643, page 26, and ibid. 1871
Examples thereof include water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters described on page 6,651.

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 and the like in addition to the above-mentioned cellulose ethers. Examples thereof include methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like. These are used within a range that does not impair the effects of the present invention.

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 cyclopentadione, bis (2-chloroethylurea), and 2-hydroxy-4,6-dichloro-. 1, 3, 5
-Triazine, U.S. Pat. Nos. 3,288,775, 2,732,303, British Patent 97.
Compounds having a reactive halogen described in 4,723, 1,167,207 and the like,
Divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat. No. 3,635,718, 3,232,763.
Compounds having reactive olefins described in U.S. Pat. No. 4,732,089, U.S. Pat. No. 2,732,
Nos. 3,316, 2,586,168 and the like, N-methylol compounds, US Pat. No. 3,1.
Isocyanates described in, for example, 03,437, U.S. Pat. No. 3,017,280, and 2,
983,611 and the like, aziridine compounds, U.S. Pat. Nos. 2,725,294 and 2,725,295, and the like, acid derivatives and U.S. Pat. Examples thereof include epoxy compounds described in 3,091,537 and the like, halogen carboxaldehydes such as mucochloric acid.
Further, an inorganic hardener can also be used, and examples of the inorganic hardener include chrome alum and zirconium sulfate, and JP-B-56-12853 and 58-58.
-32699, Belgian Patent No. 825,726, JP-A-60-225148, JP-A-51.
-126125, JP-B-58-50699, JP-A-52-54427, and U.S. Pat. No. 3-3.
Other examples include carboxyl group-activating type hardeners described in JP-A No. 21,313, and the like.

The hardener is usually used in an amount of 0.
It is used in an amount of 01 to 60% by weight, preferably 0.05 to 50
% By weight.

As the lubricant that can be used in the magnetic recording layer of the present invention, silicone oil such as polysiloxane,
Examples thereof include 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 can be used in the range of 0.5 to 20 parts by weight with respect to 100 parts by weight of the dry coating film.
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 and 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 and the} like can be mentioned.

Examples of the abrasive include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specific examples thereof include aluminum oxide (α-alumina, γ-alumina, corundum) and chromium oxide. Examples thereof include (Cr ₂ O ₃ ), iron oxide (α-Fe ₂ O ₃ ), oxides such as silicon dioxide and titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powder such as diamond. The average particle size of these is preferably 0.01 to 2.0 μm, and the magnetic powder 10
It can be added in the range of 0.5 to 500 parts by weight based on 0.

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 the metal oxide include oxides in excess of oxidation such as Nb ₂ O _{5 + x} , RhO _{2 -X} , Ir ₂ O _{3 -X.}
Oxygen deficient oxides such as Ni (OH) _x , non-stoichiometric hydrides such as Ni (OH) _x , HfO ₂ , ThO ₂ , ZrO ₂ , Ce
O ₂ , ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In
₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O
₅ or the like, or a composite oxide of these, is particularly preferable.
nO, TiO ₂ and SnO ₂ are preferred. Examples of containing different kinds of atoms include adding Al, In, etc. to ZnO, adding Nb, Ta, etc. to TiO ₂ , or SnO.
_{For 2} , it is effective to add Sb, Nb, a halogen element, or the like. Addition amount of these hetero atoms is 0.01 mol%
~ 25mol% range is preferable, but 0.1mol% ~
The range of 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 to these, conductive fine powders such as carbon black and carbon black graft polymers, nonionic surfactants such as alkylene oxides, glycerins and glycidols; higher alkyl amines, 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.

(Undercoat Layer) In order to firmly adhere the magnetic recording layer of the present invention onto the support, an undercoat layer may be provided on the support, and the support may be treated with a chemical agent or mechanically. Surface activation treatment such as treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment and ozone oxidation treatment may be performed.
Further, an undercoat layer may be provided after the surface activation treatment. The undercoat layer is preferably an aqueous latex type.

(Support) In the present invention, various supports can be used. As the support that can be used, polyethylene terephthalate, polyester film such as polyethylene naphthalate, cellulose triacetate film, cellulose diacetate film,
Examples include a polycarbonate film, a polystyrene film, and a polyolefin film.

