JP2000260016A - Magnetic recording medium, photographic sensitive material and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To fonn a lubricating protective layer which has high strength, is stable in traveling and has excellent wear resistance, and to make optical characteristics more uniform and productivity better by incorporating a polyvinyl alcohol(PVA) having a degree of polymerization of a specific value or above into the lubricating protective layer formed on the uppermost layer on the side of a nonmagnetic base having a transparent magnetic layer. SOLUTION: A binder usable for the lubricating protective layer is a PVA having the degree of polymerization of >=400 in terms of coating film strength, the uniformity of coating application, etc. The preferable degree of polymerization of the PVA is >=900. The degree of polymerization of the PVA refers to the average of the repeating number of a monomer unit per molecule of the PVA. The PVA used for the lubricating protective layer may also be used by mingling the PVA having the degree of polymerization of >=900 and the PVA having the degree of polymerization below 900. The degree of polymerization of the PVA having the degree of polymerization below 900 is preferably >=400 at this time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic recording medium having a transparent magnetic layer, a photographic light-sensitive material, and a method for producing the same, and more particularly, to a method having optical transparency and adding an image forming means to an opposite surface. The present invention relates to a magnetic recording medium that can be used.

[0002]

2. Description of the Related Art The coating technology of a magnetic recording medium has been progressing with the progress of higher density of magnetic recording and accompanying multi-layering and thinning. However, an optical recording layer is formed on a magnetic recording medium. Technology is also evolving. A photographic film with a magnetic recording layer is one example.

For example, a silver halide photographic light-sensitive material (hereinafter also simply referred to as a "light-sensitive material") has various information such as the type, serial number, manufacturer name, emulsion number, etc. Various information at the time of camera shooting such as exposure time, lighting conditions, filter used, weather, shooting size, shooting model, use of anamorphic lens, furthermore, number of prints, filter selection, customer color preference, trimming frame Various information required when creating prints such as size, the number of prints, selection of filters,
Entering various information obtained at the time of printing, such as the customer's color preference, the size of the trimming frame, etc., and other customer information, etc., from the viewpoint of management, improvement of print quality,
This is also necessary from the viewpoint of improving the efficiency of the printing operation.

In a conventional photosensitive material, it is impossible to input all of such information, and only information such as a photographing date and time, an aperture and an exposure time is optically inputted at the time of photographing. In addition, it is impossible to input the above information into the photosensitive material at the time of printing without any means.

Since the magnetic recording system is easy to record / reproduce, studies have been made on the use of the magnetic recording system for inputting the above-mentioned various information to a photosensitive material, and various techniques have been proposed.

[0006] For example, it is a special feature to provide a stripe-shaped magnetic recording layer in which ferromagnetic fine particles are dispersed on the emulsion surface or the back surface beside the image area to record information such as sound and photographing conditions. No. 50-62627, No. 49-4503
No. 3,243,376, U.S. Pat.
No. 43, etc., and on the back surface of a photographic material,
Providing a transparent magnetic recording layer having the required transparency by selecting the amount, size, etc. of the magnetic particles is disclosed in U.S. Pat.
No. 947, No. 4,279,945, No. 4,302,5
No. 23, etc. No. 4,947,
196 and WO 90/04254 describe a camera for photographing having a magnetic head together with a roll film having a magnetic recording layer containing a magnetic material capable of magnetic recording on the back surface of a photographic film.

The provision of these magnetic recording layers makes it possible to record the above-mentioned various information in the photosensitive material, which has been difficult in the past, and has the potential to record audio and image signals. ing.

However, the coating technique required for the magnetic recording layer of the photosensitive material and the physical properties of the binder include water resistance,
Very high and difficult to achieve levels such as abrasion resistance, dispersibility of magnetic powder, transparency, suitability for thin film coating, and dust generation during cutting and drilling are required. Among them, in particular the formation of the magnetic recording layer and the protective layer in the raw stage before coating the photosensitive material, traditional audio, unlike a tape such as a video, rigidity and coating composition of the support itself Completely different points, also premised on wet chemical processing such as development processing,
There are a wide variety of required quality items, such as a magnetic head after these processes and a point where the surface is rubbed when transported, and it is difficult to achieve it with existing technologies. For example,
Japanese Patent Application Laid-Open No. 7-72581 discloses the use of a water-soluble resin as a binder for a transparent magnetic layer, and shows an example in which polyvinyl alcohol is dispersed in a dispersion of magnetic powder. JP-A-7-1816
No. 12, the use of polyethylene wax on the transparent magnetic layer has been attempted. JP-A-7-219091 discloses that a fatty acid ester having a specific structure and a surfactant are combined with a transparent magnetic layer. Further, Japanese Patent Application Laid-Open No. 9-179240
Discloses a combination of a fluorine compound and hydroxylalkyl cellulose. JP-A-9-152678 discloses a technique for forming a layer to which a water-soluble binder is added on a magnetic layer. However, even with these technologies, the strength of the coating film and the stability of magnetic input and output after development,
Contamination of the developing solution due to elution of the coating film, etc., have not been completely satisfactory.

Further, various techniques have been disclosed regarding the conditions for forming a good lubricating layer, the production method, and the physical and chemical constants of the surface properties. For example, Japanese Unexamined Patent Publication No.
No. 116638 discloses a method in which a water-miscible organic solvent having a low boiling point and a high boiling point is used in combination when forming a higher fatty acid, a higher alcohol or a derivative thereof into a coating material. JP-A-4-243251 discloses that a higher fatty acid or a derivative thereof is contained in an outermost layer and, after coating, is brought into contact with a roll having a melting point or higher. JP-A-9-
Japanese Patent No. 204638 discloses a technique for setting a contact angle with water as a property value of a lubricating layer in a specific range.
Although a fluorine-based activator is added to stably perform thin film coating, it is desired to reduce the amount due to the problem of elution during development and environmental considerations that have been increasing in recent years.

When the outermost layer is hardened as a protective layer, the adhesion to the lower layer is deteriorated. When a good solvent is used, the adhesion to the lower layer is improved, but the transparency of the coating film after application is deteriorated. If a coating material having a low solid content is applied in order to make the protective layer thin, problems in the process such as uneven application and cissing failure occur. Furthermore, when a higher fatty acid ester or the like is added to impart lubricity, those having a low melting point are eluted when passing through a heated developer, and those having a high melting point are powdered on the surface after application of the raw material. Cloudy phenomena like blowing
Once it has to be dried through a heat treatment zone above the melting point. In addition, since a wax having a high melting point is usually hardly soluble in water or an organic solvent, it is dispersed in a low-viscosity paint as wax particles.However, in a drying process after application, wax particles are unevenly distributed due to a convection phenomenon in a coating film, Slip properties, water repellency, and stain adhesion of the surface after drying vary locally.
In particular, if the outermost layer during coating is to have a moderately rough surface and uniform lubricant distribution to ensure magnetic input / output stability, uneven wax particles after coating should be smoothed by post-processing. Uniformity cannot be achieved only by heating above the melting point. Further, in most conventional materials, the components of the lubricating layer are mostly fats and oils alone or those obtained by adding a binder to the fats and oils. However, the material technology is generally satisfactory with respect to the slipperiness of the medium, the adherence of dirt on the medium surface, the ability to transfer the dirt component on the medium surface to other contact members, but no material technology has been obtained. In particular, hydrophobic components, polymer components, and the like having low water solubility are preferred in order not to be easily eluted in heated water under development conditions, and hydrophilic components are preferred for reducing stains after development processing. It is preferable to use a material having excellent lubricating properties and abrasion resistance, that is, a material having good mechanical strength with respect to abrasion and sliding properties, and furthermore, when wound up and stored, it comes into contact with the emulsion layer surface. There should be no blocking, material transfer, or adverse effects on photographic performance. Due to such severe restrictions, the composition and manufacturing method of the outermost layer having a good function of a lubricating layer and a protective layer have not been achieved by the conventional technology.

Regarding the improvement of wear resistance, see JP-A-7-33.
3764 discloses a method for improving the scratch resistance by incorporating ceramic particles in the transparent magnetic recording layer.
If the stain on the film after development is transferred to a magnetic head and a magnetic signal cannot be read from the film after development, the problem cannot be solved simply by improving the scratch resistance of the magnetic recording layer. In Japanese Patent Application Laid-Open No. 10-222825, a magnetic recording layer using abrasives having different particle sizes is used, and stearic acid as a lubricant is fixed with an oxazoline group-containing polymer.
Improvement of head clogging at the time of magnetic input / output after development and improvement of durability of coating film by improving polishing property and lubricant retaining performance from the magnetic recording layer side have been proposed, but are still insufficient. is there.

With the recent improvement of image information processing technology,
The number of cases where optical information is directly read from a negative film or a positive film of a silver halide photographic light-sensitive material is increasing. For this purpose, there are methods such as addition of abrasive particles, embossing, and lamination to improve abrasion resistance and scratch resistance, but all of these methods impair optical transparency and degrade image information quality. Relatively effective means is to add abrasive particles to the protective layer, but the holding power of the abrasive particles on the surface layer is low, and due to repeated rubbing, the particles fall off, scratching the image area, and during the development process. For example, a protective layer having both a slipping layer and excellent scratch resistance has not been obtained.

[0013]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a raw material of a magnetic recording medium having a transparent magnetic layer having excellent optical characteristics. In particular, it is an object of the present invention to provide a magnetic recording medium having uniform optical characteristics and good productivity by forming a lubricating protective layer having high strength, stable running, stable and excellent wear resistance as a lubricating protective layer, and a method for producing the same.

A second object is to provide a magnetic recording medium having a lubricating protective layer having excellent blocking resistance and excellent adhesion to a lower layer by appropriately selecting the binder properties and the lubricant composition of the lubricating protective layer, and the production thereof. It is to provide a method.

A third object is to provide a magnetic recording medium having a transparent magnetic layer, which is made of a material having a good coating strength and a cleaning ability for a magnetic head, and which has very little contamination and a decrease in output of the magnetic head when inputting / outputting a magnetic signal. And a method for manufacturing the same.

A fourth object is to provide a lubricating protective layer having excellent water resistance, good wettability upon infiltration of a developing solution, low surface contamination after development processing, and fluctuation of magnetic input / output after development. An object of the present invention is to provide a magnetic recording medium for a silver halide photographic light-sensitive material and a method of manufacturing the same.

A fifth object of the present invention is to provide a magnetic recording medium in which the magnetic input / output is stabilized by making the thickness of the lubricating protective layer on the transparent magnetic layer extremely thin, and a method of manufacturing the same.

A sixth object of the present invention is to provide a photographic material obtained by coating a photographic component layer on the above-mentioned magnetic recording medium and a method for producing the same.

[0019]

The above object of the present invention is attained by the structure described in the claims.

