JPH0473738A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To decrease errors of magnetic recording and to decrease magnetic output errors under high-temp. and high-humidity conditions by using a transparent magnetic material layer and a base having a secified film thickness, thereby forming excellent images which are photographically transparent. a CONSTITUTION:This photosensitive material has photosensitive silver halide emulsion layers on at least one side of the base. Such photographic sensitive material has the transparent magnetic material layer on at least one side thereof and the coercive force thereof is >= 400Oe. The thickness of the base is 75 to 116mum. Ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metallic powder, ferromagnetic alloy powder, barium ferrite.etc., are usable as the ferromagnetic fine powder to be used for the transparent magnetic mate rial layer.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention has photographically transparent and excellent magnetic recording properties,
In particular, the present invention relates to a silver halide photographic material (hereinafter referred to as a photographic material or photosensitive material) that does not cause magnetic input/output errors even when stored for a long time.

[Conventional technology]

Photographic light-sensitive materials are generally made of silver halide, either directly or through a subbing layer, on one or both sides of a support such as cellulose triacetate, polyethylene terephthalate, paper or paper coated with polyethylene terephthalate on both sides of the paper. It is formed by coating various layers such as an emulsion layer and, if necessary, an intermediate layer, a protective layer, a filter layer, an antistatic layer, and an antihalation layer. These layers generally consist of a hydrophilic binder such as seratin.

A magnetic recording layer that is transparent to visible light is provided on the emulsion surface or back surface of the photographic light-sensitive material described above in order to magnetically record information such as audio and shooting conditions on the photographic film. There is. For example, Japanese Patent Publications No. 41-4539, No. 53-109604, No. 57-6576, etc. describe a magnetic recording layer in which ultrafine ferromagnetic particles are dispersed and is transparent to visible light. has been done.

By the way, in the photographic material having at least one transparent magnetic recording layer on one side of the support as described above,
When magnetically recording and reproducing information, a distance is created between the photosensitive material and the recording/reproducing head due to irregularities on the surface of the photosensitive material and deflection of the support, resulting in input/output errors in magnetic recording.

Especially 122μ, which is conventionally used in color negative film.
When the triacetylcellulose of M is stored in a cartridge for a long period of time, it tends to cause magnetic input/output errors due to the contact between the magnetic head and the magnetic layer due to the curling.

As a solution to this problem, there is a method of increasing the coercive force by adding a large amount of magnetic material, but this method cannot be used because the photographic transparency is lost and the sharpness and density of the image are reduced.

(Problem to be Solved by the Invention) Therefore, an object of the present invention is to provide a photographic material that is photographically transparent and has excellent magnetic properties without deteriorating the image. It is an object of the present invention to provide a photographic material having excellent magnetic properties even when the temperature is high.

(Means for Solving the Problems) These objects of the present invention are to provide a photographic light-sensitive material having a light-sensitive silver halide emulsion layer on one side of the support, at least one side of the support. This was achieved by a photographic light-sensitive material having a transparent magnetic layer, a coercive force of 400 Oe or more, and a support having a thickness of 75 to 116 μm.

The present invention will be described in detail below. First, the transparent magnetic layer used in the present invention will be described.

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 ferromagnetic alloy powder. , barium ferrite, etc. can be used.

An example of a ferromagnetic alloy powder is one in which the metal content is 75 wt% or more, and 80 wt% or more of the metal content is at least one ferromagnetic metal or alloy (Fe, Co, Ni, Fe-C).
o, Fe-Ni, Co-Ni.

Co-Fe-Ni, etc.), and the metal content is 20wt%
Other components (Al2.Si, S, Sc.

Ti, V, Cr, Mn, Cu, Zn, Y, Mo.

Rhs Pd, Ag, Sn, Sb, B, BaXTa.

W, Re, AuSHg, Pb, P, La, Ce.

Pr, Nd, Te5Bi, etc.). Further, the ferromagnetic metal component may contain a small amount of water, hydroxide, or oxide.

Methods for producing these ferromagnetic powders are known, and the ferromagnetic powder used in the present invention can also be produced according to known methods.

The shape and size of the ferromagnetic powder are not particularly limited and can be widely used. The shape may be needle-like, rice-grain-like, spherical, cubic, plate-like, etc., but needle-like and plate-like are preferable from the viewpoint of electromagnetic conversion characteristics. There are no particular restrictions on the crystallite size or non-surface area, but the crystallite size is preferably 400 Å or less, 20 bo/g or more in 5 BET, and particularly preferably 30 rd/g or more. The pH and surface treatment of the ferromagnetic powder can be used without any particular restrictions (the surface may be treated with a substance containing elements such as titanium, silicon, aluminum, etc., or it may be treated with a substance containing elements such as carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, phosphate ester,
(It may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocycle such as benzotriazole). The preferred pH range is 5-10. In the case of ferromagnetic iron oxide fine powder, it can be used without any particular restriction on the ratio of divalent iron/trivalent iron. Regarding these magnetic recording layers, Japanese Patent Application Laid-open Nos. 47-32812 and 53-109604
listed in the number.

