JPH0777759A - Photographic sensitive material having transparent magnetic recording layer - Google Patents

Abstract

PURPOSE:To prevent attachment of foreign matter causing errors on the surface of the photographic sensitive material and occurrence of read errors of magnetic signals by incorporating anionic and cationic fluorinated surfactants in the side of the transparent magnetic recording layer. CONSTITUTION:The side of the transparent magnetic recording layer contains the anionic and cationic fluorinated surfactants each represented, preferably, by formulae I and II in which Cf is a fluorinated a- valent group having 2 carbon atoms; Y is -COOM,-SO3M, or the like; M is a cation, such as an H, alkali metal, or ammonium cation; (a) is 1 or 2; Rh is a 1-20 C hydrocarbon group substituted for one of H atoms by an F atom; T is a simple chemical bond or a divalent group; X is a cation; and Z is a counter anion.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION For photographic light-sensitive materials, various information on photographic light-sensitive materials such as type / manufacturing number of photographic light-sensitive material, manufacturer's name, emulsion No., etc. Conditions, filters used, weather, shooting frame size, camera model, various information at the time of camera shooting such as use of anamorphic lens, for example, number of prints, selection of filter, customer's color preference, Various information necessary for printing, such as the size of the trimming frame,
For example, inputting various information obtained at the time of printing such as the number of prints, selection of filters, customer's color preference, size of trimming frame, and other customer information is important for management. It is also necessary to improve print quality and improve the efficiency of printing work.

In a conventional photographic light-sensitive material, it is impossible to input all the information, and
At the time of shooting, I was only optically entering information such as the shooting date / time, aperture, and exposure time. Moreover, at the time of printing, it was completely impossible to input the above information into the photographic light-sensitive material because there was no means for that.

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

For example, a stripe-shaped magnetic recording layer in which fine particles of ferromagnetic material are dispersed is provided on the emulsion surface or the back surface next to the image area, and information such as sound and photographing conditions is provided to the silver halide photographic material. Recording on material is disclosed in JP-A-50-626.
No. 27, No. 49-4503, U.S. Pat.No. 3,243,376, No. 3,220,843, etc., and also on the back surface of the silver halide photographic light-sensitive material, the amount of magnetizable particles, size, etc. Providing a transparent magnetic recording layer having the required transparency by selecting (1) is described in US Pat. Nos. 3,782,947, 4,279,945, and 4,302,523. Also, US Pat. No. 4,947,196 and WO90 / 04254 describe a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material that enables magnetic recording on the back surface of the photographic film. Has been done.

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

Conventionally, as a method of providing a magnetic recording layer to a photographic light-sensitive material, a method of providing a magnetic recording layer in a stripe shape outside a photographing screen area as represented by a movie film, and an optically transparent magnetic recording method. Two methods of providing a layer on the entire surface of the photographic light-sensitive material have been studied.

The latter photographic light-sensitive material having a transparent magnetic recording layer has the transparency necessary for the photographic light-sensitive material by, for example, appropriately selecting the amount and size of the magnetizable particles contained in the magnetic recording layer. Further, a magnetic recording layer that does not adversely affect the granularity is provided on the back surface of the photographic light-sensitive material having a transparent support. Specifically, U.S. Pat.
782,294, 4,279,945, 4,302,523
It is described in the specification etc. A signal input method to the magnetic recording layer is disclosed in WO90 / 04205 and 90/0421.
It is disclosed in Japanese Patent Publication No. 2 etc.

The photographic light-sensitive material having these transparent magnetic recording layers is subjected to development processing after printing and printing. Some photographic light-sensitive materials photographed are manually developed, but most of the photographic light-sensitive materials are developed through various rollers by an automatic processor in the laboratory. The cleanliness in the laboratory is higher than the manual development process, but it is significantly inferior to the cleanliness in the manufacturing process of photographic light-sensitive materials.
The processing agent in the developing solution is transferred to the transfer roller as the film is transferred, and many foreign substances adhere to the surface of the photographic photosensitive material. Even if these foreign matters have no problem in printing on the photosensitive material, if these foreign matters adhere to the magnetic recording surface, there is a problem in that an error occurs in writing and reading magnetic information.