(1) A transparent magnetic layer is formed on one side of the nonmagnetic support, and a lubricating protective layer is formed on the uppermost layer having the transparent magnetic layer, and the lubricating protective layer has a degree of polymerization of 400 or more. (2) A transparent magnetic layer is formed on one side of a non-magnetic support, and a lubrication protective layer is formed on the uppermost layer on the side having the transparent magnetic layer. (1) wherein the lubricating protective layer comprises polyvinyl alcohol having a degree of polymerization of 900 or more.
(3) a transparent magnetic layer is formed on one side of the non-magnetic support, a lubricating protective layer is formed on the uppermost layer having the transparent magnetic layer, and the lubricating protective layer is polymerized. Degree 90
(4) a transparent magnetic layer formed on one side of a non-magnetic support, wherein the transparent magnetic layer comprises at least one polyvinyl alcohol and a polyvinyl alcohol having a degree of polymerization of less than 900; A magnetic recording medium comprising a lubricating protective layer formed on the uppermost layer on the side having: a lubricating protective layer containing polyvinyl alcohol having a saponification degree of 90 mol% or more; A transparent magnetic layer is formed on one side, and a lubricating protective layer is formed on the uppermost layer on the side having the transparent magnetic layer.
(4) The magnetic recording medium according to (4), which contains 6 mol% or more of polyvinyl alcohol, and (6) a transparent magnetic layer is formed on one side of the non-magnetic support and has the transparent magnetic layer. (7) a magnetic recording medium, wherein a lubricating protective layer is formed on the uppermost layer on the side, and the lubricating protective layer contains polyvinyl alcohol having a saponification degree of 96 mol% or more and polyvinyl alcohol of less than 96 mol%. A transparent magnetic layer is formed on one side of the non-magnetic support, forming the uppermost lubricating protective layer on the side having the transparent magnetic layer, the content of polyvinyl alcohol contained in the lubricating protective layer, 0.5mg
/ M ² or more and 80 mg / m ² or less, the magnetic recording medium according to any one of (1) to (6), (8) a photographic photosensitive material having a transparent magnetic recording layer, (9) A photographic material having a transparent magnetic recording layer, wherein any one of the layers on the side of the magnetic recording layer contains polyvinyl alcohol and a derivative of a higher alcohol and a higher fatty acid. Any layer on the layer side contains polyvinyl alcohol and a derivative of higher alcohol and higher fatty acid, and the polyvinyl alcohol is a polyvinyl alcohol having a degree of polymerization of 400 or more and a degree of saponification of 90 mol% or more. (10) In the photographic material having a transparent magnetic recording layer, the lubricating layer is provided on the uppermost layer on the side having the magnetic recording layer. (11) The photographic light-sensitive material according to any one of (7) and (8), further comprising a protective layer, wherein the lubricant of the lubricating protective layer is carnauba wax.
In a photographic light-sensitive material having a transparent magnetic recording layer, a lubricating protective layer containing a polyvinyl alcohol having a polymerization degree of 400 or more and / or a polyvinyl alcohol having a saponification degree of 90 mol% or more as an outermost layer on the side having the transparent magnetic recording layer. The magnetic recording layer has an average primary particle size of 0.4 μm or less;
A silver halide photographic light-sensitive material characterized by containing grains having a Mohs hardness of 6 or more and grains having an average primary particle size of 0.5 μm or more and a Mohs hardness of 5 or less, (12) a photograph having a transparent magnetic recording layer In the photosensitive material, 0.5 mg of polyvinyl alcohol was added to the outermost layer on the side having the transparent magnetic recording layer.
The silver halide photographic light-sensitive material according to any one of (8) to (11), further comprising a lubricating protective layer containing at least 80 mg / m ^{2 and not} more than 80 mg / m ² .

Hereinafter, the present invention will be described in detail.

The lubricating protective layer of the present invention has a dynamic friction coefficient of 0.1 to 0.37 with respect to a stainless steel ball (5 mmφ).
A layer having a thickness of 0.3 μm or less provided on the magnetic recording layer so that the magnetic recording layer does not directly contact a support mechanism of a transport path of a device such as a camera or a developing base processor.

The binder that can be used in the lubricating protective layer of the present invention is polyvinyl alcohol having a degree of polymerization of 400 or more from the viewpoints of coating film strength, coating uniformity, and the like. The preferable polymerization degree of polyvinyl alcohol used for the lubricating protective layer of the present invention is 900 or more. In the present invention, the degree of polymerization of polyvinyl alcohol is defined as polyvinyl alcohol 1
Average of the number of repeats of monomer units per molecule. Details of the measurement method and the like are described in detail in the following literature.

Further, the polyvinyl alcohol used in the lubricating protective layer of the present invention may be used in a mixture of one having a polymerization degree of 900 or more and one having a polymerization degree of less than 900. In this case, the polymerization degree of polyvinyl alcohol having a polymerization degree of less than 900 is preferably 400 or more.

The lubricating protective layer according to the present invention has a polyvinyl alcohol having a saponification degree of 90 mol% or more from the viewpoints of solubility and dispersibility in water and an organic solvent, and elution into a developing bath during development. Can be used. The preferred degree of saponification of the polyvinyl alcohol used for the lubricating protective layer of the present invention is 96 mol% or more. The degree of saponification of polyvinyl alcohol refers to the ratio of the number of repeating units in one molecule of polyvinyl alcohol, that is, the number of units corresponding to vinyl alcohol to the total number of units corresponding to units corresponding to vinyl acetate and units corresponding to vinyl alcohol. . For example, a degree of saponification of 96 mol% means that on average, 96% of all polyvinyl acetate molecules hydrolyze units equivalent to vinyl acetate and convert them to units equivalent to vinyl alcohol. It is something that did. The specific saponification method and measurement of the degree of saponification are described in detail in the following literature.

Further, the polyvinyl alcohol used in the lubricating protective layer of the present invention may be a mixture of those having a saponification degree of 96 mol% or more and those having a saponification degree of less than 96 mol%. In this case, the degree of saponification of polyvinyl alcohol having a degree of saponification of less than 96 mol% is preferably 90 mol% or more.

In this patent, the polyvinyl alcohol which can be preferably used is mainly water-insoluble or hardly water-soluble polyvinyl alcohol, which is called completely saponified type or intermediate saponified type, and is dissolved in hot water or hot water. Can be used. Some of them are partially saponified.
Commercially available products are commercially available from Shin-Etsu Chemical Co., Ltd. and Kuraray Co., Ltd. The physical property data such as the degree of polymerization, saponification degree, and the temperature dependence of the dissolution rate for each product are described in “PVA” of the above two companies. Product Catalog ”(Shin-Etsu Chemical),“ Kuraray Povar ”
(Kuraray). For more information on polyvinyl alcohol, see "Poval" Koichi Nagano,
There are detailed descriptions in Saburo Yamane and Kentaro Toshima (Polymer Publishing Association).

Specifically, as examples of polyvinyl alcohol having a polymerization degree of 400 or more, A and C-17 manufactured by Shin-Etsu Chemical Co. , Ltd.
GP, C-20, C-25GP, MA05GP, MA-
17GP, MA-23GP, PA-05GP, PA-1
0GP, PA-15GP, PA-18GP, PA-20
GP, PA-24GP, Kuraray's PVA-105, PV
A-117, PVA120, PVA-124, PVA-
126H, PVA-135H, PVA-617, PVA
-624 and PVA-706. Examples of polyvinyl alcohol having a saponification degree of 90 mol% or more include C-05GP, C-10GP, A, MA05GP, M
A-17GP (Shin-Etsu Chemical), PVA-110, PV
A-117, PVA120, and PVA-613 (Kuraray).

In the lubricating protective layer of the present invention, in addition to the above polyvinyl alcohol, a binder may be used in combination as long as the effects of the present invention are not impaired, and widely used such as thermoplastic resins, thermosetting resins, and radiation-curing resins. be able to.
Further, a crosslinking agent may be used in combination to adjust the physical properties of the coating film and to control the surface hardness and wettability.

As the solvent used for preparing the coating liquid for the lubricating protective layer of the present invention, water and an organic solvent which forms a uniform solution by mixing with water in part or in an arbitrary ratio can be used. it can. For example, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, alcohols such as methanol, ethanol, propanol, butanol, i-butyl alcohol and i-propyl alcohol, esters such as glycol acetate, glycol dimethyl ether and glycol monoethyl Ethers, glycol ethers such as propylene glycol monomethyl ether and dioxane, N, N-dimethylformaldehyde and the like can be preferably used.

The polyvinyl alcohol used in the lubricating protective layer of the present invention is difficult to dissolve in an organic solvent. Therefore, in order to form a uniform solution, it is preferable that water contains 35% by weight or more of the solvent.

The lubricant added to the lubrication protective layer has a melting point of 5
Those having a temperature of 0 ° C. or higher are preferably used. Specifically, silicone oil such as polysiloxane, plastic fine powder such as polyethylene and polytetrafluoroethylene, higher fatty acid, higher fatty acid ester, ester of polyethylene glycol and fatty acid, ether of polyethylene glycol and aliphatic alcohol, paraffin wax, fluorocarbon It is preferred to use These can be used alone or as a mixture. The amount of these additives
From the viewpoint of lubricity, abrasion resistance of the coating film, and transparency of the coating film, it is preferable to use 5 to 95% by weight based on the dry coating film of the lubricating layer.

Specific examples of the lubricant are shown below.

CnH _{2n + 2} (n ≧ 24) 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 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.

Further, a waxy nonionic surfactant can also be used as a lubricating component.

Specifically, nC₃₀H₆₁O (CH_TwoCH_TwoO)_TenH n-C₄₀H₈₁O (CH_TwoCH_TwoO)₁₅H n-C₅₀H₁₀₁O (CH_TwoCH_TwoO)₁₆H n-C₄₀H₈₁O (CH_TwoCH_TwoO)₃₀H n-C₄₀H₈₁O (CH_TwoCH_TwoO)_TenH n-C₅₀H₁₀₁O (CH_TwoCH_TwoO)₁₆H n-C₅₀H₁₀₁O- (CH (CH_Three) CH_TwoO)_Three(C
H_TwoCH_TwoO)₁₆H n-C₅₀H₁₀₁O- (CH_TwoCH (OH) CH_TwoO)_Three
(CH (CH_Three) CH _TwoO)_Three(CH_TwoCH_TwoO)₁₅H n-C₄₀H₈₁OCOCH_TwoCH_TwoCOO (CH_TwoCH_Two
O)₁₆H n-C₅₀H₁₀₁OCOCH = CHCOO (CH_TwoCH_Two
O)₁₆H n-C₅₀H₁₀₁OCOCH_TwoCH_TwoCOO (CH_TwoCH
(OH) CH_TwoO)_Three(CH_TwoCH_TwoO)₁₅H and the like.

Further, conventionally known surfactants and the like can be added.

It is particularly preferable to use carnauba wax in combination with polyvinyl alcohol to have excellent lubricity and adhesion.

By dispersing a lubricant having a high melting point into fine particles and stabilizing the lubricant, there is a remarkable effect in improving the transparency of the coating film.

"Transparent" of the transparent magnetic layer (hereinafter also referred to as "magnetic recording layer") in the present invention means that the optical density is 1.5 or less. The optical density was measured using a Konica Sakura densitometer PDA-65. Light having a wavelength of 436 nm was vertically incident on the coating film through a filter that transmits blue light, and the light absorption by the coating film was calculated. Can be measured by the following method. Preferably, the optical density is 0.2 or less, particularly preferably 0.1 or less.

In the present invention, the magnetization intensity of the transparent magnetic layer is preferably 3 × 10 ⁻² emu or more in terms of the amount of magnetization per unit area in terms of the input and output of magnetic recording. The magnetization amount per unit area here means the intensity of magnetization per 1 m ^{2 of} the photographic light-sensitive material, that is, 1 m of the transparent magnetic layer.
It is the intensity of magnetization per ^two . The intensity of magnetization is also called magnetization, and a detailed description and a measurement method are described in “Basics of Magnetic Engineering I” (by Keizo Ota, Kyoritsu Zensho).

In the present invention, a sample vibration type magnetometer (VSM-3) manufactured by Toei Kogyo Co., Ltd. is used to saturate once with an external magnetic field of 1,000 Oe (Oe) in the coating direction of a fixed volume of coating film, and then externally. The magnetic flux density (residual magnetic flux density) when the magnetic field is reduced to 0 is measured, and the measured value is 1 m ² of the photosensitive material.
The volume was determined by converting the volume of the transparent magnetic layer included per unit. The thickness of the transparent magnetic layer is preferably 0.5 to 3.0 μm, more preferably 0.6 to 2.5 μm, and still more preferably 0.6 to 2.5 μm.
２．０2.0 μm.