The content of ferromagnetic fine powder per rn' of transparent support is
4×1O-4 to 3 g, preferably 1O-3 to 1 g, more preferably 4X1O-' to 4X1O-'g.

The binder for the magnetic recording layer used in the present invention includes known thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, and mixtures thereof, which have been conventionally used as binders for magnetic recording media. can be used.

The resin has a Tg of -40°C to 150°C and a weight average molecular weight of 10,000 to 300,000, preferably 10,000 to 100,000.

Examples of the thermoplastic resin include vinyl chloride/vinyl acetate copolymer, vinyl chloride, vinyl acetate and vinyl alcohol,
Copolymers with maleic acid and/or acrylic acid, vinyl chloride/vinylidene chloride copolymers, vinyl chloride/acrylonitrile copolymers, vinyl copolymers with ethylene/vinyl acetate copolymers, nitrocellulose, cellulose Acetate propionate, cellulose derivatives such as cellulose acetate butylene resin, acrylic pine resin, polyvinyl alcohol resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, Examples include rubber resins such as polyamide resins, amine resins, styrene-butadiene resins, and butadiene-acrylonitrile resins, silicone-based resins, and fluorine-based resins.

Among these, vinyl chloride resin is preferred because it has high dispersibility of ferromagnetic fine powder.

As the radiation-curable resin, there may be used one obtained by bonding a group having a carbon-carbon unsaturated bond as a radiation-curable functional group to the above-mentioned thermoplastic resin. Preferred functional groups include acryloyl and methacryloyl groups.

In the binder molecules listed above, polar groups (epoxy groups, CO
IM, OH, NR,, NR3XX5O, M.

O20,M, PO3M2.0205M2, where M is hydrogen, an alkali metal or ammonium, and when there is a plurality of M's in one group, they may be different from each other. (R is hydrogen or an alkyl group) may also be introduced.

The polymer binders listed above may be used alone or in combination, and can be cured by adding a known isocyanate-based crosslinking agent and/or a radiation-curable vinyl monomer.

Additionally, a hydrophilic binder can be used in the magnetic recording layer of the present invention.

The hydrophilic binder used is Research Disclosure Nα17643.26 page and Nα1
8716.651, and exemplifies water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol,
These include polyacrylic acid copolymers and maleic anhydride copolymers, and examples of cellulose esters include carboquinomethylcellulose and hydroxyethylcellulose.

Latex polymers include vinyl chloride-containing copolymers,
These include copolymers containing hnylidene chloride, copolymers containing acrylic esters, copolymers containing vinyl acetate, copolymers containing butadiene, and the like.

Among these, the most preferred is seratin.

During the manufacturing process, Seratin is manufactured by
So-called alkaline treatment (lime treatment), which involves immersion in an alkaline bath.
Any of gelatin, acid-treated seratin immersed in an acid bath, double-soaked seratin that has undergone both treatments, and enzyme-treated gelatin may be used.

If necessary, a portion may be added to colloidal albumin, casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids, such as polyvinyl alcohol, polyN - Vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates, and seratin derivatives may be used in combination with seratin.

It is preferred to harden the magnetic recording layer, which includes ceratin.

Hardeners that can be used in the magnetic recording layer include, for example, aldehyde compounds such as formaldehyde and glucuraldehyde, ketone compounds such as diacetyl and soclopentanion, bis(2-chloroethyl urea), and 2-
Hydroxy-4゜6-dichloro-1,3,5-triazine, and others U.S. Patent Nos. 3,288,775 and 2,
732.303, British Patent No. 914,723, L.
Compounds containing reactive halogens such as those described in No. 167.207, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,
5-triazine, etc. U.S. Patent No. 3,635,71
No. 8, No. 3.232763, British Patent No. 994,86
Compounds having reactive olefins, N-hydroxymethylphthalimide, and others described in US Pat. No. 2,732,31f3, No. 2. 586.
N-methylol compounds described in No. 168 etc.
Isonoanatos described in U.S. Patent No. 3,103,437 etc., U.S. Patent No. 3. Aziridine compounds described in U.S. Pat. No. 2,725.294, U.S. Pat.
Examples thereof include acid derivatives described in U.S. Pat. No. 5,295, etc., epoxy compounds described in U.S. Pat. Or, as a hardening agent for inorganic compounds, use chromium light pan, zirconium sulfate,
6-12853, 58-32699, Belky Patent No. 825,726, JP 60-225148, JP 51-126125, JP 58-50699, JP 52-54427, U.S. Patent 3,321,3
Examples include carboquine group-activated hardeners described in No. 13 and the like.

The amount of hardening agent used is usually 0.01 to dry Seratin.
-30% by weight, preferably 0.05-20% by weight.

The thickness of the magnetic recording layer is 0. 1μ to lOμ, preferably 0
．． It is 2μ to 5μ, more preferably 0.5μ to 3μ.