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 the development processing, JP-A-1-244446, 1-291248, 1-298350, 2-89045 and 2-93641, JP-A-2-181949, JP-A-2-214852, and JP-A-2-2911.
It is preferable to use a polyester having a high water content as shown in JP-A-35-35.

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 purpose of the support is to neutralize the tint of the minimum density portion, to prevent the light piping phenomenon (fogging) that occurs when light enters the film coated with the photographic emulsion layer from the edge, and to prevent halation. A dye can be contained in

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. As for the color tone, when the purpose is to prevent light piping, gray dyeing is preferable as seen in general photosensitive materials. The dyes may be used alone or in combination of two or more. Mitsubishi Kasei Co., Ltd. Diaresin, Bayer
It is possible to achieve the target by using a dye such as MACROEX manufactured by the company alone or by appropriately mixing them.

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 film light-sensitive material, an X-ray. It may be any silver halide photographic light-sensitive material such as a light-sensitive material, a light-sensitive material for printing, a light-sensitive material for microphotography.

[0086]

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 undercoating base As a polyethylene resin for a support, P-1: commercially available polyethylene terephthalate (intrinsic viscosity 0.65) P-2: 100 parts by weight of dimethyl terephthalate, ethylene glycol 64 0.1 part by weight of a hydrate of calcium acetate as an ester exchange catalyst was added to parts by weight, and transesterification reaction was carried out by a conventional method. The obtained product was added to a solution of 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: SIP) in ethylene glycol (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 / total weight of reaction product), 0.05 parts by weight of antimony trioxide, 0.13 parts by weight of phosphoric acid trimethyl ester, and Irganox 1010 (manufactured by CIBA-GEIGY) as an antioxidant were added so as to be 1% by weight based on the product polymer. Then, the temperature is gradually raised and the pressure is reduced to 280 ° C and 0.5
Polymerization was performed at mmHg to obtain a copolyester.
(Intrinsic viscosity 0.55) After vacuum drying P-1 and P-2 at 150 ° C. respectively, 3
Two of the two extruders are used for P-2, melt-extruded at 285 ° C., and the film thickness ratio of the three layers is P-2: P-1: P-2 =
The layers were joined in a T-die in a ratio of 1: 2: 3 and rapidly solidified on a cooling drum to obtain a laminated unstretched film.
Then, after longitudinal stretching (3.4 times) at 85 ° C, the temperature is 95 ° C.
The film was transversely stretched (3.4 times) and then heat set at 210 ° C. to obtain a biaxially stretched film having a film thickness of 90 μm.

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 was applied, and the following subbing coating solutions U-1 and U were applied to the outer side of the thin copolyester.
-2 is applied to a dry film thickness of 0.8 μm and 0.1 μm respectively, and the following undercoating coating solution U-3 is applied to a dry film thickness of 0.8 μm to prevent static electricity. A support having an undercoat layer formed thereon having a function was prepared.

[Undercoat Layer Coating Liquid U-1] Copolymer latex liquid of butyl acrylate / t-butyl acrylate / styrene / 2-hydroxyacrylate (weight composition ratio; 30: 20: 25: 25, solid content) 30%) 270 g Compound (A-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g These were mixed and diluted with water to give 11.

[Undercoat Layer Coating Liquid U-2] Gelatin 10 g Compound (A-1) 0.2 g Compound (A-2) 0.2 g Compound (A-3) 0.1 g Silica particles (average particle diameter: 3 μm) ) 0.1 g These were mixed and diluted with water to make 11.

[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.

[0092]

Embedded image

1-2) Coating of magnetic recording layer On the coating of the undercoat layer U-3 of the above-mentioned undercoating base, a magnetic coating material having the following composition is used to obtain a dry film thickness of 0.8 μm by using a precision extrusion coater. As described above, the magnetic substance was oriented in the coating direction in an orientation magnetic field while the coating film was not dried, so that the output was increased during magnetic recording and reproduction.