Further, the developed photographic light-sensitive material is reprinted or reprinted several times using it, but these developed photographic light-sensitive materials are often handled with bare hands. , Dust that is on your hands adheres to the photographic material, or fingerprints are attached. These also cause an error in writing and reading magnetic information.

In order to prevent dust from adhering to the photographic light-sensitive material and fingerprints on the photographic light-sensitive material, it has been devised to put the developed photographic light-sensitive material in a cartridge or the like so that a person does not directly touch it. However, another problem of discarding an unnecessary cartridge occurs, and there is also a problem in preventing the adhesion of foreign matter by putting the photographic light-sensitive material in the cartridge or the like.

Therefore, there has been a demand for the appearance of a photographic light-sensitive material which is prevented from adhering foreign matter which causes an error in writing and reading magnetic information on the surface of the photographic light-sensitive material, particularly on the magnetic recording surface side.

[0013]

The object of the present invention is to provide a surface of a photographic light-sensitive material,
In particular, it is to provide a photographic light-sensitive material in which the adhesion of foreign matter that causes an error in writing and reading magnetic information on the magnetic recording surface side is prevented.

[0014]

The above objects can be achieved by the following photographic light-sensitive materials. (1) In a photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support and a transparent magnetic recording layer on the other side, an anionic fluorine-based interface is provided on the transparent magnetic recording layer side. A photographic light-sensitive material comprising an activator and a cationic fluorine-based surfactant. (2) The photographic light-sensitive material as described in (1) above, wherein the support has a thickness of 40 to 115 μm.

The present invention will be described in more detail below.

First, the transparent magnetic recording layer will be described.

The magnetic fine powder used in the magnetic recording layer of the present invention includes metal magnetic powder, iron oxide magnetic powder, and C.
O-doped iron oxide magnetic powder, chromium dioxide magnetic powder,
A barium ferrite magnetic substance powder or the like can be used.

The method for producing these magnetic powders is known,
The magnetic powder used in the present invention can also be manufactured according to a known method.

The shape and size of the magnetic powder can be widely used without any particular limitation. As the shape, needle shape, rice grain,
It may have any shape such as a spherical shape, a cubic shape, or a plate shape, but a needle shape or a plate shape is preferable in terms of electromagnetic conversion characteristics. The crystallite size and specific surface area are not particularly limited. The magnetic powder may be surface-treated. For example, it may be surface-treated with a substance containing an element such as titanium, silicon or aluminum, or may be adsorbed with a nitrogen-containing heterocycle such as carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester or benzotriazole. It may be treated with an organic compound such as a polar compound. The pH of the magnetic powder is not particularly limited, but is preferably in the range of 5-10.

As the metal magnetic powder, for example, the metal content is 75% by weight or more, and 80% by weight or more of the metal content is a ferromagnetic metal or alloy (Fe, Co, Ni, Fe-Co, F).
e-Ni, Co-Ni, Co-Fe-Ni, etc., and other components (Al, Si, S, Sc, etc.) at 20% by weight or less.
Ti, V, Cr, Mn, Cu, Zn, Y, Mo, Rh,
Pd, Ag, Sn, Sb, B, Ba, Ta, W, Re,
Au, Hg, Pb, P, La, Ce, Pr, Nd, T
e, Bi, etc.) are included. Further, the ferromagnetic metal component may contain a small amount of hydroxide or oxide.

Examples of the iron oxide of the iron oxide magnetic material and the Co-doped iron oxide magnetic material include γ-iron oxide.
The ratio of divalent iron / trivalent iron in these iron oxides is not particularly limited.

Regarding these magnetic recording layers, Japanese Patent Laid-Open No.
-32812 and 53-109604.

Regarding the size of magnetic particles, it is "television" that there is a correlation between the size and the transparency.
Volume 20, No. 2, "Characteristics of Ultrafine Particle Semitransparent Magnetic Recording Material and Its Application". For example, in the acicular powder of γ-Fe ₂ O ₃ , the light transmittance is improved by reducing the particle size.

US Pat. No. 2,950,971 describes that a magnetic layer of magnetic iron oxide dispersed in a binder is transparent to infrared radiation. US Pat.
No. 9,945 describes that when the particle size is reduced, the wavelength is increased even when the concentration of magnetic particles in the magnetic layer is relatively high.
It is described that the transmittance of 632.8 nm helium / neon laser light is improved.