The magnetic recording layer of the present invention can be provided on the back surface of a transparent support by coating or printing. It is also preferable to create a transparent support having a magnetic recording layer by co-casting a solution of a polymer in which magnetized particles are dispersed and a solution of a polymer for creating a transparent support.

In this case, it is preferred that the two types of polymers have substantially the same composition.

The magnetic recording layer may also have functions such as improving lubricity, controlling curl, preventing static electricity, and preventing adhesion, or another functional layer may be provided to impart these functions. If necessary, a protective layer may be provided adjacent to the magnetic recording layer to improve scratch resistance.

By calendering the back surface of the transparent support having the magnetic recording layer, smoothness can be improved, and the S/N ratio of the magnetic signal can be improved. In this case, it is preferable to apply a photosensitive layer on the transparent support after calendering treatment.

As a method for applying the magnetic recording layer, air doctor coating, blade coating, air knife coating, squeeze coating impregnation coating, reverse roll coating, transfer roll coating, Kurahya coating, kiss coating, cast coating, spray coating, etc. can be used. These methods are also possible, and detailed explanations of these methods can be found in "Coating Engineering" published by Asakura Shoten, pages 253 to 277 (Showa 4).
6, 3. 20. Publication).

It is also preferable to create a transparent support having a magnetic recording layer by co-casting a solution of a polymer in which magnetized particles are dispersed and a solution of a polymer for creating a transparent support. In this case, 2
Preferably, the compositions of the different polymers are substantially the same.

By such a method, the magnetic layer coated on the support is immediately subjected to a treatment to orient the magnetic powder in the layer while drying, if necessary, and then the formed magnetic layer is dried. The conveying speed of the support at this time is usually 10 m/min to 500 m/min.
m/min, drying temperature 20°C to 120°C
controlled by The magnetic recording medium of the present invention is manufactured by subjecting the magnetic recording medium to surface smoothing if necessary. These are, for example, Japanese Patent Publication No. 40-23625, Japanese Patent Publication No. 39-28
No. 368, US-Japan Patent No. 3,473,960, and the like. Furthermore, the method disclosed in Japanese Patent Publication No. 41-13181 is considered to be a basic and important technique in this field.

Next, the 75-116 μm support of the present invention will be described.

The material for the support of the sensitive material used in the present invention is not particularly limited, but various plastic films can be used, and preferred ones include cellulose derivatives (for example, diacetyl, triacetyl, propionyl, butanoyl,
acetylpropionyl acetate, etc.), polyamides, polycarbonates described in U.S. Pat.
4-cyclohexane dimethylene terephthalate, polyethylene naphthalate, etc.), polystyrene, polypropylene, polyethylene, polysulfone, polyarylate,
Polyetherimides are preferred, and triacetylcellulose and polyethylene terephthalate are particularly preferred.

These supports of the present invention have a thickness of 75 μm or more 1
It is 16 μm, more preferably 90 μm to 115 μm.

If it is thinner than 75 μm, it is likely to be cut when sudden tensile strength is applied, and if it is larger than 116 μm, the film strength will be strong, but if it is stored in a film cartridge for a long time, it may cause poor contact with the magnetic head. Ru. In particular, when stored in a feeding type cartridge such as that disclosed in US Pat. No. 4,913.368, the magnetic properties deteriorate significantly.

These supports have plasticizers added to them for the purpose of imparting flexibility, etc.
Sometimes used. In cellulose ester, l
-Plasticizer-containing materials such as liphenyl phosphate, biphenyl diphenyl phosphate, and dimethyl ethyl phosphate are preferred.

In order to firmly adhere photographic layers (for example, a photosensitive silver halide emulsion layer, an intermediate layer, a filter layer, the transparent magnetic layer of the present invention, and a conductive layer) onto these supports, chemical treatment,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment,
After surface activation treatment such as high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., it is possible to apply photographic emulsion directly to obtain adhesive strength, or After surface treatment, or without surface treatment, an undercoat layer may be provided and a photographic emulsion layer applied thereon.

In this case, for the cellulose derivative, a single layer of a gelatin solution dispersed in a methylene chloride/ketone/alcohol mixed organic solvent is applied to provide an undercoat layer.

Chromium salts (such as chromium alum) as gelatin hardeners
, aldehydes (formaldehyde, geltaraldehyde, etc.), isocyanates, active halogen compounds (
2,4-dichloro-6-hydroquine-s-triazine, etc.), epichlorohydrin resin, and the like. These undercoating liquids can contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids,
Anti-rash agents, etc. When using the undercoat solution of the present invention, an etching agent such as resorcinol, chloral hydrate, chlorophenol, etc. can also be included in the undercoat solution.

The subbing layer of the present invention may contain inorganic fine particles such as 5I02, TiO2, or polymethyl methacrylate copolymer fine particles (1 to IO .mu.m) as a matting agent.

