JPH07191423A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To ameriorate durability, resistance to scratching and sticking while satisfactorily maintaining turbidity and surface specific resistance by providing the surface of a base with a transparent magnetic layer contg. a specific resin as a binder. CONSTITUTION:This photosensitive material has the transparent magnetic layer contg. the resin having a magnetization quantity of >=3X10<-2>emu per unit area, an optical density of <=1.5 at a wavelength of 436nm and a glass transition temp. Tg of >=50 deg.C or the resin having a glass transition temp. Tg of <=30 deg.C at a ratio of 95/5 to 60/40 by weight as the binder on the base. The term 'transparent' referred to here signifies that the optical density of the transparent magnetic layer is <=1.5. The 'magnetization quantity per unit area' refers to the intensity of magnetization per 1m<2> the transparent magnetic layer. The binder which can be adopted for a magnetic recording layer and the binder used for an under coating layer are a thermoplastic resin, radiation setting resin, thermosetting resin and other reaction type resins. The resins which are dissolved or dispersed in an org. solvent or water are usable alone or in combination.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art For silver halide photographic light-sensitive materials, for example,
Type of photographic light-sensitive material, serial number, manufacturer name, emulsion No.
Various information related to photographic light-sensitive materials, such as shooting date / time, aperture, exposure time, lighting conditions, filters used,
Various information at the time of camera shooting such as weather, size of shooting frame, model of shooting machine, use of anamorphic lens, for example, number of prints, selection of filter, customer's color preference, size of trimming frame, etc. Various information necessary for printing, such as the number of prints, filter selection, customer's color preference, trimming frame size, and other information obtained during printing, and other customer information. In terms of management, the print quality
It is also necessary to improve the efficiency of printing work.

In a conventional photographic light-sensitive material, it is impossible to input all the information, and it is necessary to optically input information such as a shooting date / time, aperture, and exposure time at the time of shooting. It wasn't too much. Moreover, at the time of printing, it was impossible to input the above information into the photographic light-sensitive material because there was no means for that.

Since the magnetic recording system is easy to record / reproduce, the use of the magnetic recording system for inputting the above various information to the photographic light-sensitive material has been studied and various techniques have been proposed.

For example, a stripe-shaped magnetic recording layer in which ferromagnetic fine particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and shooting conditions. KAISHO 50-62627, 49-4503, U.S. Pat.Nos. 3,243,376, 3,220,843, etc., and the back surface of the photographic light-sensitive material, the amount of magnetic particles, size, etc. It is described in US Pat. Nos. 3,782,947, 4,279,945, 4,302,523 and the like that a transparent magnetic recording layer having the required transparency is provided by selecting the above. Also, U.S. Pat.No. 4,947,196,
WO 90/04254 describes a photographic camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic substance that enables magnetic recording on the back surface of a photographic film.

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

By the way, a conventional method for preparing a layer in which a pigment is dispersed, such as a magnetic recording layer of a photographic light-sensitive material (hereinafter, the magnetic recording layer will be described as a representative), contains magnetic powder particles containing an organic solvent. It is dispersed in a binder and then applied to a support.The surface characteristics of magnetic powder particles are basically oxides, and since they are hydrophilic, they are more hydrophilic than lipophilic dispersion media during dispersion. It is known that medium or water is basically better.

For example, Japanese Patent Publication No. 57-6576 discloses an example in which gelatin is used as a water-soluble binder and nitrocellulose is used as a solvent-based binder. However, the optical properties and the uniform dispersibility of magnetic powder are poor, and The photographic light-sensitive material could not be put into practical use due to problems such as suitability for development (water resistance and alkali resistance) and durability (wear resistance).