Magnetic coating M-1 Cobalt-containing γ iron oxide (average major axis length 0.1 μm, Hc800oe) 5 parts by weight Tin oxide fine powder (average particle size 0.1 μm) 3 parts by weight α-alumina (average particle size 0 0.5 μm) 4 parts by weight Polyurethane latex liquid (1) (see Table 3) (Tg of resin single film = 120 ° C., weight average molecular weight 170,000, solid content 30%, solvent: water / N-methyl-2-pi) Lolidone = 4/1) 230 parts by weight Carnauba wax aqueous dispersion (solid content 20%) 12 parts by weight These were kneaded and dispersed, and filtered through a Nippon filter filter HT50 to obtain a magnetic paint. The content of the hydrophilic organic solvent in all the solvents of this paint was 19%.

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

1-3) Coating of photosensitive material layer On the surface opposite to the surface having the magnetic recording layer, the undercoat layer U-2 is formed.
Was applied, and a corona discharge of 25 W / (m ² · min) was applied thereon, and then a multilayer color light-sensitive material having the emulsion layer constitution of Example 1 of Japanese Patent Application No. 4-267697 was prepared. A photographic light-sensitive material was prepared. This was designated as Sample No. Let it be 1.

In the multilayer emulsion layer, 13.7 g of gelatin per m ² , 0.3 to 0.4 μm and 0.7 to 0.
Each 8 μm silver halide grain has an amount of 2.3 g, an appropriate amount of oil of 2.8 g, and a film thickness of 27 μm.

<Development Treatment> The produced photographic light-sensitive material was exposed imagewise, and then developed with a treatment liquid having the following treatment process and the following composition. Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was

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 add 1.01 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 is added to 1.01 pH 6.0

Fixing solution Disodium ethylenediaminetetraacetate 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 mg Sodium bisulfite 4.6 g Water was added to 1.01 pH 6.6

Stabilizer Formalin (40%) 2.0 mg Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Water was added to 1.01 in 1-2 of Example 1. The composition of the magnetic paint M-1 is shown in Table 1.
A photographic light-sensitive material was prepared in exactly the same manner as in Example 1 except that the above was changed.

[0103]

[Table 1] The composition of the magnetic coating material M-1 in 1-2) of Example 1 was changed to the following M-2.

Magnetic Paint M-2 Cobalt-containing γ-iron oxide (average major axis length 0.1 μm, Hc800oe) 5 parts by weight Polyurethane latex solution (2) (see Table 3) (Tg = 100 ° C., weight average molecular weight 80) 2,000, solid content 30%, solvent: water / dimethylformamide = 6/1) 230 parts by weight α-alumina (average particle size 0.2 μm) 3.5 parts by weight These were mixed and dispersed to obtain a magnetic coating material. The hydrophilic organic solvent content of this coating material was 14% with respect to all the solvents.
After passing the magnetic coating material through the heat treatment zone at 150 ° C to form a latex film sufficiently, carnauba wax aqueous dispersion 0.1% is overcoated to a wet film thickness of 10 µm. Layers were applied and dried.

Other than the above, a photographic light-sensitive material was prepared in exactly the same manner as in Example 1. The amount of alumina added to the binder in this sample was 5%.

A photographic light-sensitive material was prepared in exactly the same manner as above except that the kind and amount of the non-magnetic abrasive in the magnetic paint M-2 were changed as shown in Table 2.

Magnetic paint M-1 in 1-2) of Example 1
A photographic light-sensitive material was prepared in exactly the same manner except that the polyurethane latex liquids (2), (3) to (7) were used instead of the polyurethane latex (1). Table 3 shows the physical property and structure data of the polyurethane latex liquid used.

[0108]

[Table 2]

[0109]

[Table 3] Tables 4 to 6 show the results of evaluating the samples of the photographic light-sensitive materials thus obtained.

Evaluation of Photographic Photosensitive Material Each sample of the photographic photosensitive material prepared as described above was evaluated as follows. [1] Scratch test Apply a diamond needle with a tip of 0.025 mmR vertically to
Scratching was performed at a constant speed while continuously increasing the load under the environment of 60 ° C. and 60% (RH).

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 higher the value, the better. The side not having the emulsion layer before the development processing was tested.

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

A: No damage B: Although there was a sliding mark, there was no reduction in output in the magnetic recording / reproducing device C: Scratch, output in magnetic recording / reproducing device 50%
Deterioration D ... Film peeling The measurement surface was a surface having no emulsion layer before development, and the measurement environment was room temperature (25 ° C., 55% RH).