The coating liquid for forming the magnetic recording layer may be provided with a lubricant, in order to give the recording layer a function of imparting lubricity, preventing charge, preventing adhesion, improving friction resistance, improving wear resistance, and the like.
Various additives such as an antistatic agent can be added.
In addition, a plasticizer is added to impart flexibility to the magnetic recording layer, a dispersant is added to help disperse the magnetic substance in the coating solution, and an abrasive is added to prevent clogging of the magnetic head. be able to.

The above-mentioned provision of lubricity, antistatic, anti-adhesion,
It is preferable that functions such as improvement of friction resistance, improvement of abrasion resistance, and prevention of clogging of a magnetic head be provided by providing a lubrication protective layer separately from the magnetic recording layer as described in this patent.

For example, when a magnetic recording layer is provided as the lubricating protective layer of the present invention, prevention of repelling during coating and prevention of lubricating components can be achieved by the effect of forming a good film of polyvinyl alcohol and optimizing the surface tension of the coating solution. Since a uniform distribution and a more uniform thin film can be applied, better coating properties can be obtained than when a conventional lubricating layer is formed on a transparent magnetic layer.

When the magnetic recording layer is provided in the form of a stripe, a transparent polymer layer containing no magnetic material may be provided thereon to eliminate a step due to the magnetic recording layer. In this case, the transparent polymer layer may have the various functions described above.

The production method of the present invention can reduce the amount of the cross-linking agent in the lower layer because it suppresses solvent penetration and swelling into the lower layer and has excellent coating strength after drying. Even when the properties and hydrophobicity are adjusted, the applicability of the upper lubricating protective layer is stable, which is advantageous in production. It can be inferred that this is because the surface tension of the coating liquid due to polyvinyl alcohol decreases.

After the magnetic recording layer is provided, the layer is calendered to improve smoothness, and the magnetic output S
It is also possible to apply a lubrication protective layer after improving the / N ratio. In this case, it is preferable to apply the silver halide photosensitive layer after applying the lubricating protective layer.

The ferromagnetic fine powder used for the transparent magnetic material layer includes ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal powder, and ferromagnetic alloy powder. And barium ferrite.

The ferromagnetic powder can be produced according to a known method. 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 the non-surface area are also not particularly limited, but the crystallite size is preferably 400 ° or less, and the non-surface area is preferably 20 g / m ² or more by SBET, and 30 g / m ^2.
m ² or more is particularly preferred.

The pH and surface treatment of the ferromagnetic powder can be used without any particular limitation, and the preferred pH range is 5-10. In the case of the ferromagnetic iron oxide fine powder, the ratio of divalent iron / trivalent iron can be used without any particular limitation. These magnetic recording layers are described in JP-A-47-32812.
No. 53-109604.

The preferred amount of the magnetic powder used is 1 m of the light-sensitive material.
4 × 10 ⁻⁴ g or more per ² is good. If it is less than this, the input / output of the magnetic recording is hindered. The upper limit is 436 nm
Any number may be used as long as the optical density of the wavelength light is 1.5 or less, but from the viewpoint of the characteristics of the photographic light-sensitive material, it is preferably 4 g or less per 1 m ² .

In order to form an optically transparent magnetic recording layer, the binder is used in an amount of 1 to 2 parts by weight based on 1 part by weight of the magnetic powder.
It is preferable to use 00 parts by weight. More preferably, the amount is 2 to 50 parts by weight based on 1 part by weight of the magnetic substance powder. The solvent is used in such an amount that the coating can be easily performed.

Examples of the method for providing a magnetic recording layer and a protective layer on a support include an extrusion coat, an air doctor coat, a blade coat, an air knife coat, a squeeze coat, an impregnation coat, a reverse roll coat, a transfer roll coat, and a gravure coat. , Kiss coat, cast coat, spray coat and the like can be used.
In order to perform multiple stripe coating, these coating heads may be formed in multiples. Specific methods for stripe coating include, for example, JP-A-48-25503 and JP-A-48-255.
No. 04, No. 48-98803, No. 50-138037
Nos. 52-15533, 51-3208 and 5
Nos. 1-6239, 51-65606, 51-14
No. 0703, JP-B-29-4221, U.S. Pat.
Nos. 62,181 and 3,227,165 can be referred to.

In order to firmly adhere the magnetic recording layer to the support, an undercoat layer may be provided on the support. The support may be treated with a chemical, a mechanical treatment, a corona discharge treatment, a flame treatment, an ultraviolet ray, or the like. Surface activation treatment such as 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 of an aqueous latex type or an aqueous colloid type.

As the binder used for the magnetic recording layer and the undercoat layer, there are thermoplastic resins, radiation-curable resins, thermosetting resins and other reactive resins, and those which are dissolved or dispersed in an organic solvent or water alone are used. Alternatively, they can be used in combination.

Examples of the thermoplastic resin include vinyl chloride-vinyl acetate copolymer, vinyl chloride resin, vinyl acetate resin, vinyl acetate-vinyl alcohol copolymer, partially hydrolyzed vinyl chloride-vinyl acetate copolymer, vinyl chloride -Vinyl polymers such as vinylidene chloride copolymer, vinyl chloride-acrylonitrile copolymer, ethylene-vinyl alcohol copolymer, chlorinated polyvinyl chloride, ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, etc. Or a copolymer, nitrocellulose, cellulose diacetate, cellulose acetate propionate, a cellulose derivative such as cellulose acetate butyrate resin, a copolymer of maleic acid and / or acrylic acid, an acrylate ester copolymer, acrylonitrile-styrene Copolymer, chlorinated polyethylene, Acrylonitrile - chlorinated polyethylene - styrene copolymers, methyl methacrylate - butadiene - styrene copolymer, acrylic resin, polyvinyl acetal resins, polyvinyl butyral resins, polyester polyurethane resins, polyether polyurethane resins,
Polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin,
Rubber-based resins such as styrene-butadiene resin and butadiene-acrylonitrile resin, silicone-based resins, and fluorine-based resins can be used. Particularly, cellulose derivatives, especially cellulose diacetate, are preferred.

The above thermoplastic resin has a Tg of -40 to 18
0 ° C is preferred, and more preferably -30 to 150 ° C.
° C. Further, the thermoplastic resin preferably has a weight average molecular weight of 5,000 to 300,000, and more preferably has a weight average molecular weight of 10,000 to 20.
000.

The transparent magnetic layer of the present invention has a Tg of 50.
It is preferable to use a combination of a temperature of 30 ° C. or higher and a temperature of 30 ° C. or lower. About Tg here, new experimental chemistry course 19
(Polymer Chemistry II), Maruzen.

These thermoplastic resins can be used as an aqueous emulsion or an aqueous colloid solution. These synthetic resin emulsions having a particle size of 5 nm to 2 μm can be preferably used.

The radiation-curable resin is a resin that is cured by radiation such as an electron beam or ultraviolet rays, and includes a maleic anhydride type, a urethane acrylic type, an ether acrylic type, and an epoxy acrylic type. In each case, the unsaturated bond is polymerized, ring-opened, or cross-linked by light, radiation, electron beam, or the like to increase the molecular weight.

Specifically, the vinyl ester resin “Lipoxy” series (Showa Kogaku Co., Ltd.), Seika Beam P
HC / MPL series, Seika beam DP series,
Seika Beam P-1000 Series, Seika Beam
W5000 series, Seika Beam K series (Dainichi Seika Kogyo Co., Ltd.), Koei Hard A series, C series, M series, T series, D series, NS series, F series, HS series, J series (Kaoei Chemical Industry Co., Ltd.), UV curable hard coat agent DH series (Daichi Chemical Industry Co., Ltd.), Aurex series (China Paint Co., Ltd.) and the like.

Examples of the thermosetting resin and other reactive resins include phenol resin, epoxy resin, polyurethane-based curable resin, urea resin, alkyd resin, and silicon-based curable resin.

The binders listed above may have a polar group in the 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} , -OPO 3 M (M is a hydrogen atom, an alkali metal or ammonium, acid X is to form the amine salt, R represents each a hydrogen atom, an alkyl group), Is mentioned.

The above binder can be cured by using a known epoxy-based, aziridine-based, or isocyanate-based crosslinking agent or a radiation-curable resin monomer in combination. The isocyanate-based crosslinking agent is a polyisocyanate compound having two or more isocyanate groups, for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene 1,5-diisocyanate, o-toluidine Isocyanates such as diisocyanate, isophorone diisocyanate, and the reaction product of these isocyanates with polyalcohol (for example, the reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane), and the isocyanate of these isocyanates And polyisocyanate produced by condensation. Specific examples include Coronate 3041, Coronate 2471, Millionate 400 (Nippon Polyurethane).

Other hydrophilic binders usable in the magnetic recording layer, antistatic layer and undercoat layer of the present invention include, for example, Research Disclosure (RD No. 1764).
No. 3, page 26, and the same No. And water-soluble polymers, cellulose ethers, latex polymers, and water-soluble polyesters described on pages 18716 and 651.

Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, acrylic copolymers, maleic anhydride copolymers, etc. As ethers, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose,
Hydroxypropyl cellulose and the like.

When a water-soluble polymer is used, it is preferable to use a hardener. Hardening agents that can be used include aldehyde compounds, ketone compounds, compounds having a reactive halogen, compounds having a reactive olefin,
Examples include N-methylol compounds, isocyanates, aziridine compounds, acid derivatives, epoxy compounds, mucohalic acids, chromium alum, zirconium sulfate, and carboxyl group active hardeners. Hardeners are usually
It is used in an amount of 0.01 to 60% by weight, preferably 0.05 to 50% by weight, based on the resin solid content.

The lubricant usable for the transparent magnetic layer includes:
Silicon oil such as polysiloxane, plastic fine powder such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, paraffin wax,
Fluorocarbons. These can be used alone or as a mixture. These addition amounts can be used in the range of 0.5 to 20 parts by weight based on 100 parts by weight of the dried coating film. Those that can be dissolved or diffused in water are preferred.

The transparent magnetic layer preferably contains an abrasive, specifically, an abrasive having an average primary particle size of 0.4 μm or less and a Mohs hardness of 6 or more, and an abrasive having an average primary particle size of 0.5 μm or less.
It is preferable to use an abrasive having a Mohs hardness of 5 or more and a Mohs hardness of 5 or less in combination.

The term “average primary particle size” as used herein refers to a particle (primary particle) that can maintain a constant shape having a chemical bond and a crystal grain boundary after physically adsorbing or aggregating particles are dispersed. ) Means the average particle size. It is calculated by arbitrarily measuring 1000 particles from the projected image of the particles with an electron microscope.

Specific examples of the compound used in the abrasive include aluminum oxide (α-alumina, γ-alumina, corundum, etc.), chromium oxide (Cr ₂ O ₃ ), and 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 preferably 0.01 to 2.0 μm, and the binder 100
It is added in an amount of 0.5 to 300 parts by weight based on parts by weight, and the weight per unit area is 3 mg / m ^{2 to} 200 mg.
/ M ² can be used.

An antistatic layer may be provided on the transparent magnetic layer side. As the antistatic agent contained in the antistatic layer, metal oxide fine particles are preferable.

Specific examples include oxygen-excess oxides such as Nb ₂ O _{5 + X} , oxygen-deficient oxides such as RhO _{2 -X} and Ir ₂ O _{3 -X} , and oxides such as Ni (OH) _X. Specific hydride, HfO ₂ , ThO ₂ , ZrO ₂ , CeO ₂ , Z
O ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, B
aO, MoO ₂ , V ₂ O _{5, and the} like, or composite oxides thereof are preferable, and ZnO, TiO _2, and SnO ₂ are particularly preferable.