In addition, when a hydrophilic colloid such as gelatin is used on the surface opposite to the light-sensitive material layer, it causes sticking (blocking) when stacked under high temperature and high humidity and can be used as a photographic light-sensitive material. It may not be possible. It is known to prevent blocking by using a filler such as a matting agent, but it is not sufficient to improve the adhesion to the lower layer of the magnetic recording layer such as the antistatic layer while maintaining the abrasion resistance. Met. In addition, the emulsion surface is often equipped with the property of rapidly swelling with water in order to respond to development processing, but when the support is thinned due to the recent demand for weight reduction and resource saving, the hydrophilic colloid layer on the back surface is Humidity influences curl characteristics and makes photographic materials unusable in various environments.

Japanese Unexamined Patent Publication (Kokai) No. 5-45755 describes the combined use of a vinyl chloride-based copolymer having an acryloyl group and a polyurethane having an acryloyl group, but it has abrasion resistance as a binder, strength, and antistatic property. Adhesion with layers,
The problem of blocking with the photographic light-sensitive material layer has not been solved yet.

On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 5-53262 discloses that a magnetic recording layer is formed by co-casting by dispersing it in cellulose triacetate, which is the same material as that of the support. Since the strength of the support is insufficient and a halogen-containing organic solvent (such as methylene chloride) is used during film formation, there are environmental safety problems, which is not preferable for practical use.

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

In addition, by using a photographic light-sensitive material which is stacked or wound, in order to prevent fog caused by peeling electrification which occurs when peeling off, or by transportation during manufacturing and processing of the photographic light-sensitive material. It is necessary to improve the conductivity of the magnetic recording layer so that dust does not adhere to the photographic performance due to electrification due to mechanical friction.

Therefore, the binder that can be used is considerably limited, and in order to put it into practical use, a fairly high level of dispersion technology, crosslinking technology and the like were required.

[0015]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a silver halide photographic light-sensitive material having a transparent magnetic layer which is excellent in optical characteristics required for the photographic light-sensitive material. A second object is to provide a silver halide photographic light-sensitive material having a transparent magnetic layer having excellent abrasion resistance and blocking resistance by appropriately selecting the binder for the transparent magnetic layer.

A third object of the present invention is to provide a transparent magnetic layer which is excellent in conductivity and has a very small influence of fogging and dust on the photographic photosensitive layer.

A fourth object is to provide a silver halide photographic light-sensitive material having a transparent magnetic layer having very few errors when inputting and outputting a magnetic signal by using a material excellent in dispersion of magnetic powder and conductive powder and having good coating strength. To do.

[0018]

The above object of the present invention is to provide a support having a magnetization amount per unit area of 3 × 10 ^-2 emu or more.
Resins with an optical density of 1.5 or less at a wavelength of 36 nm and a glass transition temperature (Tg) of 50 ° C or higher, and glass transition temperatures
95 / 5-60 / 40 in weight ratio with resin below 30 ℃ as binder
And a silver halide photographic light-sensitive material having a transparent magnetic layer.

That is, the inventors of the present invention optimally select a resin having a glass transition temperature of 50 ° C. or more, which is excellent in strength but brittle, and a resin having a glass transition temperature of 30 ° C., which is excellent in film forming property but has a problem of tackiness. By blending in a certain amount ratio, good dispersibility of magnetic powder and conductive pigment, film forming property, strength, abrasion resistance, blocking resistance and adhesion to the lower layer are obtained.

The present invention will be described in detail below.

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

The amount of magnetization per unit area in the present invention means the intensity of magnetization per 1 m ² of the photographic light-sensitive material, that is, the intensity of magnetization per 1 m ^{2 of} the transparent magnetic layer. The strength of magnetization is also called magnetization, and a detailed explanation and measurement method are described in "Basics of Magnetic Engineering I" (Keizo Ohta, Kyoritsu Zensho).
In the present invention, a sample vibrating magnetometer (VSM-
3) is used to apply an external magnetic field of 100
The magnetic flux density (residual magnetic flux density) when the external magnetic field was reduced to 0 after being saturated once with 0 oe was measured, and this was converted into the volume of the transparent magnetic layer contained per 1 m ² of the photographic light-sensitive material. It depends on how you want it.

