JPH04293039A - Silver halide photographic sensitive material with magnetic recording element - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material with a magnetic recording layer having superior transparency to visible light and superior magnetic output reproducing characteristics. CONSTITUTION:When at least one photosensitive silver halide emulsion layer and at least one transparent magnetic recording layer are formed on a film base to obtain a silver halide photographic sensitive material, the average diameter of aggregates of a magnetic body contained in the magnetic recording layer is regulated to 0.3-1.0mum.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and in particular has a magnetic recording layer that is substantially transparent to visible light and exhibits excellent magnetic recording and reproducing properties. This invention relates to silver halide photographic materials.

0002

[Prior Art] Conventionally, silver halide photographic materials (hereinafter abbreviated as "sensitized materials") have been used to store various types of information (for example,
It is almost impossible to input information such as the date of photography, weather, magnification ratio, number of prints, etc., and it is only possible to input the date of photography optically. Furthermore, it is completely impossible to input information to the photosensitive material itself during printing, which is a major obstacle to achieving high speed and cost reduction. Inputting various information to the photosensitive material is a very important means for improving camera operability and making it simpler in the future. As an information input means, magnetic recording methods are important because they allow arbitrary input/output and are inexpensive, and have been studied for a long time. For example, by appropriately selecting the amount and size of the magnetic particles contained in the magnetic recording layer, the magnetic recording layer can be made transparent so that it has the necessary transparency for the sensitive material at the time of photographing, and also does not adversely affect the granularity. Providing a support on the back side of a photosensitive material is disclosed in US Pat. No. 3,782,947;
It is described in 4,279,945, 4,302,523, etc. Further, a signal input method to this magnetic recording layer is disclosed in W090-4205, W090-04212, and the like. By providing these magnetic recording layers and input/output methods, it is now possible to incorporate various types of information into the photosensitive material, which was difficult to do in the past. It is now possible to input and output information such as the number of reprints, the location to be zoomed in, the development of messages, etc., and the printing conditions to the magnetic layer of the photosensitive material. Furthermore, it has the potential to be applied as a signal and output means for directly outputting images from photosensitive materials for television/video images.

[0003] Japanese Patent Publication No. 57-6576 and Japanese Patent Application Laid-open No. 1983-1989, which are prior art related to sensitive materials having a transparent magnetic recording layer,
A magnetic recording layer using gamma ferric oxide, such as that used in No. 109,604, has low transmittance to light in the visible range, and the transmittance also has a large wavelength dependence, resulting in a so-called brownish color. was. When a transparent magnetic recording layer is provided within the screen of a sensitive material, the density of the magnetic material in the magnetic recording layer should be as low as possible in order to increase the light transmittance. but,
Therefore, it is difficult to extract sufficient magnetic output,
The C/N ratio also deteriorates. Furthermore, in order to increase the magnetic output, it is necessary to increase the density of the magnetic material in the magnetic recording layer. In this case, a disadvantage arises in that the light transmittance becomes low. Therefore, it has been desired to develop a method that increases the light transmittance as much as possible, provides sufficient magnetic output, and provides a sufficiently large C/N ratio. Furthermore, it has been desired to develop a magnetic recording layer in which the wavelength dependence of light transmittance is as small as possible, and which is close to so-called neutral gray.

0004

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having a magnetic recording layer that is substantially transparent to visible light, close to neutral gray, and has excellent magnetic properties. Our goal is to provide the following.

[0005]

[Means for Solving the Problems] The above object is to provide a silver halide photographic photosensitive material having at least one photosensitive silver halide emulsion layer on a film support and having at least one transparent magnetic recording layer. By a silver halide photographic light-sensitive material, the weight average particle diameter (hereinafter abbreviated as average aggregate size) of aggregates of magnetic material contained in the magnetic recording layer is 0.3 μm or more and 10 μm or less. achieved.

In the silver halide photographic material of the present invention,
The transmission density of the magnetic recording layer must be as low as possible. Further, the C/N ratio must be large enough to enable magnetic recording. Conventionally, for example, as a means of lowering the transmission density of magnetic materials, as disclosed in Japanese Patent Publication No. 42-4539, etc., the particle size of magnetic materials has been reduced to 0.07 μm.
Although it is known that the particle size is made too small, the magnetic output decreases and the C/N ratio worsens. Further, in order to increase the C/N ratio, if the density of the magnetic material is increased and the amount of magnetic material per unit area is increased, the permeation will significantly increase. As described above, it has been extremely difficult to simultaneously reduce the transmission density of the magnetic recording layer and increase the C/N ratio. As a result of intensive research, the present inventor surprisingly found that the average aggregate size of magnetic materials was 0.3 μm or more.
By making it 0 μm or less, it is possible to significantly reduce the transmission density of light, and the S/N at the time of magnetic reproduction output.
It was discovered that the ratio was sufficient. Furthermore, the wavelength dependence of the light transmission density has been significantly reduced. More preferably 0.7
The thickness is preferably from μm to 5 μm.