In the case of the composite oxide, a small amount of hetero atoms can be contained in addition to the main metal atoms.

As an example including a hetero atom, for example, ZnO
For Al, In, etc. for TiO _{2 and} N for TiO ₂
b, Ta, etc., and Sb, N for SnO ₂
The addition of b, a halogen element or the like is effective. The addition amount of these different atoms is preferably in the range of 0.01 to 25 mol%, and particularly preferably in the range of 0.1 to 15 mol%.

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

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 Salts of other heterocyclic compounds, cationic surfactants such as phosphonium or sulfonium, carboxyl group, phosphate group, sulfate group,
Examples include anionic surfactants containing an acidic group such as a phosphate group, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric acid or phosphate esters of amino alcohol. Polyvinyl alcohol used in the present invention is also excellent in dispersibility of these antistatic agents,
Good conductivity can be imparted to the support including the transparent magnetic layer. Incidentally, the surfactant may be contained as a substituent of the polymer. Further, an antistatic agent may be contained in the transparent magnetic layer.

The transparent magnetic layer and antistatic layer of the present invention may contain a matting agent. As the matting agent, it is preferable to use the above-mentioned abrasive having an average primary particle diameter of 0.2 μ or more. In addition, the resin particles are insoluble in ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol, ethanol and isopropyl alcohol, esters such as ethyl acetate and butyl acetate, and aromatics such as toluene and xylene. It is also preferable to use resin particles having a particle size of 0.2 μ to 1.5 μ or less.

The preferred particle size of the matting agent is from 0.2 μ to 1.0 μ. The addition amount of the matting agent is 0.5 mg /
from m ² 50mg / m ² is preferred.

In the present invention, various supports can be used. Specifically, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), cellulose triacetate (TAC) film, cellulose diacetate (DA)
C) Films, polycarbonate films, polystyrene films, polyolefin films and the like can be mentioned.

The polyester support is not particularly restricted but includes aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol and 1,4-butanediol. Condensation polymers with alkylene glycols, for example, polyethylene terephthalate, polyethylene-2,6-dinaphthalate, polypropylene terephthalate, polybutylene terephthalate, and the like, and copolymers thereof are exemplified. In particular, JP-A-1-244446 and JP-A-1-212424 disclose curl habit recoverability after development processing.
No. 8, No. 1-298350, No. 2-89045, No. 2-93641, No. 2-181749, No. 2-21
It is preferable to use a polyester having a high water content as disclosed in JP-A No. 4852 and JP-A-2-291135. These polyesters may have a polar group and other substituents.

The support of the present invention may be PET or PEN.
Is preferred. These polyesters are preferably stretched in an area ratio of 4 to 16 times in order to satisfy the mechanical strength, dimensional stability and the like of the film support.

On the support, there are provided 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 softener, and a fluidizer. , A thickener, an antioxidant, and the like.

The support is neutralized in color at the minimum density portion, and light piping phenomenon (edge fogging) that occurs when light enters the film coated with the photographic emulsion layer from the edge.
Dyes can be contained for the purpose of preventing bleeding and preventing halation.

The type of the dye is not particularly limited. When a polyester film is used as the support, it is preferable that the dye has excellent heat resistance in the film forming step, and examples thereof include an anthraquinone-based chemical dye. Also, as the color tone,
For the purpose of preventing light piping, gray dyeing is preferable as seen in general photographic materials. The dyes may be used alone or in combination of two or more. Commercial products: Diaresin, Baye, manufactured by Mitsubishi Chemical Corporation
The target can be achieved by using a dye such as MACROLEX, manufactured by r company, alone or in an appropriate mixture.

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

The photographic light-sensitive material of the present invention has a photographic component layer on the side opposite to the side having the transparent magnetic layer. This photographic constituent layer may be applied after the transparent magnetic layer is applied or may be applied before the transparent magnetic layer is applied, but may be applied after the transparent magnetic layer is applied. preferable.

[0090]

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

Example 1 (Preparation of Undercoating Base) 20 W / m ^{2 on} both sides of a polyethylene-2,6-naphthalate base (85 μm thick)
-Min corona discharge treatment to prepare undercoating solutions U-1 and U-2 having the following composition on one side, and apply them in order from the base side to a dry film thickness of 0.5 μm and 0.2 μm. On the other side, an undercoating coating solution U-3 or S-1 having the following composition was prepared, and applied in order from the base side to a dry film thickness of 0.1 μm and 0.2 μm to have an antistatic function. A support having an undercoat layer formed thereon was prepared. In the following examples, “parts” of each material indicates “parts by weight” unless otherwise specified.

Undercoat layer coating liquid (U-1) butyl acrylate / t-butyl acrylate / styrene / 270 parts 2-hydroxyethyl methacrylate copolymer latex liquid (weight composition ratio = 30: 20: 25: 25, solid content 30%) Surfactant (A-1) 0.5 part Hardener (H-1) 1 part Pure water 730 parts Undercoat layer coating liquid (U-2) Styrene / maleic acid copolymer latex liquid (solid 100% Surfactant (A-1) 0.5 part Hardener (H-2) 0.1 part Matting agent (silica particles having an average particle diameter of 0.6 μm) 0.5 part Pure water 900 Part Undercoat layer coating liquid (U-3) butyl acrylate / t-butyl acrylate / styrene / 270 parts 2-hydroxyethyl methacrylate copolymer latex liquid (weight composition ratio, same as solid content U-1) Surfactant (A 1) 0.5 part Hardener (H-1) 1 part Pure water 730 parts Undercoat layer coating solution (S-1) Tin oxide fine powder (average particle size 0.1 μm) 60 parts (Ishihara Sangyo Co., Ltd.) Manufacture: SN100P) Sulfo group-containing polyester latex (solid content 30%) 120 parts Hydroxyl group-containing acrylate latex 12 parts (solid content 30%) Surfactant (A-1) 1 part Pure water 1200 parts The structure is as follows.

[0093]

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(H-2) CH ₃ SO ₃ (CH ₂ ) ₃ OSO ₂ CH ₃ (coating of magnetic recording layer and lubricating layer)
-1) and a coating liquid for lubricating protective layer (W-1) are prepared according to the following formulation, and a coating liquid for magnetic layer (M-1) is applied to the undercoating layer S-1 (corresponding to the conductive layer) of the undercoating treatment base. ) Was applied to the coated surface, and while the coating film was not dried, the magnetic powder was oriented in the application direction in an orientation magnetic field of 60 Gauss to increase the output of magnetic recording. Subsequently, (W-1) was applied in an atmosphere at room temperature, and the raw material after application was introduced into a drying zone.
While passing the controlled drying air, and dried sufficiently. Subsequently, the drying zone in the latter half was set to 100 ° C., and the coating surface was completely dried while being brought into contact with the mirror-finished metal guide roll, cooled, and then wound up. The original volume after application is 50 ℃
Was left in the oven for 3 days to sufficiently react the crosslinking agent to obtain a magnetic recording medium.

Magnetic Layer Coating Solution (M-1) The following composition P-1 was stirred and mixed, and then dispersed by a sand mill.

(P-1) Cobalt-containing γ-iron oxide (average major axis length 0.12 μm, 7 parts minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, specific surface area 40 m ² / g , Hc = 750 Oe) α-alumina (average particle diameter: 0.3 μm) 4 parts Crosslinked polymethyl methacrylate resin particles (particle diameter: 1.1 μm) 0.3 parts Polyurethane (molecular weight: 40,000, sulfonic acid group in one molecule: 1.) 5 parts) 1 part Methyl ethyl ketone 10 parts Cyclohexanone 10 parts The above P-1 is diluted with the following resin solution for dilution LD-1 and stirred and mixed.

(LD-1) Cellulose diacetate 136 parts Cyclohexanone 900 parts Acetone 900 parts After further dispersing this coating solution in a sand mill, 30 parts of Coronate L (50% solids) was added, stirred, and filtered with a filter. Thus, a magnetic layer coating liquid M-1 was obtained. Lubricating protective layer coating liquid (W-1) Polyvinyl alcohol 50 parts (Poval A, Shin-Etsu Chemical) Carnauba wax 50 parts Water 500 parts While stirring the above, stirring and mixing at 100 ° C to produce a yellow suspension, After confirming the melting of the polyvinyl alcohol, while maintaining the liquid temperature at 90 ° C., the mixture was sufficiently dispersed with a sand mill to become translucent. Then, the liquid temperature was gradually lowered to obtain an undiluted solution 1. The solvent was diluted appropriately with a solvent of / 1, so that the solid content of the coating solution became the value shown in Table 1, filtered, and then used as a lubricating protective layer coating solution (W-1).

(Evaluation of Magnetic Recording Medium) With respect to Sample 1 thus obtained, applicability, processability of blocking property, finished quality, devitrification, and adhesion to a support were evaluated. In addition, magnetic input / output and fluctuation were measured, and the uniformity of coating and the aggregation state of the magnetic material were evaluated.

(Evaluation of Coating Property) The state immediately before the application of the lubricating protective layer before the base entered the drying zone was visually observed and classified as follows.

：: good coating state △: coating failure such as mottled unevenness, uneven streaks, etc., and the range of practical application possible is somewhat narrow ×: unpractical level (evaluation of blocking property) coating, transport, cutting In each step, the blocking property was evaluated. A: No problem at the time of unwinding of the original winding B: Cracking and peeling sound when unwinding the original winding, but not affecting the surface quality C: Peeling sound In addition, the change in gloss and roughness of the coated surface can be partially and clearly observed by visual inspection, which affects the yield. (Evaluation of finish quality and dryness) Observing the sample taken out of the oven and visually checking the surface of the coated surface to check the variation in uniformity and turbidity as follows It was kind.

：: Good transparency, uniform appearance in appearance ：: Uniform, but slightly white cloudiness slightly reflected by reflected light over the entire surface over the light.

X: White cloudy part and transparent part are seen as mottled, and this is a level that requires post-processing.

Xx: Obviously non-uniform, uneven thickness due to drying air and aggregation during drying are observed in some places, and it is difficult to put into practical use. (Evaluation of turbidity (haze value)) manufactured by Mitsubishi Kasei Kogyo Co., Ltd. Was measured using a turbidimeter SEP-PT-501D.

(Evaluation of Adhesive Property) A cellophane tape was adhered to a sample in a fixed area and a constant load was applied with a rubber roller, and then peeled off, and the peeled area of the back surface (magnetic recording layer) was examined.
It was calculated from the area ratio to the portion where the tape was first applied.

[0105] The sample which was not peeled at all was 0%, and the sample whose lubrication protection or magnetic recording layer was completely transferred to the cellophane tape side was 100%. When peeling off only the lubrication protection layer,
The surface to be evaluated was determined by observing the surface with a microscope and using reflection infrared spectroscopy.

(Preparation of Photosensitive Material) A surface opposite to the surface having the magnetic recording layer of Sample 1, that is, 25 on the undercoat layer U-2
After a corona discharge of W / m ² · min, a multilayer color photosensitive material having the following constitution was prepared.

First layer diacetylcellulose g Alumina sol AS-100 (aluminum oxide) 0.8 g (manufactured by Nissan Chemical Industries, Ltd.) Second layer diacetylcellulose 100 mg stearic acid 10 mg silica fine particles (average particle size 0.2 μm) 50 mg (silver halide Preparation of color light-sensitive material)
Each layer having the following composition was provided on Sample No. 1 to prepare Sample 101 as a multilayer color photosensitive material.

(Composition of photosensitive layer) The coating amount is expressed in terms of g / m ² in terms of metallic silver for silver halide and colloidal silver, and g / m ^{2 for} couplers and additives.
The amount was expressed in m ² , and the sensitizing dye was expressed in mol per mol of silver halide in the same layer.