The amount of magnetization per unit area of the transparent magnetic layer is 3
If it is less than × 10 ^-2 emu, the input / output of magnetic recording will be hindered.

In the present invention, the thickness of the transparent magnetic layer is 0.
01 to 20 μm is preferable, 0.05 to 15 μm is more preferable, and 0.1 to 10 μm is further preferable.

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to impart functions to the magnetic recording layer such as imparting lubricity, preventing electrification, preventing adhesion, and improving friction and abrasion characteristics. Various additives such as agents can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and for preventing clogging of the magnetic head. An abrasive can be added to the. The above-mentioned functions such as imparting lubricity, preventing electrification, preventing adhesion, improving friction / abrasive properties, and preventing clogging of the magnetic head may be imparted by providing these functional layers separately from the magnetic recording layer. For example, when the magnetic recording layer of the present invention is provided on the antistatic layer, it is possible to form a uniform thin film due to its good film-forming property. Therefore, it is better than the case where the conventional transparent magnetic layer is formed on the antistatic layer. Antistatic property can be obtained. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance. When the magnetic recording layer is provided in a stripe shape, a transparent polymer layer containing no magnetic material may be provided thereon to eliminate the step due to the magnetic recording layer. In this case, the transparent polymer layer may have various functions described above. Since the binder system of the present invention is excellent in film-forming property and strength, it can be dispersed in combination with not only the magnetic powder but also the above various additives, and it is also possible to reduce the constituent layers of the photographic light-sensitive material, which is advantageous in production. is there.

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

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

The ferromagnetic powder used in the present invention can be manufactured by a known method.

The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like, but needle shape and plate shape are preferable in terms of electromagnetic conversion characteristics. The crystallite size and non-surface area are not particularly limited, but the crystallite size is 400 Å or less, SBET is 20 m ² / g
The above is preferable, and 30 m ² / g or more is particularly preferable. The pH and surface treatment of the ferromagnetic powder can be used without particular limitation. The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular limitation on the ratio of divalent iron / trivalent iron. These magnetic recording layers are described in JP-A-47-32812 and 53-109604.

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

The pigment powder including the magnetic material is dispersed together with a binder dissolved in water or a binder emulsified in water to form a coating solution. The method for dispersing the pigment powder including the magnetic material is not particularly limited, and the order of adding the components and the like can be set appropriately. An ordinary kneader can be used for the preparation of the magnetic paint. In this case, it is preferable to disperse the magnetic particles one by one as much as possible without damaging the magnetic particles.

To form an optically transparent magnetic recording layer, the binder is used in an amount of 1 to 20 with respect to 1 part by weight of the magnetic powder.
It is preferable to use 0 part by weight. More preferably, it is 2 to 50 parts by weight with respect to 1 part by weight of the magnetic powder. Further, the solvent is used in such an amount that the coating can be easily performed.

To prevent aggregation of the aqueous emulsion, pH
A regulator and a surfactant may be added.

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

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

The undercoat layer is preferably an aqueous latex type.

The binder that can be used in the magnetic recording layer and the binder that is used in the undercoat layer are thermoplastic resins, radiation-curable resins, thermosetting resins and other reactive resins, which are dissolved or dispersed in an organic solvent or water. These can be used alone or as a mixture.

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

The above-mentioned thermoplastic resin has a glass transition temperature Tg.
Is −40 ° C. to 180 ° C., preferably −30 ° C. to 150 ° C., the weight average molecular weight is preferably 5,000 to 300,000, and more preferably, the weight average molecular weight is 10,000.
~ 200,000. In the transparent magnetic layer of the present invention, those having a Tg of 50 ° C. or higher and those having a Tg of 30 ° C. or lower are used in combination.

The glass transition temperature Tg is described in detail in Maruzen, New Experimental Chemistry Course 19 (Polymer Chemistry II).