The present invention will be explained in detail below. The average aggregate size in the present invention refers to the weight average particle size of aggregates. In the magnetic recording layer, the particle size Ri of the magnetic particles is
When there are Ni particles (i=1, 2, . . . ), the weight average particle diameter is defined as Rn=ΣNiRi2/ΣNiRi. In the present invention, aggregates of magnetic particles are used. Examples of ferromagnetic powders used as primary particles of magnetic particle aggregates include ferromagnetic iron oxide fine powder, Co-containing ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic alloy powder, and Ba ferrite powder. , iron carbide powder, iron nitride powder, etc. The primary particles are preferably single-domain particles from the viewpoint of magnetic recording (coercivity). The acicular ratio of ferromagnetic iron oxide and chromium dioxide is about 2/1 to 20/1, preferably 5/1.
1 or more, and an average length in the range of about 0.05 to 2.0 μm is effective. The ferromagnetic alloy powder has a metal content of 75 wt% or more, and 80 wt% or more of the metal content is a ferromagnetic metal (i.e., F
e, Co, Ni, Fe-Ni, Co-Ni, Fe-Co
-Ni) with a major axis of about 1.0 μm or less. Ba
Particles of ferrite with a size of 0.05 to 1 μm are used. Any magnetic material may be used as the magnetic material used in the present invention. There are no particular limitations on the method for creating the magnetic aggregate. For example, coating liquids for magnetic materials are usually created through processes such as kneading, coarse dispersion, and fine dispersion, but the dispersion process weakens the dispersion so that aggregates of 0.3 μm to 10 μm remain. There is a way to distribute it. There is also a method of sintering a magnetic material, then crushing and classifying it again, and creating a film or fiber with particles and a small amount of binder.
There is a method of cutting the material into pieces with a size of 3 to 10 μm. The average aggregate size of magnetic particles is 0.3 μm or more and 10 μm
The following are desirable. If the aggregate size is 0.3 μm or less, the optical density becomes high, which is not preferable. C if it is 10μm or more
/N deteriorates, which is unfavorable in terms of magnetic performance. Furthermore, 0
．． The thickness is preferably 5 μm or more and 5 μm or less. It is preferable that the distribution of the average aggregate size of the magnetic material is as narrow as possible. The average aggregate size of magnetic particles is evaluated by a method using light (for example, a light scattering method, an optical correlation method, an optical diffraction method, etc.), a method of measuring the particle size from an electron micrograph image, or the like. The content of magnetic fine particles in the magnetic recording layer in the present invention is 1 m2
The amount is preferably 0.01 g or more and 3.0 g or less. If the content is less than 0.01g, the magnetic output will decrease and C
/N becomes bad, so it is not preferable. If the content is too large, the optical density becomes high, which is not preferable. Preferably 0.0
The amount is preferably 5g to 1g.

[0008] The binder for the magnetic recording layer used in the present invention may be any of the known thermoplastic resins, thermosetting resins, radiation curable resins, reactive resins, and conventional binders for magnetic recording media. Mixtures of these, hydrophilic binders such as gelatin can be used. The resin has a Tg of -40°C to 150°C and a weight average molecular weight of 5,000 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 copolymers such as vinyl chloride/vinylidene chloride copolymers, vinyl chloride/acrylonitrile copolymers, ethylene/vinyl acetate copolymers, nitrocellulose, triacetyl Cellulose, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate resin, acrylic resin, polyvinyl acetal resin,
Rubber resins such as polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, butadiene acrylonitrile resin,
Examples include silicone resins and fluororesins. Among these, vinyl chloride resin and triacetyl cellulose are preferred because they have high dispersibility of ferromagnetic fine powder.

The above-mentioned thermosetting resin or reactive resin has a molecular weight that becomes extremely large when heated.
For example, phenolic resin, phenoxy resin, epoxy resin, curable polyurethane resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic reaction resin, epoxy-polyamide resin, nitrocellulose-smelamine resin, high molecular weight polyester resin and isocyanate. Mixture of prepolymers, urea formaldehyde resin,
Included are mixtures of low molecular weight glycols/high molecular weight diols/polyisocyanates, polyamine resins, and mixtures thereof. Further, as the radiation-curable resin, a resin obtained by bonding a group having a carbon-carbon unsaturated bond as a radiation-curable functional group to the above-mentioned thermoplastic resin is used. Preferred functional groups include acryloyl and methacryloyl groups. In the bond molecules listed above, polar groups (epoxy group, CO2 M, OH, NR2, NR3 M,
SO3 M, OSO3 M, PO3 M2, OPO3
M2, provided that M is hydrogen, an alkali metal or ammonium, and when a plurality of M's are present in one group, they may be different from each other. R is hydrogen or an alkyl group. ) may be introduced. The 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.