First layer: Antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound ( SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: Low sensitivity red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 increase Sensitizing dye (SD-1) 2.0 × 10 ^-4 sensitizing dye (SD-2) 1.4 × 10 ^-4 sensitizing dye (SD-3) 1.4 × 10 ^-5 sensitizing dye (SD- 4) 0.7 × 10 ^-4 cyan coupler (C-1) 0.53 colored cyan coupler (CC-1) 0.04 DIR compound (D-1) 0.025 high boiling point solvent (OIL-3) 48 Gelatin 1.09 Fourth layer: middle-sensitivity red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C .34 sensitizing dye (SD-1) 1.7 × 10 -4 Sensitizing dye (SD-2) 0.86 × 10 -4 Sensitizing dye (SD-3) 1.15 × 10 -5 Sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C-1) 0.33 colored cyan coupler (CC-1) 0.013 DIR compound (D-1) 0.02 high boiling point solvent (OIL-1) 0.16 gelatin 0.79 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion D 0.95 sensitizing dye (SD-1) 1.0 × 10 ^-4 sensitizing dye (SD-2) 1 2.0 × 10 ^-4 sensitizing dye (SD-3) 1.2 × 10 ^-5 cyan coupler (C-2) 0.14 colored cyan coupler (CC-1) 0.016 high boiling point solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Chin 0.80 Seventh layer: low sensitivity green-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 -5 Sensitizing dye ( SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 8th layer: Intermediate layer Gelatin 0.41 9th layer: Medium sensitivity green-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD- 6) 1.2 × 10 ^-4 sensitizing dye (SD-7) 1.2 × 10 ^-4 sensitizing dye (SD-8) 1.2 × 10 ^-4 magenta coupler (M-1) 0.04 magenta Coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (D-2) 25 DIR compound (D-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: High sensitivity green-sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD- 6) 7.1 × 10 ^-5 sensitizing dye (SD-7) 7.1 × 10 ^-5 sensitizing dye (SD-8) 7.1 × 10 ^-5 magenta coupler (M-1) 0.09 colored Magenta coupler (CM-1) 0.011 High boiling solvent (OIL-4) 0.11 Gelatin 0.79 11th layer: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC-1) 0.15 High boiling solvent (OIL-2) 0.19 gelatin 1.10 12th layer: low-sensitivity blue-sensitive layer silver iodobromide emulsion A 0.12 silver iodobromide emulsion B 0.24 silver iodobromide emulsion C 0.12 sensitized dye (SD-9) 6.3 × 10 -5 sensitizing dye (SD-10) 1.0 × 1 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (D-4) 0.04 DIR compound (D-5) 0.02 High boiling solvent (OIL-2) 0.42 Gelatin 1.40 13th layer: Highly sensitive blue-sensitive layer Silver iodobromide emulsion C 0.15 Silver iodobromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 increase Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 14th layer: 1st protective layer Iodobromide Silver emulsion (average particle size 0.08 μm, silver iodide content 1.0 mol%) 0.40 Ultraviolet absorber (UV-1) 0.065 High boiling solvent (OIL-1) 0.07 High boiling solvent ( OIL-3) 0.07 gelatin 0.65 15th layer: 2nd protective layer Polymethyl methacrylate DOO addition to the (average particle size 3 [mu] m, monodispersity 3.5) 0.018 lubricant (WAX-1) 0.04 Gelatin 0.55 In addition the compositions, coating aid Su-1, dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, average molecular weight: 10,000
0 and an average molecular weight of two AF-s of 1,100,000
2, and the preservative DI-1 were added.

The emulsions used in the above samples are as follows. Incidentally, the average particle size is shown by a particle size converted into a cube.

Each emulsion was optimally subjected to gold / sulfur sensitization.

[0112]

[Table 1]

Emulsions F to M each contained 1 × metal in the remarks column.
It contains 10 ^-5 mol / 1 mol Ag, and iodine or PTTS (paratoluenethiosulfonic acid) is added during grain formation. Emulsion J has about 20 dislocation lines per grain in the fringe portion of silver halide grains.

The samples were simultaneously coated with a multi-slide hopper type coater on the first time from the first layer to the eighth layer, and on the second time on the ninth to sixteenth layers.

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[0120]

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[0121]

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[0122]

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[0124]

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[0125]

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In the emulsion layer of the sample, the silver coating amount was 6.
25 mg / m ² , dry film thickness was 18 μm, and specific photographic sensitivity was ISO420.

<Development> The prepared photosensitive material was developed according to the following processing steps.

Processing step Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Rinse 2 minutes 10 seconds Fix 4 minutes 20 seconds Rinse 3 minutes 15 seconds Stabilization 1 minute 05 seconds Processing solutions used in each step The composition 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-hydroxyethyl) amino 4.5 g-2-methylaniline sulfate Add water to make 1 liter, and adjust to pH 10.0.

Bleaching solution Ferric ammonium salt of ethylenediaminetetraacetic acid 100.0 g Disodium salt of ethylenediaminetetraacetic acid 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water is added to 1 liter to adjust the pH to 6.0.

Fixer Disodium ethylenediaminetetraacetate 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 g Sodium bisulfite 4.6 g Water is added to 1 liter to adjust the pH to 6.6.

Stabilizer Formalin (40%) 2.0 mg Polyoxyethylene-p-monononylphenyl ether 0.3 g (average degree of polymerization: 10) Water was added to make up to 1 liter.

Example 2 In Example 1, (W-1) of the lubricating protective layer was changed to the following (W-
A sample was prepared in the same manner except that the method was changed to 2), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-2) Polyvinyl alcohol 50 parts (PVA-613, Kuraray) Carnauba wax 50 parts Water 500 parts While stirring the above, stirring and mixing were carried out at 50 ° C. to form a yellow suspension. After preparing and confirming the melting of polyvinyl alcohol, the temperature was raised and the liquid temperature was kept at 90 ° C., and the mixture was sufficiently dispersed with a sand mill to become translucent. It is diluted appropriately with a solvent having a weight ratio of water / methanol of 1/1 so that the solid content of the coating solution becomes the value shown in Table 1. After filtration, the solution is used as a lubricant protective layer coating solution (W-2). Using.

Example 3 In Example 1, the lubricating layer coating solution (W-1) was prepared by the following method (W-
A sample was prepared in the same manner except that the method was changed to 3), and the magnetic recording medium and the photographic material were evaluated.

Lubricating protective layer coating liquid (W-3) Polyvinyl alcohol 50 parts (PVA-103, Kuraray) Carnauba wax 50 parts Water 500 parts The above was mixed at room temperature with stirring to produce a yellow suspension. After the melting of polyvinyl alcohol was confirmed, the temperature was raised and the liquid temperature was kept at 90 ° C., and the mixture was sufficiently dispersed with a sand mill to become translucent. It was appropriately diluted with a solvent having a weight ratio of methanol of 1/1 so that the solid content of the coating solution became the value shown in Table 1, filtered, and used as a coating solution for lubricating protective layer (W-3). .

Example 4 Sample 4 was prepared in the same manner as in Example 1 except that the coating liquid (W-1) for the lubricating protective layer was changed to the following (W-4), and the magnetic recording medium and the photographic material were evaluated. Was done.

Coating solution for lubricating protective layer (W-4) Polyvinyl alcohol 10 parts (C-17GP, Shin-Etsu Chemical) Carnauba wax 50 parts Water 200 parts The above was mixed at 100 ° C. while stirring to form a yellow suspension. After preparing and confirming the melting of the polyvinyl alcohol, while raising the temperature and keeping the liquid temperature at 90 ° C., the mixture was sufficiently dispersed with a sand mill to become translucent, and the liquid temperature was gradually lowered to obtain a stock solution 4. It was appropriately diluted with a solvent having a weight ratio of water / methanol of 1/1 so that the solid content of the coating solution became the value shown in Table 1, filtered, and used as a lubricating protective layer coating solution W-4. .

Example 5 A lubricating protective layer coating liquid (W-5) was prepared in exactly the same manner as in Example 1 except that 50 parts of carnauba wax of the lubricating layer protective coating liquid (W-1) were not added. A sample was prepared in the same manner as in Example 1, and the magnetic recording medium and the photographic photosensitive material were evaluated.

Example 6 The coating liquid (W-1) for the lubricating protective layer of Example 1 was prepared using the following (W-
A sample was prepared in the same manner except for changing to 6), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-6) 50 parts of polyvinyl alcohol (Poval C-05GP, Shin-Etsu Chemical) 50 parts of carnauba wax 500 parts of water After the suspension was prepared and the melting of the polyvinyl alcohol was confirmed, the dispersion was sufficiently dispersed with a sand mill to become translucent while maintaining the liquid temperature at 90 ° C., and then the liquid temperature was gradually lowered to obtain an undiluted solution 6. / Methanol in a weight ratio of 1/1 and appropriately diluted so that the solid content of the coating solution becomes the value shown in Table 1, filtered, and used as a lubricating protective layer coating solution (W-6). Was.

Example 7 The coating liquid (W-1) for the lubricating protective layer of Example 1 was prepared using the following (W-
A sample was prepared in the same manner except that the sample was changed to 7), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-7) Polyvinyl alcohol 50 parts (PVA-103, Kuraray) Carnauba wax 50 parts Water 500 parts While stirring the above, stirring and mixing at 100 ° C. to form a yellow suspension After preparing and confirming the melting of the polyvinyl alcohol, while maintaining the liquid temperature at 90 ° C., the mixture was sufficiently dispersed by a sand mill to become translucent, and then the liquid temperature was gradually lowered to obtain an undiluted solution 7. It was appropriately diluted with a solvent having a weight ratio of 1/1 so that the solid content of the coating liquid became the value shown in Table 1, filtered, and then used as a lubricating protective layer coating liquid (W-7).

Comparative Example 1 The lubricating protective layer coating solution (W-1) of Example 1 was
A sample was prepared in the same manner except for changing to 8), and the magnetic recording medium and the photographic material were evaluated.

Lubricating protective layer coating liquid (W-8) Polyvinyl alcohol 50 parts (MP203, Kuraray) Carnauba wax 50 parts Water 500 parts While stirring the above, stirring and mixing were carried out at 80 ° C. to produce a yellow suspension. After confirming the melting of the polyvinyl alcohol, while maintaining the liquid temperature at 90 ° C., the mixture was sufficiently dispersed with a sand mill to become translucent. Then, the liquid temperature was gradually lowered to obtain a stock solution 8, which was then dissolved in a weight ratio of water / methanol. It was appropriately diluted with a 1/1 solvent so that the solid content of the coating solution became the value shown in Table 1, filtered, and then used as a lubricating protective layer coating solution (W-8).

Comparative Example 2 The coating liquid (W-1) for the lubricating protective layer of Example 1 was prepared as follows.
Except for changing to 9), make a sample in exactly the same way,
The magnetic recording medium and the photosensitive material were evaluated.

Coating solution for lubricating protective layer (W-9) 50 parts of polyvinyl alcohol (PVA203, Kuraray) 500 parts of water While stirring the above, stirring and mixing were performed at 40 ° C. to prepare a uniform solution, which was used as a stock solution 9. Is appropriately diluted with a solvent having a water / methanol ratio of 1/1 by weight so that the solid content of the coating solution becomes the value shown in Table 1, filtered, and then filtered, followed by coating with a lubricant protective layer coating solution (W-9). Used as

Example 8 The coating liquid (W-1) for the lubricating protective layer of Example 1 was prepared by the following method (W-1).
A sample was prepared in the same manner except that the sample was changed to 0), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-10) Polyvinyl alcohol 50 parts (PA-05GP, Shin-Etsu Chemical) Carnauba wax 50 parts Water 500 parts While stirring the above, stirring and mixing at 100 ° C., yellow suspension After the melting of the polyvinyl alcohol was confirmed, the dispersion was sufficiently dispersed with a sand mill while maintaining the liquid temperature at 90 ° C. to become translucent.
With a solvent having a water / methanol weight ratio of 1/1,
It was appropriately diluted so that the solid content of the coating solution became the value shown in Table 1, filtered, and used as a lubricating protective layer coating solution (W-10).