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

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

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

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

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

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

When using a water-soluble polymer, it is preferable to use a hardener. Hardeners that can be used include aldehyde compounds, ketone compounds, reactive halogen-containing compounds, reactive olefin-containing compounds, N-methylol compounds, isocyanates, aziridine compounds, acid derivatives. Examples thereof include epoxy compounds, halogen carboxaldehydes, chromium alum, zirconium sulfate, and a carboxyl group-activating type hardener. The hardener is usually used in an amount of 0.01 to 60% by weight, preferably 0.05 to 50% by weight, based on the resin solid content.

Lubricants usable in the transparent magnetic layer of the present invention include silicone oils such as polysiloxane, fine plastic powders such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, paraffin wax, and fluorocarbons. To be Specifically, these can be used alone or in combination. The addition amount of these is 0.5 to 100 parts by weight of the dry coating film.
It can be used in the range of 20 parts by weight. Those which can be dissolved or diffused in water are preferable.

Examples of the abrasive that can be used in the transparent magnetic layer of the present invention include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specifically, aluminum oxide (α-alumina, γ -Alumina, corundum, etc.), chromium oxide (Cr ₂ O ₃ ), iron oxide (α-Fe ₂ O ₃ ), silicon dioxide,
Examples thereof include oxides such as titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powder such as diamond.
The average particle size of these is preferably 0.01 to 2.0 μm, and can be added in the range of 0.5 to 300 parts by weight with respect to 100 of the magnetic powder.

As the antistatic agent contained in the transparent magnetic layer of the present invention, fine particles of metal oxide are preferable. Examples include oxygen-rich oxides such as Nb ₂ O _{5 + X} , RhO _2-X , I
Oxygen-deficient oxides such as r ₂ O _{3-X, non-} stoichiometric hydrides such as Ni (OH) _X , HfO ₂ , ThO ₂ , ZrO ₂ , CeO ₂ , ZnO, Ti
O ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O ₅
Etc., or composite oxides of these are preferable, and particularly ZnO, TiO ₂
And SnO ₂ are preferred. Examples of containing different kinds of atoms include adding Al, In, etc. to ZnO and Nb, Ta to TiO ₂ .
Etc., and addition of Sb, Nb, halogen elements, etc. to SnO ₂ is effective. Addition amount of these hetero atoms is 0.01mo
The range of l% to 25mol% is preferable, but 0.1mol% to 15mol%
Is particularly preferred.

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

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

The binder system of the present invention is also excellent in dispersibility of these antistatic agents, and therefore can impart good conductivity to the transparent magnetic layer.

The surfactant may be contained as a substituent of the polymer.

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

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

The polyester support is not particularly limited, but aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and ethylene glycol, 1,3-propanediol, 1,4-butanediol, etc. Condensation polymers with alkylene glycols such as polyethylene terephthalate, polyethylene-2,6
-Dinaphthalate, polypropylene terephthalate, polybutylene terephthalate and the like, or copolymers thereof.

In particular, from the curl recovery property after development processing, JP-A 1-244446, 1-291248, 1-298350, 2-89045, 2-93641, Ibid 2-181749
It is preferable to use a polyester having a high water content as shown in JP-A No. 2-214852, JP-A No. 2-291135 and the like.

These polyesters may have polar groups and other substituents.

In the present invention, the support is preferably polyethylene terephthalate or polyethylene naphthalate.

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

For the support, a matting agent, an antistatic agent, a lubricant,
Surfactants, stabilizers, dispersants, plasticizers, UV absorbers,
Conductive substances, tackifiers, softening agents, fluidity imparting agents, thickeners, antioxidants and the like can be added.

The support is used for the purpose of neutralizing the tint of the minimum density portion, preventing the light piping phenomenon (fogging) that occurs when light enters the film coated with the photographic emulsion layer from the edge, and preventing halation. Dyes can be included.