The isocyanate crosslinking agent is a polyisocyanate compound having two or more isocyanate groups, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5-diisocyanate. , isocyanates such as o-toluidine diisocyanate, isophorone diisocyanate, triphenylmethane diisocyanate, reaction products of these isocyanates and polyalcohols,
and polyisocyanates produced by condensation of these isocyanates. These polyisocyanates are available from Nippon Polyurethane Industries Co., Ltd. as Coronate L, Coronate HL, Coronate H, and Coronate EH.
Ronate 2014, Coronate 2030, Coronate 2
031, Coronate 2036, Coronate 3015, Coronate 3040, Coronate 3041, Millionate MR, Millionate MTL, Daltosec 1350, Daltosec 2170, Daltosec 2280, Takenate D102, Takenate D11 from Takeda Pharmaceutical Co., Ltd.
0N, Takenate D2, Takenate D202, from Sumitomo Bayer Co., Ltd., Sumidur N75, Desmodur L, Desmodur 1L, Desmodur N, Desmodule HL, from Dainippon Ink and Chemicals Co., Ltd., Burnock D850, It is commercially available under trade names such as Burnock D802.

The radiation-curable vinyl monomer is a compound that can be polymerized by radiation and has one or more carbon-carbon unsaturated bonds in its molecule, such as (meth)acrylic esters, (meth) Examples include acrylamides, allyl compounds, vinyl esters, vinyl heterocyclic compounds, N-vinyl compounds, styrene, (meth)acrylic acid, crotonic acid, itaconic acid, and olefinic acid. Among these, diethylene glycol di(
Polyethylene glycol (meth)acrylates such as meth)acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate
Acrylate, dipentaerythritol penta(meth)
Acrylate, dipentaerythritol hexa(meth)
Examples include acrylates and reaction products of polyisocyanates and hydroxy (meth)acrylate compounds. These crosslinking agents are preferably 5 to 45 wt% of the total binder including crosslinking agents.

[0012] Also, as a hydrophilic binder, Research Disclosure No. 17643, page 26, and the same No. 18716, page 651,
Examples include water-soluble polymers, cellulose esters, latex polymers, and water-soluble polyesters. Examples of water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, and maleic anhydride copolymers, and examples of cellulose esters include carboxymethyl cellulose and hydroxyethyl cellulose. It is. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene anhydride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Among these, gelatin is most preferred. Further, gelatin derivatives and the like may be used in combination with gelatin.

As the gelatin, any of so-called lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, gelatin derivatives, modified gelatin, etc. can be used, and among them, lime-treated gelatin and acid-treated gelatin are preferably used. Preferably, the magnetic recording layer containing gelatin is hardened. Hardeners that can be used in the magnetic recording layer include, for example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis(2-chloroethyl urea), 2-hydroxy-4, 6-dichloro-1
, 3,5-triazine, etc. U.S. Pat. No. 3,288
, No. 775, No. 2,732,303, British Patent No. 97
Compounds containing reactive halogens, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, as described in No. 4,723, No. 1,167,207, etc. , and other compounds containing reactive olefins such as those described in U.S. Patent No. 3,635,718, U.S. Patent No. 3,232,763, and British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Patent No. 2,732,316,
N-methylol compounds described in US Pat. No. 2,586,168, isocyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017
, No. 280, No. 2,983,611, etc., U.S. Patent No. 2,725,294
No. 2,725,295, etc., epoxy compounds described in U.S. Patent No. 3,091,537, etc., and halogencarboxaldehydes such as mucochloric acid. Can be done. Or, as a hardening agent for inorganic compounds, use chromium alum, zirconium sulfate, Japanese Patent Publication No. 12853/1985, Japanese Patent Publication No. 58-3269.
No. 9, Belgian Patent No. 825,726, JP-A-60-2
No. 25148, No. 51-126125, Special Publication No. 1983-
No. 50699, JP-A No. 52-54427, U.S. Patent No. 3
, 321, 313, etc. Examples include carboxyl group-activated hardeners. The amount of hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight, based on the dry gelatin.

The ratio of the magnetic material to the binder (weight of magnetic material):(weight of binder) is preferably in the range of 1:2 to 1:100. When the amount of magnetic material is greater than 1:2, the optical density increases and transparency decreases. If the ratio of binder is more than 1:100, the C/N ratio during magnetic recording becomes poor, which is disadvantageous in terms of magnetic properties. The thickness of the transparent magnetic recording layer is 0.1 to 10 μm, preferably 0.2 to 5 μm. The maximum value of spectral density in the visible range of the magnetic recording layer is 0.
．． It is preferably 15 or less. This corresponds to a light transmittance of 70.8% or more. If the maximum value of the spectral density in the visible range of the magnetic recording layer is greater than 0.15, it cannot be used for photographic purposes. The gray level of the magnetic recording layer is 0.70
The above is preferable. The gray level is defined by the following formula. (Gray degree)=Dmin/Dmax Here, Dmax represents the maximum value of the spectral density in the visible range of the magnetic recording layer, and Dmin represents the minimum value of the spectral density in the visible range of the magnetic recording layer. Photographically, it is preferable that the degree of gray is as high as possible. A gray level of 0.70 or more is photographically acceptable, but a gray level of 0.70 or less causes significant coloring of the magnetic recording layer, making it unsuitable for photography. As for the magnetic output, it is preferable that the C/N ratio is 20 dB or more.