The undercoating liquid according to the present invention can be applied using generally well-known coating methods such as dip coating, air knife coating,
Curtain coat method, roller coat method, wire bar code method, gravure coat method, or U.S. Patent No. 2,68
Coating can be carried out by the extrusion coating method using a hopper as described in the specification of No. 1,294.

As appropriate, U.S. Pat. No. 2,761,791, 3,
No. 508.947, No. 2,941,898, and 3°5
Two or more layers can be coated simultaneously by the method described in No. 26,528, "Coating Engineering" by Yuji Harasaki, p. 253 (published by Asakura Shoten, 1973).

Next, the photographic material of the present invention will be described in detail.

The sensitive material of the present invention is composed of a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer, etc., and these are mainly used as a hydrophilic colloid layer.

In that case, binders for the hydrophilic colloid layer include, for example, proteins such as seratin, colloidal albumin, and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids. Examples include polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof and partially hydrolyzed dispersions, dextran, polyvinyl acetate, polyacrylic ester, Ronne, etc. Mixtures of two or more of these colloids may also be used.

Among these, the most used is seratin or its derivatives. The term seratin referred to here refers to so-called lime-treated seratin, acid-treated seratin, and enzyme-treated seratin.

In the present invention, anionic, nonionic, cationic, and betaine fluorine-containing surfactants can also be used in combination.

These fluorine-containing surfactants are disclosed in JP-A-49-10722, British Patent No. 1,330,356, and JP-A-51847.
No. 12, No. 54-14224, No. 50-113221
No. 4,335°201, U.S. Pat. No. 4,347.
No. 308, British Patent No. 1.417,915, Special Publication No. 5
No. 2-26687, No. 57-26719, No. 59-3
No. 8573, JP-A-55-149938, JP-A No. 54-4
No. 8520, No. 54-14224, No. 58-2002
No. 35, No. 57- ], No. 46248, No. 58196
No. 544, British Patent No. 1,439,402, etc.

Preferred specific examples of these are described below.

F-I C, F,, SO, K F 2 (Near F15C○0NaF-3C, H.

C, F, □SO, N-CH2C00K Ch H+ C, F,, So, N+CH2CHCH20÷l+cH2
++5O3N aH C,H.

C, F, SO, N+CH2CH2O÷1(-CH2-)-t3
02N aCIF,,CH,CH,0OC-CH2C
,H,,0OC-CH CH.

S　Oh　N　a CH.

Na C,, H2 C,F,, SO2N-f-CH2CH20-)-,, H
In the present invention, a nonionic surfactant may be used.

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

Compound example N-I C,, H21COO(-CHICH20+8
HC1yH33COO+Ct(, cHto÷5+CH2
-CH-CH2+ s + CH2Ct(J+sHH N-3C,tH,,O+CH2CH20-)-,2HC
The layer to which the fluorine-containing surfactant and nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic material, for example, a surface protective layer. , an emulsion layer, an intermediate layer, an undercoat layer, a base layer, a base layer, etc.

The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention may range from 0.0001 g to 1 g per square meter of the photographic material, more preferably from 0.0005 to 0.5 g.

Particularly preferred is 0.0005g to 0.2g. Moreover, two or more types of these surfactants of the present invention may be mixed.

Also, nitylene glycol, propylene glycol, l,
Polyomal compounds, such as those shown in JP-A-54-89626, may be added to the protective layer or other layers of the present invention.

Other known surfactants may be added alone or in combination to the photographic constituent layer of the present invention. They are used as coating aids or are sometimes applied for other purposes such as emulsion dispersion, sensitization and other improvements in photographic properties.

Also, in the present invention, lubricating compositions, such as U.S. Pat. No. 3,079,837, U.S. Pat. Modified silicones such as those shown in No. 537 and JP-A-52-129520 can be included in the photographic constituent layer.

The photographic light-sensitive material of the present invention has a photographic constituent layer in which U.S. Pat.
No. 411,911, 3. 411. 912, Japanese Patent Publication No. 45-5331, etc., may be included.

The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardening agents (singly or in combination).

Representative examples of silver halide color photographic materials particularly preferred in the present invention include color reversal films and color negative films.

In particular, a general color negative film is a preferred color photographic material.

The following description will be made using a general color negative film.

The light-sensitive material of the present invention only needs to have at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on the support. There are no particular limitations on the number and order of layers and non-photosensitive layers. A typical example is a silver halide photographic material having on its support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the photosensitive layer is generally a unit photosensitive layer. A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer between each layer may be provided between the silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
No. 037, No. 6]-20038, such as couplers, DIR compounds, etc. may be included, and a commonly used color mixing inhibitor may be included.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are used in West German Patent No. 1 121.470 or British Patent No. 923,045, Japanese Patent Application Laid-open No. 57112751, German Patent No. 62
-200350, 62-206541, 62-
No. 206543, No. 56-25738, No. 62-63
No. 936, No. 59-202464, Special Publication No. 55-34
No. 932 and No. 49-15495.