Example 9 The coating liquid (W-1) for the lubricating protective layer of Example 1 was prepared by the following method (W-1).
A sample was prepared in the same manner except that the method was changed to 1), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-11) Polyvinyl alcohol 50 parts (MA-05GP, Shin-Etsu Chemical) Carnauba wax 50 parts Water 500 parts While stirring above, stirring and mixing at 100 ° C, yellow suspension After confirming the melting of the polyvinyl alcohol, the dispersion was sufficiently dispersed with a sand mill while maintaining the liquid temperature at 90 ° C. to become translucent.
With a solvent having a water / methanol weight ratio of 1/1,
It was appropriately diluted so that the solid content of the coating solution became the value shown in Table 1, filtered, and used as a lubricant protective layer coating solution (W-11). Example 10 The lubricating protective layer coating solution (W-1) of Example 1 was prepared using the following (W-1)
Samples were prepared in the same manner except for changing to 2), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-12) 8 parts of polyvinyl alcohol (PVA-203, Kuraray) 8 parts of polyvinyl alcohol (Poval A, Shin-Etsu Chemical) Carnauba wax aqueous dispersion solution (wax solid content 25%) 60 parts Average Particle size 0.05 μm Water 500 parts The above-mentioned polyvinyl alcohol is first heated and dissolved in water and 500 parts and stirred. After confirming the melting of the polyvinyl alcohol, the liquid temperature is lowered to 30 ° C. or less, and then carnauba wax is added. 60 parts of an aqueous dispersion was added and mixed to obtain a stock solution 12, which was appropriately diluted with a solvent having a water / methanol weight ratio of 1/1 such that the solid content of the coating solution became the value shown in Table 1. hand,
After filtration, it was used as a lubricating protective layer coating solution (W-12).
In addition, the carnauba wax aqueous dispersion stock solution was prepared by the method described below.

* Method for preparing stock solution of carnauba wax Carnauba wax 10 parts nC ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₆ H 2 parts Water 36 parts After heating and dissolving each of the above components at 100 ° C., disperse with a high-speed homogenizer. After cooling, a slightly translucent yellow translucent stock solution was prepared.

Example 11 The coating liquid (W-12) for the lubricating protective layer of Example 10 was prepared as follows.
A sample was prepared in the same manner except that the sample was changed to -13), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-13) Polyvinyl alcohol 8 parts (C-10GP, Shin-Etsu Chemical) Polyvinyl alcohol 8 parts (MA-05GP, Shin-Etsu Chemical) Carnauba wax aqueous dispersion stock solution (wax solid content 25%) 60 Part average particle diameter 0.05 μm water 500 parts The above polyvinyl alcohol is first heated and dissolved in 500 parts of water and stirred. After confirming the melting of the polyvinyl alcohol, the liquid temperature is lowered to 30 ° C. or less, An aqueous dispersion of carnauba wax (60 parts) was added and mixed to obtain a stock solution 13, which was appropriately mixed with a solvent having a weight ratio of water / methanol of 1/1 so that the solid content of the coating solution became the value shown in Table-1. Dilute,
After filtration, it was used as a coating liquid for lubricating protective layer (W-13).

Example 12 The coating liquid (W-12) for the lubricating protective layer of Example 10 was prepared as follows.
A sample was prepared in the same manner except that the sample was changed to -14), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-14) 8 parts of polyvinyl alcohol (C-25GP, Shin-Etsu Chemical) 8 parts of polyvinyl alcohol (MA-23GP, Shin-Etsu Chemical) Carnauba wax aqueous dispersion solution (wax solid content 25%) 60 Part average particle diameter 0.05 μm water 500 parts The above polyvinyl alcohol is first heated and dissolved in 500 parts of water and stirred. After confirming the melting of the polyvinyl alcohol, the liquid temperature is lowered to 30 ° C. or less, An aqueous dispersion of carnauba wax (60 parts) was added and mixed to obtain a stock solution 14, which was appropriately mixed with a solvent having a weight ratio of water / methanol of 1/1 so that the solid content of the coating solution became the value shown in Table-1. Dilute,
After filtration, it was used as a lubricating protective layer coating solution (W-14).

Example 13 The lubricating protective layer coating solution (W-12) of Example 10 was
A sample was prepared in the same manner except that the sample was changed to -15), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-15) 8 parts of polyvinyl alcohol (A, Shin-Etsu Chemical) 8 parts of polyvinyl alcohol (C-05GP, Shin-Etsu Chemical) Carnauba wax aqueous dispersion (25% solid content of wax) 60 parts Average Particle size 0.05 μm Water 500 parts The above-mentioned polyvinyl alcohol is first heated and dissolved in water and 500 parts and stirred. After confirming the melting of the polyvinyl alcohol, the liquid temperature is lowered to 30 ° C. or less, and then carnauba wax is added. An aqueous dispersion (60 parts) was added and mixed to give a stock solution 15, which was appropriately diluted with a solvent having a water / methanol weight ratio of 1/1 so that the solid content of the coating solution became the value shown in Table-1. hand,
After filtration, it was used as a coating liquid for lubricating protective layer (W-15).

Example 14 The lubricating protective layer coating solution (W-12) of Example 10 was prepared using the following (W
A sample was prepared in the same manner except that the sample was changed to -16), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-16) 8 parts of polyvinyl alcohol (C-17GP, Shin-Etsu Chemical) 8 parts of polyvinyl alcohol (PVA-103GP, Shin-Etsu Chemical) Carnauba wax aqueous dispersion solution (wax solid content 25%) 60 Part average particle diameter 0.05 μm water 500 parts The above polyvinyl alcohol is first heated and dissolved in 500 parts of water and stirred. After confirming the melting of the polyvinyl alcohol, the liquid temperature is lowered to 30 ° C. or less, 60 parts of an aqueous dispersion of carnauba wax was added and mixed to obtain a stock solution 16, which was mixed with a solvent having a weight ratio of water / methanol of 1/1 so that the solid content of the coating solution was adjusted to the value shown in Table-1. Dilute,
After filtration, it was used as a coating liquid for lubricating protective layer (W-16).

Example 15 The lubricating protective layer coating solution (W-1) of Example 1 was prepared using the following (W-1)
A sample was prepared in the same manner except that the sample was changed to 7), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (W-17) Polyvinyl alcohol 50 parts (MA-23GP, Shin-Etsu Chemical) Carnauba wax 100 parts nC ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₆ H 5 parts Water 500 parts While stirring the above, the mixture was stirred and mixed at 70 ° C. to produce a yellow suspension. After confirming the melting of polyvinyl alcohol, the mixture was sufficiently dispersed by a sand mill while maintaining the liquid temperature at 90 ° C. by raising the temperature. After it became translucent, the liquid temperature was gradually lowered to make a stock solution 17, which was a solvent having a water / methanol weight ratio of 1/1, so that the solid content of the coating solution became the value shown in Table-1. After diluting as appropriate and filtering, the lubricant protective layer coating solution (W-17)
Used as

Example 16 In Example 1, the slurry composition (P-1) of the magnetic layer coating liquid (M-1) was changed to the following (P-2), and the lubricating protective layer (W-1) was changed to the following (X-1). A sample was prepared in the same manner as in Example 1 except for changing to -1), and the magnetic recording medium and the photographic material were evaluated.

(P-2) Cobalt-containing γ-iron oxide (average major axis length 0.12 μm, 7 parts minor axis length, 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, specific surface area 40 m ² / g, Hc = 750 Oe) Crosslinked polymethyl methacrylate resin particles (particle diameter 1.1 μm) 0.3 parts Polyurethane (molecular weight 40,000, containing 1.5 sulfonic acid groups in one molecule) 1 part Methyl ethyl ketone 10 parts Cyclohexanone 10 parts Lubrication protective layer Coating liquid (X-1) 25 parts of polyvinyl alcohol (MA-23GP, Shin-Etsu Chemical) 25 parts of polyvinyl alcohol (C-17GP, Shin-Etsu Chemical) 50 parts of carnauba wax 500 parts of water A yellow suspension was prepared, and after melting of polyvinyl alcohol was confirmed, the temperature was raised and the liquid temperature was kept at 90 ° C., and sufficiently dispersed by a sand mill. After it became translucent, the liquid temperature was gradually lowered to make a stock solution 18, which was a solvent having a water / methanol weight ratio of 1/1 so that the solid content of the coating solution became the value shown in Table-1. After being appropriately diluted and filtered, it was used as a coating liquid (X-1) for a lubricating protective layer.

Example 17 A sample was prepared in the same manner as in Example 16 except that (P-2) of the magnetic recording layer was changed to the following (P-3). The materials were evaluated.

(P-3) Cobalt-containing γ-iron oxide (average major axis length 0.12 μm, 7 parts, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, specific surface area 40 m ² / g, Hc = 750 Oe) α-alumina (average particle size 0.3 μm) 4 parts Polyurethane (molecular weight 40,000, containing 1.5 sulfonic acid groups in one molecule) 1 part Methyl ethyl ketone 10 parts Cyclohexanone 10 parts Comparative Example 3 In Example 16, A sample was prepared in the same manner as in Example 16 except that (X-1) of the lubricating protective layer was changed to the following (X-2), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (X-2) Carnauba wax 50 parts n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H 5 parts Water 500 parts The above components were mixed and dispersed at 95 ° C. with stirring. To make a yellow suspension, adjust the temperature and keep the liquid temperature at 90 ° C,
After sufficiently dispersing with a sand mill to become translucent, the liquid temperature was gradually lowered to obtain a stock solution 19, which was a solvent having a weight ratio of water / methanol of 1/1, and the solid content of the coating solution was as shown in Table 1. , And the mixture was filtered and then used as a coating liquid for lubricating protective layer (X-2). Example 18 In Example 16, the slurry composition (P-2) of the magnetic layer coating liquid (M-1) was changed to the following (P-4), and the lubricating protective layer (X-1) was changed to the following (X-3). A sample was prepared in the same manner as in Example 16 except that the magnetic recording medium and the photographic material were evaluated.

(P-4) Cobalt-containing γ-iron oxide (average major axis length 0.12 μm, 7 parts, minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, specific surface area 40 m ² / g, Hc = 750 Oe) α-alumina (average particle diameter 0.3 μm) 4 parts Cross-linked polymethyl methacrylate resin particles (particle diameter 1.1 μm) 0.3 parts Polyurethane (molecular weight 40,000, 1.5 sulfonic acid groups per molecule) 1 part Carnauba wax 2 parts Methyl ethyl ketone 10 parts Cyclohexanone 10 parts Lubricating protective layer coating solution (X-3) Polyvinyl alcohol 15 parts (MA-23GP, Shin-Etsu Chemical) Polyvinyl alcohol 30 parts (C-17GP, Shin-Etsu Chemical) Water 450 Part While stirring the above, the mixture was mixed at 90 ° C. to confirm the melting of the polyvinyl alcohol, and then cooled to obtain a stock solution 20, which was mixed with water / methanol. A solvent weight ratio of 1/1, the amount with the solid content of the coating solution was diluted appropriately so that the values in Table -1 were used after filtration, the lubricating protective layer coating solution as (X-3).