[0015] The transparent magnetic recording layer can be provided by coating or printing. As the application method, various methods such as doctor coating, extrusion coating, slide coating, roller coating, and gravure coating can be considered. Alternatively, a support having a magnetic recording layer may be created by co-casting a polymer solution in which magnetic particles and ultrafine particles having a high refractive index are dispersed and a polymer solution for forming the support. In this case, it is preferable that the polymer in which the magnetic particles and ultrafine particles are dispersed is substantially the same as the polymer for preparing the support. Improved lubricity and antistatic properties for the magnetic recording layer.
It may also have functions such as preventing adhesion and improving friction and wear characteristics, or it may provide these functions by providing another functional layer. Specifically, antistatic agents, lubricants, abrasives, matting agents, surfactants, and the like can be contained. If necessary, a protective layer may be provided adjacent to the magnetic recording layer to improve scratch resistance. After providing the magnetic recording layer, it is also possible to perform a calendering process on this layer to improve smoothness and improve the C/N ratio of the magnetic output.

[0016] As the film support in the present invention,
Although not particularly limited, various plastic films can be used, and preferred ones include cellulose derivatives (e.g., diacetyl-, triacetyl-, propionyl-,
butanoyl, acetylpropionyl acetate, etc.), polyamides, polycarbonates described in U.S. Pat. Methylene terephthalate, polyethylene 1,2-diphenoxyethane-4,
(4'-dicarboxylate, polybutylene terephthalate, polyethylene naphthalate), polystyrene, polypropylene, polyethylene, polymethylbentene, polysulfone, polyethersulfone, polyarylate, polyetherimide, etc., and particularly preferred are triacetyl cellulose, It is polyethylene terephthalate. A plasticizer may be added to these supports for the purpose of imparting flexibility. Particularly for cellulose esters, plasticizer-containing materials such as triphenyl phosphate, biphenyl diphenyl phosphate, and dimethyl ethyl phosphate are commonly used. The thickness of these supports varies depending on the polymer type, but the thickness ranges from a sheet of about 1 mm to 2 mm.
Thin films up to about 0 μm can be used depending on the purpose, but those with a thickness of 50 μm to 300 μm are commonly used. The molecular weight of these support polymers is preferably 10,000 or more, more preferably 20,000 to 80,000. The support may contain a dye for the purpose of neutralizing the base color, preventing light piping, and preventing halation.

In order to firmly adhere photographic layers (for example, photosensitive silver halide emulsion layer, intermediate layer, filter layer, magnetic recording layer, conductive layer) to 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, activated plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment, it is possible to apply photographic emulsion directly to obtain adhesive strength, or to obtain adhesive strength by directly applying photographic emulsion to these surfaces. After processing or without surface treatment, an undercoat layer may be provided, and a photographic emulsion layer may be applied thereon. For cellulose derivatives, a single layer of a gelatin solution dispersed in a methylene chloride/ketone/alcohol mixed organic solvent is applied to provide an undercoat layer. As the gelatin hardening agent, the above-mentioned hardening agents can be used. The undercoat liquid can contain various additives as necessary. Examples include surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, and antifogging agents. When using the undercoating liquid of the present invention, resorcinol, chloral hydrate,
Etching agents such as chlorophenol and the like can also be included in the undercoat solution. The undercoat layer of the present invention is made of SiO
2. Inorganic fine particles such as TiO2 or polymethyl methacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent.

The undercoat liquid according to the present invention can be applied by a generally well-known coating method, such as a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method, a gravure coating method, or a coating method according to US Pat. Coating can be carried out by an extrusion coating method using a hopper as described in Japanese Patent No. 2,681,294. As appropriate, U.S. Patent No. 2,761,7
No. 91, No. 3,508,947, No. 2,941,898, and No. 3,526,528, by the method described in "Coating Engineering" by Yuji Harasaki, page 253 (published by Asakura Shoten in 1973), etc. Two or more layers can be applied simultaneously.

The sensitive material of the present invention is composed of a silver halide emulsion layer, a magnetic recording layer, a back layer, a protective layer, an intermediate layer, an antihalation layer, etc., but these are mainly used in the hydrophilic colloid layer. . In that case, binders for the hydrophilic colloid layer include, for example, proteins such as gelatin, 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 copolymers, polyacrylamide or derivatives and partially hydrolyzed dispersions thereof, dextran, polyvinyl acetate, polyacrylic esters, rosin, and the like. A mixture of two or more of these colloids may be used if necessary. Among these, gelatin or its derivatives are most used, and gelatin here refers to so-called lime-treated gelatin, acid-treated gelatin, and enzyme-treated gelatin.

The photographic light-sensitive material of the present invention contains US Pat. No. 3,411,911 and US Pat.
The polymer latex described in Japanese Patent Publication No. 45-5331 and the like 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 photosensitive material having at least one photosensitive layer on a support consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different photosensitivity. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in multilayer silver halide color photographic light-sensitive materials, 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 above-mentioned 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.