Silver halide grains include those with regular crystals such as cubes, octahedrons, and dodecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with crystal defects such as twin planes. or a combination thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less or dog-sized grains of up to about 10 microns in projected area diameter, and may be a polydisperse emulsion or a monodisperse emulsion.

A silver halide photographic emulsion that can be used in the present invention is, for example, Research Disclosure (RD) N.

17643 (December 1978), pp. 22-23,
1. Emulsion preparation
on and types)” and same No. 187
16 (November 1979), p. 648, “Physics and Chemistry of Photography J” by Krafkide, published by Beaumontel (P, Gl.
afkides, Chemie ef Ph1siqu
e Photographique, Paul Mon
tel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, F, Duffin, P.
photographic emulsion chem
istry (Focal Press, l 96
6) ), "Manufacture and Coating of Photographic Emulsions" by Serifman et al.
, Published by Focal Press (V, L, Zelikman
et al., Making and Coating
Photographic Emulsion, Fo
Cal Press, ] 964).

U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
No. 4 and British Patent No. 1. 413. Monodispersed emulsions such as those described in No. 748 are also preferred.

Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described by Cutoff, Photographic Science and Engineering.
ence and Engineering), No. 14
Vol. 248-257 (1970): U.S. Patent No. 4.
434゜226, 4,414,310, 4,
433.048, 4,439,520, and British Patent No. 2,112,157.

The crystal structure may be --like, or it may have a layered structure in which the inside and outside have different halogen compositions, or it may have a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

Also, mixtures of particles of various crystal forms may be used.

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The efficiency of the present invention is particularly noticeable when emulsions sensitized with gold compounds and sulfur-containing compounds are used.

Additives used in such processes are Research Disclosure No. 1 7643 and Research Disclosure No. 18.
716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below.

Additive type RD17643 RD18716
■ Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers
Same as above 4 Whitening agent 24 pages 8 Dye image stabilizer 25 pages 9 Hardening agent 26 pages 651 pages left column 10 Binder 26 pages same as above 11 Plasticizers, lubricants 27 pages 650 pages right column Also, deterioration of photographic performance due to formaldehyde gas In order to prevent
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 435,503.

Various color couplers can be used in the present invention, specific examples of which can be found in the aforementioned Research Dis') o-')
+ - (RD) Na l 7643, VII-C-G
It is described in the patent described in .

Examples of high boiling solvents used in oil-in-water dispersion methods are described in U.S. Pat. No. 2,322,027 and others.

Specific examples of high boiling point organic solvents with a boiling point of 175°C or higher at normal pressure used in the aqueous oil droplet dispersion method include phthalic acid esters, esters of phosphoric acid or phosphonic acid, benzoic acid esters, amides, Examples include alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives, and hydrocarbons. In addition, as an auxiliary solvent, the boiling point is about 30°C or higher, preferably 50°C or higher, about 160°C.
Organic solvents of C or lower can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Pat.
, 54L No. 230, etc.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and the film swelling rate T'A is preferably 30 seconds or less.

The film thickness means the film thickness measured at 25° C. and 55% relative humidity (2 days), and the film swelling rate Ty2 can be measured according to a method known in the art. For example, a swellometer (swelling membrane) of the type described by A. Green et al. in Photographic Science and Engineering, Vol. 19, No. 2, pp. 124-129. 1% is defined as the saturated film thickness, which is 90% of the maximum swelling film thickness reached when treated with a color developing solution at 30°C for 3 minutes and 15 seconds, and until this 1% film thickness is reached. defined as the time of

The membrane swelling rate T'A can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating.

Further, the swelling rate is preferably 150 to 400%. Swelling rate is calculated from the maximum swollen film thickness under the conditions mentioned above, using the formula:
It can be calculated according to (maximum swelling film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD, N
a17643, pages 28-29, and the same N.

Development processing can be carried out by the usual method described in 615 left column to right column of No. 18716.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound No. 7, No. 3,342,59
No. 9, Schiff base-type compounds described in Research Disclosure No. 14,850 and Research Disclosure No. 15.159, Research Disclosure No. 1
3.924.

Next, a preferable form of the photosensitive material of the present invention is a roll-shaped film that allows signals to be easily input to the transparent magnetic recording layer when the film is transported in a camera or printer. In this roll-shaped film, the image exposure area l
The area of the piece shall be 350 mm or more and 1200 mm or less,
The magnetic information recording space is preferably 15% or more of the area of the above-mentioned image exposure section (2) frame. in particular,
Preferably, the number of perforations per screen is less than 135 formats. It is particularly preferable that the number of perforations per frame is 4 or less.

It is also possible to optically input information into the magnetic information recordable space using a light emitter such as an LED. It is also preferable to input magnetic information and optical information in this space in a superimposed manner. Magnetic recording format is world public 90-0
Preferably, the method disclosed in No. 4205 is followed.