Example 19 In Example 16, (P-2) of the magnetic recording layer was changed to the following (P-5), and (X-1) of the lubricating protective layer was changed to (X-
A sample was prepared in the same manner as in Example 16 except for changing to 2), and the magnetic recording medium and the photographic material were evaluated.

(P-5) Cobalt-containing γ-iron oxide (average major axis length 0.12 μm 7 parts minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2 Specific surface area 40 m ² / g, Hc = 750 Oe) α-alumina (average particle diameter 0.3 μm) 4 parts Cross-linked polymethyl methacrylate resin particles (particle diameter 1.1 μm) 0.3 parts Polyurethane (molecular weight 40,000, 1.5 sulfonic acid groups per molecule) (Containing) 1 part Polyvinyl alcohol (MP205: Kuraray) 5 parts Methyl ethyl ketone 10 parts Cyclohexanone 10 parts Example 20 In Example 1, the composition (S-1) of the undercoat layer coating liquid was changed to the following (S-2), and lubrication protection was performed. (W-1) of the layer is replaced with (X-
Except having changed to 2), a sample was prepared in the same manner as in Example 1,
The magnetic recording medium and the photosensitive material were evaluated.

Undercoat layer coating solution (S-1) Tin oxide fine powder (average particle size: 0.1 μm) 60 parts (manufactured by Ishihara Sangyo Co., Ltd .: SN100P) Sulfo group-containing polyester latex (solid content: 30%) 110 parts Hydroxyl group-containing acrylate latex 12 parts (solid content 30%) Polyvinyl alcohol aqueous solution (solid content 10%) 30 parts (C-17GP, Shin-Etsu Chemical) Surfactant (A-1) 1 part Pure water 1200 parts Examples 21 In Example 16, the composition (S-1) of the undercoat layer coating liquid was (S-2), and (P-2) of the magnetic recording layer was the following (P-
A sample was prepared in the same manner as in Example 16 except that (X-1) of the lubricating protective layer was changed to (X-4), and the magnetic recording medium and the photographic material were evaluated.

(P-6) Cobalt-containing γ-iron oxide (average major axis length 0.12 μm, 7 parts minor axis length 0.015 μm, Fe ²⁺ / Fe ³⁺ = 0.2, specific surface area 40 m ² / g, Hc = 750 Oe) α-alumina (average particle diameter: 0.3 μm) 4 parts Crosslinked polymethyl methacrylate resin particles (particle diameter: 1.1 μm) 0.3 parts Polyurethane (molecular weight: 40,000; sulfonic acid groups in one molecule: 1.5) 1 part) Polyvinyl alcohol (MP202: Kuraray) 0.6 part Methyl ethyl ketone 10 parts Cyclohexanone 10 parts Lubricant protective layer coating solution (X-4) Polyvinyl alcohol 50 parts (C-17GP, Shin-Etsu Chemical) Carnauba wax 25 parts Water 500 Part The above was mixed at 100 ° C. while stirring to produce a yellow suspension. After confirming the melting of polyvinyl alcohol, the temperature was raised to 90 ° C. While maintaining the dispersion, the mixture was sufficiently dispersed in a sand mill to become translucent, and then the liquid temperature was gradually lowered to obtain a stock solution 21, which was used in a solvent having a weight ratio of water / methanol of 1/1 and the solid content of the coating solution was reduced. It was appropriately diluted to the value shown in Table 1, filtered, and used as a coating liquid for lubricating protective layer (X-4). Examples 22 to 26 In Example 1, (W
A sample was prepared in the same manner except that the type of polyvinyl alcohol in the composition of -1) and the type and ratio of the wax component to be added were changed as shown in Table 2, and the magnetic recording medium and the photographic material were evaluated. Was.

Example 27 (Preparation of Undercoating Base) 700 W / m2 on both sides of polyethylene-2,6-naphthalate base (85 μm thick)
^A plasma treatment is performed in an argon atmosphere for ² min to prepare an undercoat coating solution (U-4) having the following composition on one side, and apply it to a dry film thickness of 0.1 μm from the base side. A conductive layer coating solution (S-3) having the following composition was prepared and applied so that the amount of the conductive fine particles became 200 mg / m ² to prepare a support having an antistatic function and an undercoat layer formed thereon. .

Undercoat layer coating liquid (U-4) Gelatin 5 parts Acetic acid 1 part Surfactant (A-1) 0.5 parts Epoxy crosslinking agent 1 part Water 730 parts Methanol 730 parts Undercoat layer coating liquid (S- 3) Tin oxide fine powder (average particle size 0.1 μm) 120 parts (Ishihara Sangyo Co., Ltd .: SN100P) Gelatin 12 parts Surfactant (A-1) 3 parts Epoxy cross-linking agent 5 parts Pure water 1200 parts (magnetic) (Coating of Recording Layer and Lubricating Layer) In the magnetic layer coating solution (M-1) of Example 1, the coronate L of (LD-1) was Coronate 2471, and the (W-1) of the lubricating protective layer was the following (X −
A sample was prepared in the same manner as in Example 1 except that the sample was changed to 10), and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (X-10) 60 parts of polyvinyl alcohol (C-17GP, Shin-Etsu Chemical) 60 parts of polyvinyl alcohol (MA-17GP, Shin-Etsu Chemical) nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) 40 parts of ₁₆ H 60 parts of C ₂₇ H ₅₅ COOC ₂₈ H ₅₇ 2,000 parts of water 2000 parts of the above were mixed at 100 ° C. while stirring to produce a yellow suspension. After melting of polyvinyl alcohol was confirmed, the temperature was raised. While keeping the liquid temperature at 90 ° C., the mixture was sufficiently dispersed with a sand mill to become translucent. Then, the liquid temperature was gradually lowered to obtain a stock solution 27, which was coated with a solvent having a water / methanol weight ratio of 1/1. After diluting as appropriate so that the solid content of the liquid becomes the value shown in Table 1, filtering, and then applying the lubricating protective layer coating liquid (X-10)
Used as

Examples 28 to 33 Y-1 to Y-6 were prepared by changing the composition of the lubricating protective layer coating solution (W-12) of Example 10 as shown in Table 3, and the other examples were the same as in Example 10. Samples of Examples 28 to 33 were prepared in the same manner as described above, and the magnetic recording medium and the photographic material were evaluated.

Coating solution for lubricating protective layer (Y-1 to Y-6) Polyvinyl alcohol described in Table-3 (C-17GP, Shin-Etsu Chemical) Polyvinyl alcohol described in Table-3 (MA-23GP, Shin-Etsu Chemical) Carnauba wax aqueous dispersion (Wax solid content: 25%) Table-3 Average particle size: 0.05 μm Water: 500 parts First, the above polyvinyl alcohol was heated and dissolved in 500 parts of water and stirred to confirm the melting of the polyvinyl alcohol. After lowering the temperature to 30 ° C. or lower, carnauba wax aqueous dispersions were added and mixed with parts by weight of each listed in Table 3 to give stock solutions 28 to 33, which were dissolved in a solvent having a water / methanol weight ratio of 1/1, The coating liquid was appropriately diluted so that the solid content of the coating liquid became the value shown in Table 1, filtered, and used as a lubricating protective layer coating liquid (Y-1 to Y-6).

Examples 34 to 37 Examples 34 to 37 were repeated in the same manner as in Example 27 except that the coating liquid (X-10) for the lubricating protective layer was changed to (T-1 to T-4) shown in Table 1. Samples Nos. To 37 were prepared, and the magnetic recording medium and the photographic material were evaluated.

Examples 38 to 49 In Example 27, the coating liquid (X-10) for the lubricating protective layer was prepared using (Z-1 to Z-4, V-1 to V-4 and U-1 to U-
Samples of Examples 38 to 49 were prepared in the same manner as in Example 4 except that the amount was changed to 4) and the amount was changed as shown in Table 1, and the magnetic recording medium and the photographic photosensitive material were evaluated.

Comparative Examples 4 to 11 In Example 1, the composition of (W-1) was changed to the following (A-1 to (A-1)).
A-7), and the type of each component to be added was changed as shown in Table 1, and if necessary, the amount was adjusted to the value shown in Table 1.
Samples of Comparative Examples 4 to 11 were prepared in exactly the same manner as in Example 1 except that the lubricating protective layer coating solution diluted with a solvent having a weight ratio of water / methanol 1/1 was used. Was evaluated.

Coating solution for lubricating protective layer (A-1) FC-431 2 parts Water 500 parts Methanol 500 parts This was applied so that the coating amount of the fluorine-based activator was 1.0 mg / m ² .

Coating solution for lubricating protective layer (A-2) FC-431 20 parts Water 500 parts Methanol 500 parts This was applied so that the coating amount of the fluorine-based activator was 10 mg / m ² .

Coating solution for lubricating protective layer (A-3) FC-431 20 parts Carnauba wax aqueous dispersion (wax solid content 25%) 60 parts Average particle size 0.05 μm Water 500 parts Methanol 500 parts This is a fluorine-based activator Was applied so that the coating weight of was 10 mg / m ² .

Coating solution for lubricating protective layer (A-4) Carnauba wax aqueous dispersion (wax solid content: 25%) 60 parts Average particle size: 0.05 μm Was appropriately diluted so that the amount of the solid content became the value shown in Table 1, filtered, and used as a coating liquid for a lubricating protective layer.

Coating solution for lubricating protective layer (A-5) Hydroxypropyl cellulose 15 parts Carnauba wax aqueous dispersion stock (wax solid content 25%) 60 parts Average particle diameter 0.05 μm Water 500 parts While stirring and mixing the above at room temperature, Make a stock solution, and use this
With a solvent having a weight ratio of methanol of 1/1, the coating solution is appropriately diluted so that the solid content of the coating solution becomes the value shown in Table 1, and after filtration,
It was used as a lubricating protective layer coating solution (A-5).

Coating Solution for Lubricating Protective Layer (A-6) 15 parts Carboxymethylcellulose cellulose 15 parts Carnauba wax aqueous dispersion (solid content: 25%) 60 parts Average particle diameter 0.05 μm Water 500 parts While stirring and mixing the above at room temperature, Make a stock solution, and use this
With a solvent having a weight ratio of methanol of 1/1, the coating solution is appropriately diluted so that the solid content of the coating solution becomes the value shown in Table 1, and after filtration,
It was used as a lubricating protective layer coating solution (A-6).

Coating solution for lubricating protective layer (A-7) Gelatin 3 parts Acetic acid 1 part Carnauba wax aqueous dispersion (25% solid content of wax) 16 parts Average particle size 0.05 μm Epoxy crosslinking agent 1 part (Denacol EX521 Nagase Kasei Water 500 parts The above was stirred and mixed to obtain a stock solution, which was used as a solvent having a water / methanol weight ratio of 1/1.
The mixture was appropriately diluted to a value of 1, filtered, and used as a coating liquid for a lubricating protective layer (A-7).

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

(Evaluation of Photographic Material) Each sample of the photographic material prepared as described above was evaluated as follows. (Durability test) The sample was fixed on a carrier that reciprocated horizontally for a distance of 15 cm with the measurement surface of the sample facing upward, and a 150 g load was applied from above with a stainless steel ball (5 mmφ). Slide the carrier at a speed of 10 cm / sec.
Zero reciprocation was repeated. The degree of damage after the end of the test was measured according to the rank shown below. The measurement surface is a surface having no emulsion layer after development, and the measurement environment is room temperature (25 ° C./55% R).
H).