[0022] 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, 59-113438, 59-113440, 6
1-20037 and 61-20038, such as couplers, DIR compounds, etc., may be included, and a commonly used color mixing prevention layer may be included.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are disclosed in West German Patent No. 1,121,470, British Patent No. 923,045, and Japanese Patent Application Laid-Open No. 11275/1983.
No. 1, No. 62-200350, No. 62-206541
No. 62-206543, No. 56-25738,
It is described in Japanese Patent Publication No. 62-63936, Japanese Patent Publication No. 59-202464, Japanese Patent Publication No. 55-34932, and Japanese Patent Publication No. 49-15495.

Silver halide grains include those having regular crystals such as cubes, octahedrons, and tetradecahedrons, those having irregular crystals such as spherical and plate shapes, and crystals such as twin planes. It may be one with defects or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 μm or less or large grains with a projected area diameter of about 10 μm.
It may be a polydisperse emulsion or a monodisperse emulsion.

Silver halide emulsions that can be used in the present invention are:
For example, Research Disclosure (RD) No. 1
7643 (December 1978), pp. 22-23, “I.
Emulsion preparation
and types)”, and the same No. 18716 (
(November 1979), 648 pages, "Physics and Chemistry of Photography" by P. Glafkide, published by P. Glafk.
ides, Chmicet Physique Pho
tographique, Paul Montel,
G.F. Duffin, Photo
graphic emulsion chemist
y (Focal Press, 1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V.L. Zelikman et al., M
making and coating photogr
aphic Emulsion, FocalPres
s, 1964) and others. U.S. Patent No. 3,574,628, 3
, 655,394 and British Patent No. 1,413,748
The monodisperse emulsions described in No. 1, etc. 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 in Photographic Science and Engineering by Guto
ff, Photographic Science
and Engineering), Volume 14, 248~
257 pages (1970); U.S. Patent No. 4,434,22
No. 6, No. 4,414,310, No. 4,433,048
No. 4,439,520 and British Patent No. 2,112
, No. 157, etc., it can be easily adjusted. The crystal structure may be uniform, the inside and outside may have different halogenated compositions, or it may have a layered structure. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded. Also, a mixture 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 listed in Research Disclosure No.
17643 and No. 18716, 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.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat. No. 4,411,9
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 87 and No. 4,435,503.

Various color couplers can be used in the present invention, specific examples of which are shown in Research Disclosure (RD) No. 1 mentioned above. 17643, VII-C~G
It is described in the patent described in . Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, and
, No. 401,752, No. 4,248,961, Special Publication No. 5
No. 8-10739, British Patent No. 1,425,020,
No. 1,476,760, U.S. Patent No. 3,973,96
No. 8, No. 4,314,023, No. 4,511,649
Preferred are those described in European Patent No. 249,473A and the like.

As the magenta coupler, 5-pyrazolone and pyrazole azole compounds are preferred, and are described in US Pat. No. 4,310,619, US Pat. ,061,
No. 432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), Japanese Patent Application Publication No. 1983-
No. 43659, No. 61-72238, No. 60-357
No. 30, No. 55-118034, No. 60-18595
No. 1, U.S. Patent No. 4,500,630, U.S. Patent No. 4,540
, No. 654, No. 4,556,630, WO (PCT)
Particularly preferred are those described in No. 88/04795.

Cyan couplers include phenolic and naphthol couplers, and are described in US Pat.
No. 52,212, No. 4,146,396, No. 4,22
No. 8,233, No. 4,296,200, No. 2,369
, No. 929, No. 2,801,171, No. 2,772,
No. 162, No. 2,895,826, No. 3,772,0
No. 02, No. 3,758,308, No. 4,334,00
No. 1, No. 4,327,173, West German Patent Publication No. 3, 3
No. 29,729, European Patent No. 121,365A, European Patent No. 2
No. 49,453A, U.S. Patent No. 3,446,622;
No. 4,333,999, No. 4,753,871, No. 4,451,559, No. 4,427,767, No. 4
, No. 690,889, No. 4,254,212, No. 4,
Preferred are those described in No. 296,199, JP-A-61-42658, and the like.

Colored couplers for correcting unnecessary absorption of coloring dyes are available in Research Disclosure No.
．． Section VII-G of 17643, U.S. Patent No. 4,163
, 670, Japanese Patent Publication No. 57-39413, US Pat. Nos. 4,004,929 and 4,138,258, and British Patent No. 1,146,368. Couplers whose colored dyes have excessive diffusivity include U.S. Patent No. 4,366,237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3,234,533 are preferred. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820; 4,080,211;
It is described in Patent No. 4,367,282, No. 4,409,320, No. 4,576,910, British Patent No. 2,102,173, etc. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are described in the patents described in the aforementioned RD 17643, Section VII-F,
Those described in JP-A-57-151944, JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, and US Pat. No. 4,248,962 are preferred. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,097,14
No. 0, No. 2,131,188, JP-A-59-1576
No. 38 and No. 59-170840 are preferred.