The type of dye is not particularly limited, but when a polyester film is used as the support, it is preferable that it has excellent heat resistance in the film forming process, and examples thereof include anthraquinone chemical dyes. Further, as the color tone, when it is intended to prevent light piping, gray dyeing is preferable as seen in general light-sensitive materials. As the dye, one kind or a mixture of two or more kinds may be used. Mitsubishi Kasei Co., Ltd. Diaresin, Bayer MACROLEX
It is possible to achieve the target by using such dyes alone or in an appropriate mixture.

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

[0066]

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

Example 1 1-1) Preparation of undercoating base As a polyester resin for a support, S-1: commercially available polyethylene terephthalate (intrinsic viscosity)
0.65, film thickness 90 μm) S-2: To 100 parts by weight of dimethyl terephthalate and 64 parts by weight of ethylene glycol, 0.1 part by weight of hydrate of calcium acetate as an ester exchange catalyst was added, and transesterification reaction was carried out by a conventional method. 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: S
IP) ethylene glycol solution (concentration 35% by weight) 28 parts by weight (5 mol% / total ester bond), polyethylene glycol (abbreviation: PEG) (number average molecular weight: 4,000) 11 parts by weight (8.5% by weight / reaction product) Total weight), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.13 part by weight, Irganox 1010 (CIBA-GEIGY as an antioxidant
(Made by the company) was added so that it might be 1 weight% with respect to the product polymer. Then gradually raise the temperature and reduce the pressure to 280 ° C, 0.5 mm
Polymerization was carried out with Hg to obtain a copolyester. (Intrinsic viscosity 0.55, film thickness 90 μm) [Preparation of support] After vacuum drying S-1 and S-2 at 150 ° C., use two of three extruders for S-2.
Melt extrusion at 285 ° C. and film thickness ratio of 3 layers is S-2: S-
The layers were joined in a T-die so as to be 1: S-2 = 1: 2: 3, and were rapidly solidified on a cooling drum to obtain a laminated unstretched film. At this time, the thickness of each layer was controlled by adjusting the extrusion amount of each material. Next, lengthwise stretching at 85 ℃ (3.4 times)
After that, the film was transversely stretched (3.4 times) at a temperature of 95 ° C., and then heat-set at 210 ° C. to obtain a biaxially stretched film having a thickness of 90 μm.

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

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

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

[Undercoat Layer Coating Liquid U-3] Copolymer latex liquid of butyl acrylate / styrene / glycidyl acrylate 103 g (weight composition ratio; 40:20:40, solid content 30%) Compound (A-1) 0.3 g Hexamethylene-1,6-bis (ethyleneurea) 0.4 g Tin oxide fine powder (average particle size 0.1 μm) Ishihara Sangyo; SN100P 49.3 g These are mixed and dispersed in water and diluted with water to 1 liter. .

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

[0073]

[Chemical 1]

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

[Magnetic Paint M-1] Cobalt-containing gamma iron oxide (average major axis length 0.2 μm, minor axis length 0.02 μm) 10 parts by weight Fe ²⁺ / Fe ³⁺ = 0.3, specific surface area 35 m ² / g, Hc 70Ooe Polyester wax liquid 520 parts by weight (Tg = 67 ° C, number average molecular weight 22,000, solid content 30%) Polyester latex liquid 310 parts by weight (Tg = 18 ° C, number average molecular weight 17,000, solid content 30%) And used magnetic paint.

1-3) Coating of Lubricant Layer A lubricant coating solution dispersed in a water / methanol mixed solution was prepared so that carnauba wax was contained in the magnetic recording layer in an amount of 0.2%, and the wax was applied. The amount of coating was 0.1 g / m ² .

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

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

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

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

Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing with water 2 minutes 10 seconds Fixing 4 minutes 20 seconds Washing with water 3 minutes 15 seconds Stability 1 minute 05 seconds The treatment liquid composition used in each step is as follows. It was on the street.