When the photosensitive material of the present invention is used in the form of a roll, it is preferably stored in a cartridge. The most common cartridge is the current 135 format cartridge. Other cartridges proposed in the following patents can also be used. (Jitsukai 58-673
No. 29, JP-A-58-181035, JP-A-58-1
No. 82634, Utility Model Application No. 1952.36/1982, U.S. Patent No. 4,221,479, Japanese Patent Application No. 57785/1983,
Patent Application No. 183344/1983, Patent Application No. 63325638
No., Japanese Patent Application No. 1-21862, Japanese Patent Application No. 125362,
Japanese Patent Application No. 1-30246, Japanese Patent Application No. 1-20222, Japanese Patent Application No. 1-21863, Japanese Patent Application No. 1-37181, Japanese Patent Application No. 1-33108, Japanese Patent Application No. 1-85198, Particularly preferred is a cartridge having a means for controlling the attitude of the cartridge in the camera . (Patent application Hei 1-21489
No. 5) Next, the cartridge used in the present invention is mainly composed of synthetic plastic.

In molding the plastics of the present invention, a plasticizer is mixed with the plastics as necessary. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone,
Representative examples include di-n-octyl succinate, bromonaphthalene, and butyl palmitate.

Specific examples of plastic materials used in the present invention are listed below, but the invention is not limited thereto.

Specific examples include polystyrene, polyethylene, polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylic resin, vinyl formal resin, Particularly preferred plastic materials for the present invention are polystyrene, polyethylene, polypropylene, etc., including vinyl butyral resin, polyethylene terephthalate, Teflon, nylon, phenolic resin, melamine resin, etc.

Furthermore, the cartridge of the present invention may contain various antistatic agents. Antistatic agents are not particularly limited, and include carbon black, metal oxide particles, nonions, anions, cations, betaine surfactants, nonions, anions,
Cationic and betaine polymers can be preferably used. These antistatic cartridges are described in JP-A-1-312537 and JP-A-1-312538.

Cartridges are usually manufactured using plastic mixed with carbon black or pigments to provide light-blocking properties.

Furthermore, although the current size of the cartridge may be maintained, it is effective to reduce the size of the camera by changing the diameter of the cartridge, which is currently 25 m/m, to 22 m/m or less, preferably 20 m/m or less, and 14+++/m or more. Also, with current cartridges,
The tip of the spool on the side that engages with the camera's film drive unit protrudes and is an impediment to miniaturization of cameras, so it is preferable to eliminate this portion. As a result, currently approximately 3
The volume of the cartridge, which is 5ci, can be reduced. The volume of the cartridge case is 30ci or less, preferably 25cn
It is preferable to set it to less than f, more preferably less than 20ci.

The weight of the plastic used for the cartridge and cartridge case is 1g or more and 25g or less, preferably 5g.
The amount is 15g or less.

The ratio of the internal volume of the cartridge case to the plastic used in the cartridge and cartridge case is 4~
0.7, preferably 3-1.

In the case of the cartridge containing the 135 color photosensitive material according to the present invention, the total weight of the plastic used for the cartridge and the cartridge case is usually 1 g or more and 25 g or less, preferably 5 g or more and 15 g or less.

Next, the form of the cartridge containing the color sensitive material described in the present invention will be described.

The cartridge of the present invention is not particularly limited in its form, but is preferably compatible with commercially available cameras. Furthermore, it may be used in a new camera that is compatible with a cartridge containing the color photosensitive material of the present invention. Specific examples of these cartridges are shown in FIG. 1 (further, FIGS. 2 to 4 for the internal structure, and FIG. 5 for the magnetic recording track of the film).

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these.

Example 1 l-1) Preparation of base 7 - Co-cast cellulose triacetate dope and cellulose triacetate dope in which Fe2es (specific surface area 25 m/g, made by Ficer (USA)) is dispersed to form a transparent base with a thickness of 2μ. A film base with a magnetic recording layer was prepared. γ・Fe
The amount of 2O+ applied is 0.14g/r+? Met.

(The film thickness of the cellulose triacetate support is listed in Table 1).

A back layer having the composition shown below was provided on this base to form a base for a photosensitive material. Note that the surface having the magnetic recording layer was used as the back layer.

(Back layer composition) 1st layer Cellulose triacetate 0.1g/m Ethylene glycol 0.08 〃0.05 l/2nd layer Cellulose diacetate 0.32g/rrl Aerosil 0 02 No I(n) CIiH
+IlC00CtoH+(n)0.02 Poly(methyl methacrylate/styrene) (molar ratio 95
:5, average particle size 2. 0 μm) 0.01 〃 The obtained base has a coercive force of 500 to 550 Oe and a squareness ratio of 0.70 to 0.75.
It was confirmed that the signal input method disclosed in No. 5 is possible.

■-2) Preparation of photosensitive material After corona discharge treatment is applied to the side opposite to the back layer of the undercoated cellulose triacetate film support, each layer having the composition shown below is coated in multiple layers to prepare a multilayer color photosensitive material. A sample was prepared.