Other couplers that can be used in the photosensitive material of the present invention include US Pat. No. 4,130,42
Competitive couplers such as those described in U.S. Pat. No. 4,283, et al.
No. 472, No. 4,338,393, No. 4,310,6
Multi-equivalent coupler described in No. 18 etc., JP-A-60-18
D described in No. 5950, JP-A No. 62-24252, etc.
IR redox compound releasing couplers; DIR coupler releasing couplers; D. No. 11449, same 24
241, bleach accelerator-releasing couplers described in JP-A-61-201247, etc., ligand-releasing couplers described in U.S. Pat. No. 4,553,477, etc., JP-A-63-7
Examples include couplers that release leuco dyes as described in No. 5747. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. The boiling point at normal pressure used in the oil-in-water dispersion method is 175
Specific examples of organic solvents with high boiling points above °C include phthalic acid esters, esters of phosphoric acid or phosphonic acid, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, and aniline derivatives. , hydrocarbons, etc. In addition, as an auxiliary solvent, the boiling point is 30°C or higher, preferably 50°C or higher and about 160°C.
The following organic solvents can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexane, 2-ethoxyethyl acetate, diethyl formaldehyde, and the like. Specific examples of latex dispersion processes, effects, and latex for impregnation are described in U.S. Pat.
It is described in No. 230, etc.

The photosensitive material of the present invention has a total thickness of all hydrophilic colloid layers on the side having the emulsion layer of 28 μm or less,
In addition, the membrane swelling rate T1/2 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 T1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photographic Science and Engineering) by A. Green et al.
Photogr. Sci. Eng. ), Volume 19, No. 2,
It can be measured by using a swell meter (swell meter) of the type described on pages 124 to 129, and T1/2 is 90% of the maximum swollen film thickness reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. % is the saturated film thickness, and it is defined as the time required to reach the film thickness of T1/2. The membrane swelling rate T1/2 is
It can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions during coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen membrane pressure under the conditions described above according to the formula: (maximum swollen membrane pressure - membrane thickness)/film thickness.

The color photographic light-sensitive material according to the present invention has the above-mentioned RD. No. 17643, pages 28-29, and the same No. 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, indoaniline compounds of U.S. Pat. No. 3,342,597, Research Disclosure No. 14,850 and U.S. Pat.
, 13,924.
listed in the number.

The photosensitive material of the present invention is preferably in the form of a roll, which allows signals to be easily input to the magnetic recording layer when the film is transported in a camera or printer. In this roll-shaped film, the area of one frame of the exposed screen is 350
mm2 or more and 1200 mm2 or less, and the magnetic information recordable space is 15 mm2 or more than the area of 1 frame of the above screen exposure area.
% or more is preferable. Specifically, it is preferable to reduce the number of perforations per screen to less than 135 formats. It is particularly preferable that the number of perforations per frame is 4 or less.

[0038] Information is optically transmitted to the magnetic information recordable space using a light emitter such as an LED at a film swelling rate of T1/2.
can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions during coating. Further, the swelling rate is preferably 150 to 400%. The swelling ratio can be calculated from the maximum swollen membrane pressure under the conditions described above according to the formula: (maximum swollen membrane pressure - membrane thickness)/film thickness.

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. (Utility Model Application No. 58-67329, JP-A-58-18103
No. 5, No. 58-182634, Utility Model Application No. 58-1952
No. 36, U.S. Patent No. 4,221,479, Patent Application No. 1983
-57785, 63-183344, 63-3
No. 25638, Japanese Patent Application No. 1-21862, No. 1-253
No. 62, No. 1-30246, No. 1-20222, No. 1-21863, No. 1-37181, No. 1-331
No. 08, No. 1-85198, No. 1-172595,
No. 1-172593, No. 1-214895, U.S. Patent No. 4,846,418, No. 4,848,693,
(No. 4,832,275) Furthermore, the cartridge used in the present invention may be one mainly composed of synthetic plastic. Further, the cartridge may contain various antistatic agents.

[0040]

[Examples] The present invention will be explained in more detail with reference to specific examples below, but the invention is not limited to the examples unless it goes beyond the gist of the present invention.

(Evaluation Method) 1) Optical Density Measurement Using a spectrophotometer UV-2100 manufactured by Shimadzu Corporation, the spectral density of each sample was measured in the wavelength range of 400 nm to 700 nm. Let D be the maximum value of the spectral density in the wavelength range of 400 nm to 700 nm. 2) Gray degree measurement Based on the spectral density measurement results, the gray degree is defined by (gray degree)=Dmin/D (Dmin is the minimum value of spectral density at 400 to 700 nm). 3) C/N ratio measurement Each sample was measured with a track width of 1.5 mm and a head gap of 5.
After recording a recording density signal of 1000 bpi at a feed speed of 30 mm/s using a head capable of input/output of 1000 turns, the C/N ratio is calculated when the signal is read out using the same head at the same speed. Represented by S. 4) Measurement of average aggregate size Measurement was performed using MasterSizer manufactured by MALVERN. As the average agglomerate size, the weight average particle diameter was adopted.