Color developer Diethylenetriaminepentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 g 4- (N-Ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 l pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0g Ammonium nitrate 10.0g Water added 1.0l pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium 1.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0mg Sodium bisulfite 4.6g Water added 1.0l pH 6.6 Stabilizer Formalin (40%) 2.0mg Polyoxyethylene-p-monononylphenyl Ether (average polymerization degree 10) 0.3 g Water to make 1.0l Example 2, Table 1 the composition of the magnetic coating M-1 in Comparative Examples 1 and 2 1-2 in Example 1)
A photographic light-sensitive material was prepared in exactly the same manner as in Example 1 except that the above was changed.

[0083]

[Table 1]

Examples 3 to 6 and Comparative Examples 3 to 7 The composition of the magnetic paint M-1 in 1-2) of Example 1 was changed as described below according to the adjusting method and the lubricant coating of 1-3). A photographic light-sensitive material was prepared in exactly the same manner as in Example 1 except that the working solution was 0.2% carnauba wax in toluene.

[Magnetic Paint G-1] Cobalt-containing gamma iron oxide (average major axis length 0.2 μm, minor axis length 0.02 μm) 10 parts by weight (Fe ²⁺ / Fe ³⁺ = 0.3, specific surface area 35 m ² / g, Hc700oe) Nitrocellulose (Asahi Kasei Co., Ltd .; Cernova BTH1 / 2, Tg = 150 ° C) Polyurethane (Toyobo Co., Ltd .; UR-8300, Tg = 23 ° C) shown in Table 2 250 parts by weight cyclohexanone 500 parts by weight methyl ethyl ketone Toluene 500 parts by weight These components were mixed with a dissolver and then dispersed with a sand grinder to obtain a magnetic paint.

[0086]

[Table 2]

Examples 7 and 8, Comparative Examples 8 to 10 The procedure of Example 1 was performed in exactly the same manner except that the composition of the undercoating coating solution U-3 in 1-1) of Example 1 was changed to the following U-4. , Sample 1
Samples 14 to 20 corresponding to sample 7 were prepared.

[Undercoating liquid U-4] Polyester latex liquid (solid content 30%) 223 g Tin oxide fine powder (average particle size 0.1 μm, Ishihara Sangyo; SN100P) 107 g These are mixed and dispersed to prepare water / isopropanol. 1000 g of a 3: 1 mixture was added.

[0089]

[Table 3]

<< Evaluation of Photosensitive Material >> Each sample of the photographic photosensitive material prepared as described above was evaluated as follows.

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

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

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

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

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

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

[5] Evaluation of magnetic recording output error Using a signal input method disclosed in W / O90-04205, a photographic film magnetically input only once from the back layer before development was used.
After the development processing, the output operation was performed 500 times with the magnetic head, and the number of times of error was shown. The error is the first output value
It is 100% and is less than 70%.

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

Rank Area of bonded portion A 0 to 10% B 10 to 30% C 30 to 50% D 50 to 80% E 80 to 100% The evaluation results are shown in Table 4 below. It was confirmed that the photographic light-sensitive material of the present invention was photographically transparent, had excellent sharpness and graininess, and had no problem as a photograph.

[0100]

[Table 4]

[0101]

As demonstrated in the examples, according to the present invention, durability, scratches, sticking, etc. can be improved while maintaining good turbidity and surface resistivity. When the mixing ratio of resins having different glass transition temperatures is out of the range of the present invention, the input / output error tends to increase. Further, the one in which the polyester resin is used for the undercoat layer (conductive layer) has improved transparency, conductivity and scratches.

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

Claims (1)

[Claims] 1. The amount of magnetization per unit area is 3 on the support.
× 10 ^-2 optical density at a wavelength of 436nm or more emu is 1.5 or less, the glass transition temperature (Tg) of 50 ° C. or more resins and the glass transition temperature of 30 ° C. or less of the resin in a weight ratio as a binder 95 / A silver halide photographic light-sensitive material having a transparent magnetic layer contained in a ratio of 5 to 60/40.