(Photosensitive layer composition) A photosensitive layer was prepared in exactly the same manner as the photosensitive layer described in Example 1 of JP-A-2-93641.

(Processing of sample) The sample was cut into a 24-shot film having a width of 135 mm and the format shown in FIG. 1.

These samples were developed as follows.

Color development 3 minutes 15 seconds Bleach White 6 minutes 30 seconds Water Wash 2 minutes 10 seconds Fixed arrival time: 4 minutes 20 seconds Water Wash 3 minutes 15 seconds Safe, fixed, 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriamine pentaacetic acid j-hydroxyethylidene 1,1-diphosphonic acid sodium sulfite potassium carbonate potassium bromide potassium iodide hydroxolamine sulfate 4-(N-ethyl-N-β hydroxyethylamino) -2-methylaniline sulfuric acid Add salt water and add 0g 4,5g 1,01 H 10,0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium chloride Ammonium bromide 10.0g 150.0g Ammonium nitrate 10.0g Add water 1. offp) - (6,0 Fixer ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0d Sodium bisulfite 4.6g Add water
1.01p86.6 Stabilizing liquid formalin (40%) 2.0J polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add 0.3g water 1.01 (1) Transmittance test Unexposed Using a sample that has been developed and fixed,
The total light transmittance was measured. Table 1 shows the relative transmittance, with the sample containing no magnetic material being set as 100. The total light transmittance is ASTMD.
-1003.

(2) Evaluation of output errors in magnetic recording A sensitive material magnetically input from the back side using the signal input method disclosed in World Publication No. 90-04205 mentioned above was outputted 300 times with a magnetic head, and the number of errors was calculated. Indicated.

The photosensitive material was evaluated immediately after being rolled into the cartridge for the first time, and on an undeveloped film that had been left for one month under the temperature and humidity conditions shown in Table 1. The measurements were performed at 25°C and 160% RH.

The thickness of the support of the present invention is as shown in Table 1.
-1 to 1-3 had excellent magnetic output characteristics not only immediately after rolling but also after being stored under low humidity, high temperature and high humidity conditions. On the other hand, comparative samples 1-4 to 1-5 consisting of supports having a thinner or thicker film thickness than those of the present invention.
The results showed that the magnetic output noise error greatly increased with long-term storage.

From the above, the support of the present invention was found to have excellent magnetic properties, significantly different from conventional knowledge.

Example 2 2-1) Preparation of support A film base was prepared by casting a cellulose triacetate dope. (The film thickness is shown in Table 2).

The following backing layer was provided on one side (backing layer) of this base.

(a) Back first layer cellulose triacetate ethylene glycol SnO+, /Sbz○, /SO/1, average particle size O1 0.1g/resistant 0.08/102 (mole ratio 90/1 12μm) 0 2 ll (b) Back 2nd layer Butyl acetate/vinyl chloride polymer (50/50) 2.5 g/m Cobalt-doped iron oxide fine powder 0.20" (c) Back 3rd layer Polymethyl methacrylate 0.32 g/m Aerosil 0.02” poly(methyl methacrylate/divinyl styrene) (molar ratio 95:5) (average particle size 2, Oμm) 0
．． 01'ノC,5H,,C00C,. )l
,, 0.01'' The coercive force of all the back surfaces prepared was approximately 1000 Oe.

2-2) Preparation of photosensitive material layer A photosensitive material layer was applied to the layer on the opposite side of the hack of the supports prepared in Examples 1-2) and 2-1 in the same manner.

The prepared samples 2-1 to 2-6 were evaluated as shown in Table 2.

As shown in Table 2, the sample has the film thickness of the support of the present invention! -1 to 2-3 have excellent magnetic properties, but comparative samples 2-4 to 2-6 have support film thicknesses other than those of the present invention.
A magnetic output error occurred during long-term storage.

Example 3 A support and a back surface were prepared in exactly the same manner as in Example 2-1). On the surface opposite to the back surface of the support, JP-A-2-85 was applied.
The reversal color emulsion layer described in No. 4 Example 1 Sample 101 was coated. In addition, the development process used Fuji Photo Film (CR-56 process of Kikki color reversal process).

Samples 11 to 3-3 of the present invention were excellent in permeability and magnetic properties. In contrast, Comparative Samples 3-4 to 3-6 showed significant deterioration in magnetic properties after long-term storage.

Example 4 4-1) Preparation of support Polyethylene terephthalate was uniaxially stretched and polyethylene was coated on both sides.
(vinylidene/acrylonitrile/itaconic acid; molar ratio 92:5:3) aqueous dispersion (N content after stretching: 1.5 g/
m), Todenrugensense Sodium Sulfonate (2mg/
m), Nrika particles (average particle size 0.3 μm; 20 m)
g/m), polystyrene particles (average particle size 1.0 μm
; 2mg/m), 2-hydroxy-4,6-dichloro-1,,3,54 riazine (35mg/m), trimethylolpropane trianlysine (10mg/m)
) was coated and stretched again during drying to create a first layer of hnylidene chloride for undercoating the support. The thickness of the polyethylene terephthalate at this time was as shown in Table 4.