Example 1 C with a length of 0.1 μm, a needle ratio of 8, and a holding force of 850 Oe.
Magnetic fine particles of o-containing γ ferric oxide were each dispersed using a sand grinder. The dispersion time was varied depending on the sample to create magnetic coating liquids with varying degrees of dispersion. The formulation of the magnetic coating liquid is as follows. magnetic material

10 parts by weight vinyl chloride copolymer acrylate (acid value 13, molecular weight 20,000, average acryloyl group content 2.8 pieces/molecule)

60 parts by weight urethane acrylate (acid value 10, molecular weight 10,000, average acryloyl group content 3 pieces/molecule)

40 parts by weight stearic acid
4
Part by weight Butyl stearate

4 parts by weight methyl ethyl ketone

800 parts by weight of the above coating solution is applied to the entire surface of a 120 μm thick transparent PET support using an extrusion coating method in different thicknesses. Before the coating solution dried, a treatment was performed using a cobalt magnet so that the magnetic material was sufficiently oriented. After drying the solvent, calendering was performed and the film was wound. D was measured using the support as a reference sample. Table 1 shows D, S, and gray degree. D
If it is 0.15 or less, there will be no problem photographically. Further, if S is 20 dB or more, there will be no practical problem in terms of magnetic properties. It is preferable that the gray degree is 0.70 or more. It can be seen that Sample 1-A has an average particle size of 0.1 μm and is almost dispersed into primary particles.

[0043]

[Table 1]

From Table 1, when the average aggregate size is smaller than 0.3 μm, D becomes larger than 0.15, the light transmittance decreases, and it cannot be used for photographic purposes. Furthermore, if the average aggregate size is larger than 10.0 μm, S becomes smaller than 20 dB, making magnetic recording impossible. Samples 1-C, 1-D, 1-E, 1-F, 1-G, 1 according to the present invention having an average aggregate size of 0.3 μm or more and 10 μm or less
-J, 1-N, 1-O, and 1-P have D of 0.15 or less and S of 20 dB or more, so it can be seen that they have excellent optical properties and magnetic properties. Among them, samples 1-E, 1-F, 1-G, 1-J, 1-N, and 1-O with an average aggregate size of 0.7 μm or more and 5 μm or less are D
is less than 0.05 and S is more than 25 dB, so
Especially excellent. Regarding the amount of applied magnetic material, samples 1-H with an average aggregate size of 2.0 μm to 1-
Among M, samples 1-I, 1-J, 1-K, and 1-L, which are 0.01 g/m2 or more and 3.0 g/m2 or less, are D
is 0.15 or less, S is 20 dB or more, and the optical characteristics are
It can be seen that the magnetic properties are excellent. It can be seen that the gray level increases as the average agglomerate size increases and approaches neutral gray. The gray degree is determined by the average agglomerate size, and when the average agglomerate size is 0.3 μm or more, it becomes 0.70 or more, which indicates that the gray degree is excellent.

Example 2 The magnetic material used in Example 1 was dispersed in the following dispersion formulation using a paint shaker. As in Example 1, the dispersion time was varied depending on the sample to create magnetic coating liquids with varying degrees of dispersion. magnetic material
100
Part by weight Cellulose triacetate (Mw: 80,000)
900 methylene chloride

3800 The above coating solution is applied to the entire surface of the cellulose tricetate support at various thicknesses using an extrusion coating method. Before the coating solution dried, a treatment was performed using a cobalt magnet so that the magnetic material was sufficiently oriented. After drying the solvent, calendering was performed and the film was wound. The S and D values of the obtained sample were measured in the same manner as in Example 1. The results are shown in Table 2. By using the magnetic material of the present invention with an average aggregate size of 0.3 μm or more and 10 μm or less (Samples 2-C to 2-K), it is possible to obtain a transparent magnetic recording layer with excellent optical properties and magnetic properties. I understand.

[0046]

[Table 2]

Example 3 Using the magnetic material of Example 1, the following magnetic liquid was prepared using a paint shaker. magnetic material

0.15 parts by weight Cellulose triacetate
10
．． 0 parts by weight triphenyl phosphate
1.0 parts by weight biphenyl diphenyl phosphate
0.6 parts by weight methylene chloride
79.5 parts by weight methanol
3.5 parts by weight n-butanol
5.8
Parts by weight The following dope solution was also prepared. cellulose triacetate
23.0 parts by weight triphenyl phosphate
2.3 parts by weight biphenyl diphenyl phosphate
1.3 parts by weight Methylene chloride

65.7 parts by weight methanol

2.9 parts by weight n-butanol
A 4.8 parts by weight dry film was co-cast on a casting band using a composite slit die so that the thickness of the magnetic liquid was 5 μm and the dope liquid was 110 μm, and the magnetic liquid was the upper layer. It was filmed. Using these samples as supports, a multilayer color photosensitive material was coated in exactly the same manner as the photosensitive layer described in Example 1 of JP-A-2-93,641. At this time, with the magnetic recording layer as the back surface,
After glow discharge treatment was performed on the opposite side, the above photosensitive layer was applied in multiple layers. The layer structure of the photosensitive layer is shown in FIG. Sample X is a sample in which only a sensitive material is coated without providing a magnetic recording layer.