[3] Noise Level Evaluation During Magnetic Recording / Reproduction Using a recording / reproducing magnetic head for an audio tape recorder, a rectangular wave having a recording wavelength of 20 μm was set to the optimum recording current value of the medium for recording. This was reproduced with the same head at a constant speed, and the medium noise was measured.

The noise level of each magnetic recording layer was quantified by standardizing the amount of magnetic powder per unit coating area of the magnetic recording layer.

The higher the noise, the poorer the dispersion of the magnetic powder, and the less uniform the contact of the noise with the magnetic recording layer, the poorer the magnetic recording layer.

[4] Sticking test Four pieces of each sample were cut into a size of 35 mm width and 70 mm length, and were kept at 23 ° C. and 80% without touching each other.
Store under a RH atmosphere for 24 hours a day. After that, 4 sheets were piled up with the emulsion layer on top, sandwiched with cardboard of the same size, and a load of 800 g was applied to the entire surface.
Store for 3 days (72 hours) in an atmosphere of 80 ° C and 80% RH. This sample was taken out, each section was peeled off, and the areas of the bonded portions on the front surface and the back surface at three locations were measured, and the average value was taken as the adhesion resistance.

Rank Area of bonded portion A 0 to less than 10% B 10 to less than 30% C 30 to less than 50% D 50 to less than 80% E 80 to 100%

[5] Turbidity The turbidity meter SEP-PT-501D manufactured by Mitsubishi Chemical Corporation was used to measure each sample immediately before coating the photosensitive material layer. [6] Continuous coating stability Using a coater head with a coating width of 70 cm, the number of coating streak failures that occurred when coating was continuously performed for 1200 m at a coating speed of 170 m / min was counted as an index of continuous coating stability.

0 to 1 is OK, but 5 or more are difficult to commercialize.

[0121]

[Table 4]

From this, the average particle size of the magnetic powder and the coercive force (H
It can be seen that by setting c) within the range of this patent, a transparent magnetic recording layer excellent in noise level and dispersibility can be obtained.

When the molecular weight of polyurethane is 50,000 or more and the hydrophilic organic solvent is 30% or less, a magnetic recording layer excellent in durability, transparency and dispersibility can be formed.

[0124]

[Table 5]

From the above, the combination of non-magnetic particles having the particle size and Mohs hardness within the range of this patent and the water-based polyurethane latex was excellent in scratch resistance, durability, sticking property to emulsion surface, and head suitability. A transparent magnetic recording layer can be formed.

[0126]

[Table 6]

[0127]

EFFECTS OF THE INVENTION According to the present invention, by using a polyurethane having a weight average molecular weight of 50,000 or more, particularly, the main chain of the polyurethane is an aliphatic type having the range of the present invention and Tg of 90 ° C. or more. By using the water-dispersed polyurethane, it is possible to supply a magnetic coating material for a transparent magnetic recording layer in which the adhesion to the emulsion surface, durability and continuous coating stability are well balanced.

Claims (6)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on at least one side of a support, wherein at least one surface of the silver halide photographic light-sensitive material has an average major axis length. 0.6 μm or less, H
A silver halide photographic light-sensitive material comprising at least one transparent magnetic recording layer containing magnetic powder particles having c of 700 to 1000 oersteds and polyurethane having a weight average molecular weight of 50,000 or more. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the transparent magnetic recording layer is dispersed in an aqueous solvent. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the aqueous solvent contains a hydrophilic organic solvent in an amount of 30% by weight or less. 4. The transparent magnetic recording layer has a grain size of 0.05 to 3 .mu.m.
The silver halide photograph according to any one of claims 1 to 3, characterized in that non-magnetic particles having a hardness of 6 and a Mohs hardness of 6 or more are contained in an amount of 0.5 to 15% by weight with respect to the polyurethane in the magnetic recording layer. Photosensitive material. 5. The silver halide photographic light-sensitive material according to claim 1, wherein the main chain of the polyurethane comprises an aliphatic isocyanate and an aliphatic polyester polyol or an aliphatic polycarbonate polyol. material. 6. The silver halide photographic light-sensitive material according to claim 1, wherein the Tg of the polyurethane is 90 ° C. or higher.