After further corona discharge treatment on both sides, gelatin (0.2 g/m), poly(polymerization degree 10) oxyethylene dodenyl ether (2 mg/m), (CH2=CH
-3O2NHCH2→-z (10 mg/?) was applied to prepare a support as a second undercoat layer.

4-2) Creation of back surface The following bank layer was applied to one side of the undercoated support created in 4-1).

b) Back 1st layer Cobalt-doped iron oxide fine powder (contained as a ceratin dispersion. Average particle size 0.08 μm) 0.2 g/m ceratin 3 1/(CH2=CH3O
2NHCH, CH2NH÷2COO, 1'1 0.02g/Popori (Ethyl acrylate) (Average particle size 0.08μm) 1 〃口）Back 2nd
Layer Ceratin 0.12 Sodium polyacrylate (average molecular weight 150,000) 0.03 Sn○2/5b20s/S i02 fine particles (mole ratio 9
0/l O/L particle size 0.12 μm) 0.2〃 Sodium dodecylbenzene sulfonate 0.02〃 C) Hack 3rd layer ceratin polymethyl methacrylate (average particle size 1.5 μm) Cetyl stearate 1 (Dob Dispersed with Sodium Silhensensulfonate) Socium di(2-ethylhexyl)sulfosuccina-1・0°0°Ol ■ 0.01 no/C,H.

C, F,, SO, NCH2C00K 0.0] Emulsion of the present invention The coercive force of the obtained back layer was 950 to 1000 Oe.

``Cetyl stearate was added with 3% by weight of sodium dodecylbenzene sulfonate as a solid content, pulverized using a vibrating ball mill (using zirconia beads with a diameter of 1 +++++++), and added to the coating solution.

The average particle diameter of the obtained fine powder was 0.15 μm, and more than 90% (volume distribution) of it was 0.3 μm or less.

4-3) Preparation of emulsion layer surface On the opposite side of the support having the back surface prepared in 4-2), the emulsion layer of Sensitive material 1 of Example 1 of JP-A-2-93641 was coated in exactly the same manner.

Development processing was carried out using Example I of the present invention.

The characteristics of the obtained sample were evaluated in exactly the same manner as in Example 1 and are shown in Table 4.

As shown in Table 4, Samples 4-1 to 4-3 of the present invention exhibit excellent magnetic properties, but Comparative Samples 4-4 to 4-6 had problems with magnetic output errors after long-term storage.

(Effects of the Invention) By using a transparent magnetic layer and a support with a constant thickness, the present invention provides excellent photographic transparency and reduces errors in magnetic recording immediately after being wound into a cartridge. In addition, it was an excellent photographic material with few magnetic output errors even after being stored for a long time under low humidity or high temperature and high humidity conditions.

[Brief explanation of drawings]

Fig. 1 is a perspective view of a photographic film cartridge according to the present invention, Fig. 2 is a plan view showing the state of the leading end of the photographic film, Fig. 3 is a sectional view of the cartridge, and Fig. 4 shows the inside of the cartridge. FIG. Also, Figure 5 ((5-1
, (5-2)) are plane and cross-sectional views of the magnetic recording track layer. [Explanation of symbols] l...... Photographic film cartridge 2...
... Spool 3 ... Photographic film 4 ... Patrone body 5 ... Film drawer lower ...
... Perforation 8 ... Protrusion 9 ... Protrusion 10 ... Hole 11 ...... Notch 12...Film pull-out passage 13...
..... Step portion 14 ..... Emulsion constituent layer I5 ..... Support 16 ..... Transparent magnetic layer 17 ....・・・・・・Antistatic layer 10 Scratch resistant layer + Lubricating layer 18・・・・・・1 frame

Claims (6)

[Claims] (1) A silver halide photographic material having a light-sensitive silver halide emulsion layer on at least one side of a support, the photographic material having a transparent magnetic layer on at least one side, the coercive force of which is 400 Oe or more, and the thickness of the support is 75 to 116 μm. (2) The silver halide photographic material according to claim 1, wherein the photographic material is a color photographic material. (3) The ferromagnetic material used in the transparent magnetic layer is ferromagnetic iron oxide fine powder, Co-doped ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic alloy fine powder, ferromagnetic The silver halide photographic light-sensitive material according to claims 1 and 2, which is a metal fine powder and barium ferrite. (4) The silver halide photographic material according to claims 2 and 3, wherein the support has a composition of triacetylcellulose or polyethylene terephthalate and derivatives thereof. (5) Patent claim 3 in which the transparent magnetic layer is on the back layer side
The silver halide photographic material described in Items 1 and 4. (6) The silver halide photographic material according to claims 4 and 5, wherein the outermost layer on the back layer side contains a matting agent with a thickness of 1 to 3 μm.