A: No damage B: Although there is a sliding mark, there is no decrease in the output of the magnetic recording / reproducing apparatus. C: There is flaw, and the output of the magnetic recording / reproducing apparatus is 50.
%: D: film peeling occurs (water resistance test) Each sample is fixed on a flat plate reciprocating horizontally for a distance of 5 cm with the measurement surface of the sample facing upward, and water / ethanol = 4/1 from above. Felt (5mm)
Corner) was pressed with a load of 100 g. The plate on which the sample was placed was run at a speed of 10 cm / sec, and reciprocation was repeated 30 times. The load resistance during running was classified into the following five ranks, and the degree of water resistance was measured according to the following ranks.

A: Running load, no change in coating film surface B: Running load increases by 5% to 10% in 20 passes C: Running load, 10% in 20 passes ~ 25% increase,
The lubrication protection layer is clearly deteriorated from the change in the gloss of the rubbing part. D: In two to five passes, the running load rises rapidly and noise is generated when sliding. E: From the beginning, High running load, not very practical (dirt adhesion test)
A solution that has been concentrated to 0 times (reduced water dilution is reduced to 1/30) is mixed, and the sample that has been subjected to normal development processing is mixed with 1 sample.
After infiltration for 0 minutes, the film was pulled up and air-dried under the environment of 23 ° C. and 50% with the coated surface vertical.

The stain of this sample was evaluated according to the following criteria.

・ ・ ・: No change in appearance and usable as a photographic film △: scale-like stains are visible in the periphery, but acceptable for practical use ×: solidification of adhered solids (Head dirt test) A commercially available audio head is pressed against the magnetic layer side at the center in the width direction of a developed long negative film having a total length of 20 m, and the head is examined from the emulsion side. 10cm / sec supported by a rubber roll that rotates to hold down the gap
c was run. Using this traveling system, two samples
After reciprocating, head dirt and output drop were monitored.

The dirt on the head was observed under a microscope and evaluated on a five-point scale.

5: The head gap and the periphery are clean in the initial state.

4 ... The gap is clean, but the end of the head that is weak against the rubber roll is slightly stained. 3 ... The gap is still visible, but 30% of the total area of the stain is covered. 2 ... A lot of dirt is applied to the gap, and the output decreases.

1... The entire surface of the head is stained brown, and no output signal is output.

Regarding the decrease in the output, when the decrease was large from the first output signal, the running was stopped immediately and the surface of the head was confirmed. The larger the numerical value of the five levels, the less the head becomes dirty, but the less foreign matter adheres to the head. However, since the adhesion of foreign matter to the head is measured, failures such as a drop in magnetic output due to the gap in the head described later or a dropout in which foreign matter adheres to the head instantaneously and detaches immediately will not occur. Measured separately.

(Coefficient of dynamic friction) JI using stainless steel balls
It was measured by the S method. For the measurement, an average value of 10 samples at different sampling positions was obtained for each evaluation sample.
At this time, the values were classified into two types, those with large fluctuations in the measured values in the longitudinal direction and the width direction, and those with small fluctuations, for reference. It has been empirically found that those with large fluctuations require caution when transporting in a manufacturing process or traveling with equipment.

(Evaluation of magnetic input / output) A color photosensitive material having a transparent magnetic layer cut and packaged to a width of 24 mm
A signal was recorded according to the S standard, and the sample that was confirmed to be recorded was reproduced in a minilab under the above-mentioned development processing conditions to prepare a developed film on which a magnetic signal was recorded. This was immediately passed through an APS standard printer (manufactured by Konica) and passed through an ANC (auto negative carrier) to monitor the reproduced signal. The number of drops in output relative to the reference signal and instantaneous signal dropouts were measured for each of the 40 cartridges.

Table 4 summarizes the results of the evaluation.
In addition, it was confirmed that the photosensitive materials of the respective examples of the present invention were photographically transparent, had excellent sharpness and granularity, and had no problem as a photograph.

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[Table 6]

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[Table 7]

[0209]

As demonstrated in the examples, according to the present invention, a magnetic recording medium having high optical transparency and less occurrence of coating failure, that is, good productivity and good transparency is manufactured. be able to. Further, it was found that the magnetic recording medium of the present invention can be used for a photographic material having a transparent magnetic layer. Thereby, the object of the present invention has been achieved.

It has also been found that by appropriate selection of a binder for the transparent magnetic layer and the lubricating layer, a magnetic recording medium for a photographic photosensitive material having a transparent magnetic layer and a lubricating layer having good abrasion resistance and adhesion can be obtained. .

Further, a method for producing a magnetic recording medium having good coating strength, excellent water resistance, little development stain, and stable magnetic input / output has been established.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) G11B 5/84 G11B 5/84 BFterm (Reference) 2H023 CD08 CD09 FA09 GA02 GA03 HA04 4F100 AA19H AA20H AA23H AA28 AH02C AJ06 AJ11C AJ11H AK12 AK12J AK21C AK24 AK24J AK25 AK25H AK25J AK42 AK51 AK80 AL01 AL05C AL06C AR00A AR00B AR00D BA03 BA04 BA05 BA07 BA10A BA10C BA10D CA18 CA20 CA23B CA30C DE01B DE01H EH461 EH462 GB41 GB90 JA07C JB07 JG06A JG06B JK01 JK06 JK09 JK12B JK12H JK16C JL00 JN01B JN17D YY00B YY00C YY00H 5D006 AA01 BA09 BA19 CC01 CC04 FA00 FA05 5D112 AA05 AA07 AA08 AA11 AA22 BC01

Claims (24)

[Claims] 1. A transparent magnetic layer is formed on one side of a nonmagnetic support, and a lubricating protective layer is formed on the uppermost layer having the transparent magnetic layer, and the lubricating protective layer has a degree of polymerization of 400 or more. A magnetic recording medium comprising polyvinyl alcohol. 2. A transparent magnetic layer is formed on one side of a non-magnetic support, and a lubricating protective layer is formed on the uppermost layer having the transparent magnetic layer, wherein the lubricating protective layer has a degree of polymerization of 900 or more. 2. The composition according to claim 1, further comprising polyvinyl alcohol.
The magnetic recording medium according to the above. 3. A transparent magnetic layer is formed on one side of the non-magnetic support, and a lubricating protective layer is formed on the uppermost layer having the transparent magnetic layer, wherein the lubricating protective layer has a degree of polymerization of 900 or more. A magnetic recording medium comprising polyvinyl alcohol and polyvinyl alcohol having a degree of polymerization of less than 900, respectively. 4. A transparent magnetic layer is formed on one side of a non-magnetic support, and a lubricating protective layer is formed on the uppermost layer on the side having the transparent magnetic layer. % Of polyvinyl alcohol. 5. A transparent magnetic layer is formed on one side of a non-magnetic support, and a lubricating protective layer is formed on the uppermost layer having the transparent magnetic layer. 5. The magnetic recording medium according to claim 4, wherein the magnetic recording medium contains polyvinyl alcohol in an amount of at least 1%. 6. A transparent magnetic layer is formed on one side of a non-magnetic support, and a lubricating protective layer is formed on the uppermost layer having the transparent magnetic layer. % Of polyvinyl alcohol and less than 96 mol% of polyvinyl alcohol. 7. A transparent magnetic layer is formed on one side of a nonmagnetic support, and a topmost lubricating protective layer on the side having the transparent magnetic layer is formed. Polyvinyl alcohol contained in the lubricating protective layer Is 0.5 mg / m ² or more, 80 mg
/ Magnetic recording medium according to any one of claims 1 to 6, characterized in that m is ² or less. 8. A photographic photosensitive material having a transparent magnetic recording layer, wherein any one of the layers having the magnetic recording layer contains polyvinyl alcohol and a derivative of a higher alcohol and a higher fatty acid. material. 9. A photographic photosensitive material having a transparent magnetic recording layer, wherein any one of the layers having the magnetic recording layer contains polyvinyl alcohol and a derivative of a higher alcohol and a higher fatty acid, and the polyvinyl alcohol is The photographic light-sensitive material according to claim 7, which is a polyvinyl alcohol having a degree of polymerization of 400 or more and a degree of saponification of 90 mol% or more. 10. A photographic light-sensitive material having a transparent magnetic recording layer, wherein a lubricating protective layer is provided on the uppermost layer on the side having the magnetic recording layer, and the lubricant of the lubricating protective layer is carnauba wax. The photographic light-sensitive material according to any one of claims 8 and 9, wherein 11. A photographic light-sensitive material having a transparent magnetic recording layer, wherein the outermost layer on the side having the transparent magnetic recording layer contains polyvinyl alcohol having a polymerization degree of 400 or more and / or polyvinyl alcohol having a saponification degree of 90 mol% or more. And a particle having an average primary particle size of not less than 6 μm and an average primary particle size of not less than 0.5 μm and a Mohs hardness of not more than 5 in the magnetic recording layer. A photographic light-sensitive material comprising: 12. In a photographic photosensitive material having a transparent magnetic recording layer, the outermost layer on the side having the transparent magnetic recording layer contains polyvinyl alcohol of 0.5 mg / m ² or more and 80 mg / m ² or more.
The photographic light-sensitive material according to any one of claims 8 to 11, further comprising a lubricating protective layer containing at most / m ² . 13. A magnetic recording method comprising: coating a dispersion of a transparent magnetic substance and a coating liquid containing polyvinyl alcohol having a degree of polymerization of 400 or more on one side of a nonmagnetic support. The method of manufacturing the medium. 14. The polymerization degree of the polyvinyl alcohol is 9
14. The method for manufacturing a magnetic recording medium according to claim 13, wherein the value is not less than 00. 15. A dispersion liquid in which a transparent magnetic substance is dispersed and a coating liquid containing a polyvinyl alcohol having a degree of polymerization of 900 or more and a polyvinyl alcohol having a degree of polymerization of less than 900 are coated on one side of a nonmagnetic support. A method for producing a magnetic recording medium, which comprises applying. 16. A magnetic method comprising: coating a dispersion of a transparent magnetic material on one side of a non-magnetic support and a coating solution containing polyvinyl alcohol having a saponification degree of 90 mol% or more. Manufacturing method of recording medium. 17. The method according to claim 16, wherein the degree of saponification of the polyvinyl alcohol is 96 mol% or more. 18. A coating solution containing, on one side of a non-magnetic support, a dispersion in which a transparent magnetic material is dispersed, and a polyvinyl alcohol having a saponification degree of 96 mol% or more and a polyvinyl alcohol of less than 96 mol%, respectively. And a method for producing a magnetic recording medium. 19. The magnetic recording medium according to claim 13, wherein the content of the polyvinyl alcohol is 0.5 mg / m ² or more and 80 mg / m ² or less. Production method. 20. A layer containing polyvinyl alcohol, a higher alcohol and a derivative of a higher fatty acid is provided on one side of the nonmagnetic support, and a photosensitive layer is provided on the side opposite to the side having the coated layer. A method for producing a photographic light-sensitive material, comprising applying a layer. 21. The method according to claim 20, wherein the polyvinyl alcohol has a degree of polymerization of 400 or more and a degree of saponification of 90 mol% or more. 22. The photographic light-sensitive material according to claim 20, wherein the coating solution containing the polyvinyl alcohol and a derivative of a higher fatty acid further contains carnauba wax. Method. 23. On one side of the non-magnetic support, a transparent magnetic material having an average primary particle size of 0.4 μm or less, particles having a Mohs hardness of 6 or more and an average primary particle size of 0.5 μm or more. , A dispersion in which particles having a Mohs hardness of 5 or less are dispersed, and a degree of polymerization of 400
Above polyvinyl alcohol and / or saponification degree 9
A method for producing a photographic light-sensitive material, comprising applying a coating solution containing 0 mol% or more of polyvinyl alcohol and applying a photosensitive layer on the other side of the non-magnetic support. 24. The photographic photosensitive material according to claim 20, wherein the content of the polyvinyl alcohol is 0.5 mg / m ² or more and 80 mg / m ² or less. Method.