[0048] Sample Processed. These samples were developed as follows. Color development 3 minutes 15 seconds bleaching
Wash with water for 6 minutes and 30 seconds
Fixed for 2 minutes and 10 seconds
4 minutes 20 seconds washing with water 3 minutes 1
Stable for 5 seconds 1 minute 05 seconds The composition of the treatment liquid used in each step was as follows. Color developer diethylenetriaminepentaacetic acid 1.0
g1-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
Add 1.3 g hydroxylamine sulfate 2.4 g 4-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate 4.5 g water
1.0 lpH 10.0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g
Ammonium bromide 1
50.0 g ammonium nitrate
Add 10.0 g water
1.0 l
pH 6.0 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0 g
sodium sulfite
4.0 g ammonium thiosulfate aqueous solution (70%
) 175.0 ml sodium bisulfite
Add 4.6 g water
1.0
lpH 6.6 Stabilized liquid formalin (40%)
2.0ml polyoxyethylene-p-
Monononylphenyl ether (average degree of polymerization 10
) Add 0.3 g water
1.0 l

Using sample X as a reference sample, the spectral density of the obtained sample was measured. Further, S was also measured, and the results for D and S were exactly the same as in Example 2.

Example 4 Particle size 0.07 μm, plate ratio 5, holding power 900 Oe
Hexagonal plate-shaped barium ferrite magnetic fine particles were dispersed using a sand grinder according to the following formulation. By varying the dispersion time in the sand grinder, aggregates with different particle sizes were created. Sample 4-A uses magnetic fine particles that have not been subjected to this operation. The average aggregate size of the magnetic material is as shown in Table 3. magnetic material

10 parts by weight vinyl chloride copolymer acrylate (acid value 13, molecular weight 20,000, average acryloyl group content 2.8 pieces/molecule)

60 parts by weight urethane acrylate (acid value 10, molecular weight 10,000, average acryloyl group content 3 pieces/molecule)

40 parts by weight stearic acid
4
Part by weight Butyl stearate

4 parts by weight methyl ethyl ketone

The thickness of 800 parts by weight of the above coating liquid was changed to 110 parts by weight.
Coating is performed on the entire surface of a transparent cellulose triacetate support of μm size using an extrusion coating method. Before the coating solution dried, a treatment was performed using a cobalt magnet so that the magnetic material was sufficiently oriented. After drying the solvent, calendering was performed and the film was wound. S for each sample
and D were evaluated. The results are shown in Table 3. It can be seen that Sample 4-A is almost dispersed into primary particles.

[0051]

[Table 3]

As can be seen from Table 3, even when the magnetic material is Ba ferrite, the average aggregate size of the present invention is 0.3μ.
m or more and 10 μm or less, the magnetic material has a D of 0.15 or less,
Moreover, S is 20 dB or more, indicating that both optical properties and magnetic properties are excellent. In particular, the average agglomerate size is 0.
When it is 7 μm or more and 5 μm or less, D is 0.05 or less,
It can be seen that S is 25 dB or more, which is particularly excellent. The gray degree in the case of Ba ferrite was 0.70 or more for all samples.

[0053]

[Effects of the invention] 1. By using the magnetic material of the present invention,
It becomes possible to obtain a silver halide photographic material having a magnetic recording layer having excellent transparency to visible light and excellent magnetic output reproduction characteristics.

[Brief explanation of drawings]

FIG. 1 shows a multilayer color photosensitive layer as described in Example 3.

[Explanation of symbols]

1...Support 2… Anti-halation layer 3… Middle class 4...First red-sensitive emulsion layer 5… Second red-sensitive emulsion layer 6…Third red-sensitive emulsion layer 7… Middle class 8...First green-sensitive emulsion layer 9... Second green emulsion layer 10...Third green emulsion layer 11...Yellow filter layer 12... First blue-sensitive emulsion layer 13... Second blue-sensitive emulsion layer 14…Third blue-sensitive emulsion layer 15... First protective layer 16…Second protective layer

Claims (5)

[Claims] Claim 1. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a film support and at least one transparent magnetic recording layer, wherein the magnetic recording layer includes: A silver halide photographic light-sensitive material, characterized in that the weight average particle diameter of the magnetic substance aggregates contained is 0.3 μm or more and 10 μm or less. 2. The silver halide photographic material according to claim 1, wherein the weight average particle diameter of the aggregate of the magnetic fine particles is 0.7 μm or more and 5 μm or less. [Claim 3] The content of the magnetic substance is 0 per 1 m2.
．． 3. The silver halide photographic material according to claim 1, wherein the silver halide photographic material has a weight of 01 g or more and 3.0 g or less. 4. The silver halide photographic material according to claim 3, wherein the magnetic recording layer has a maximum spectral density in the visible range of 0.15 or less. 5. The silver halide photographic material according to claim 4, wherein the gray degree of the magnetic recording layer defined by the following formula is 0.70 or more. (Gray degree)=Dmin/Dmax (Here, Dmax represents the maximum value of spectral density in the visible range of the magnetic recording layer, and Dmin represents the minimum value of spectral density in the visible range of the magnetic recording layer.)