However, when the magnetic recording layer is provided in the image forming region of the silver halide color photographic light-sensitive material, not only the red region but also the green region and the blue region must have high light transmittance.

In order to increase the light transmittance in the red region, the green region and the blue region, the particle size of the magnetic particles is reduced and the coating amount of the magnetic particles is also limited.

If the particle size of the magnetic particles is reduced to a certain extent or more, the required magnetic characteristics cannot be obtained. Therefore, it is preferable to make the particle size of the magnetic powder small within the range where the required magnetic characteristics are obtained. Further, if the coating amount of the magnetic particles is reduced to a certain extent or more, the required magnetic characteristics cannot be obtained, so it is preferable to reduce the coating amount within the range where the required magnetic characteristics are obtained.

Practically, the coating amount of the magnetic powder is 0.001
A to 3 g / m ^2, more preferably from 0.01 to 1 g / m ^2, particularly preferably 0.2 g / m ² or less.

As the binder used in the magnetic recording layer, known thermoplastic resins, radiation-curable resins, thermosetting resins, and other reactive resins conventionally used as binders for magnetic recording media are used. Mixtures of can be used.

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

The above-mentioned thermoplastic resin has a Tg of -40 ° C to 150 ° C.
C., preferably 60.degree. C. to 120.degree. C., and the weight average molecular weight is preferably 5,000 to 300,000, more preferably 10,000 to 200,000.

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

Examples of thermosetting resins and other reactive resins include phenolic resins, amino resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, and silicone-based curable resins.

The binders listed above may have polar groups in their molecules. The polar group is an epoxy group, -C
_{OOM, -OH, -NR 2, -NR} 3 X, -SO 3 M, -
_{OSO 3 M, -PO 3 M 2} , -OPO 3 M (M each hydrogen, an alkali metal, an ammonium, X is a counter ion to form a quaternary ammonium salt, R represents each represent hydrogen, an alkyl group.) And so on.

A hydrophilic binder may also be used as the binder of the magnetic recording layer of the present invention.

The hydrophilic binder usable in the present invention is, for example, Research Disclosure No. 1764.
Examples thereof include water-soluble polymers, cellulose ethers, latex polymers and water-soluble polyesters described on pages 3, 26, and No. 18716, page 651.

As the water-soluble polymer, gelatin, gelatin derivative, casein, agar, sodium alginate, starch, polyvinyl alcohol, acrylic acid type copolymer,
Examples thereof include maleic anhydride copolymers, cellulose ethers such as carboxymethyl cellulose and hydroxyethyl cellulose, and latex polymers such as vinyl chloride copolymers, vinylidene chloride copolymers and acrylic ester copolymers. Examples of the latex include polymers, vinyl acetate-based copolymers and butadiene-based copolymers. Of these, gelatin is the most preferable.

The gelatin may be unmodified or modified. Further, a part thereof is colloidal albumin, casein, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids, for example,
It may be replaced with polyvinyl alcohol, poly N-vinylpyrrolidone, an acrylic acid-based copolymer, polyacrylamide or a derivative thereof, a partial hydrolyzate, a gelatin derivative or the like.

The hydrophilic binder containing gelatin is preferably hardened. Examples of hardeners that can be used include
Aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2
-Hydroxy-4,6-dichloro-1,3,5-triazine, U.S. Pat. Nos. 3,288,775, 2,732,303, British Patent 974,723, 1,167,207, etc. Reactive halogen-containing compounds, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, U.S. Pat. Nos. 3,635,718, 3,232,763, and British Patent Compounds having a reactive olefin described in 994,869, etc., N-hydroxymethylphthalimide, US Pat. Nos. 2,732,316, 2,586,1
N-methylol compounds described in 68, etc., isocyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017,280,
2,983,611 and other aziridine compounds, U.S. Pat.No. 2,725,294, and 2,725,295
Acid derivatives described in U.S. Pat.
Examples thereof include epoxy compounds described in 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Inorganic hardeners can also be used, and examples of the inorganic hardeners include chrome alum and zirconium sulfate.
Japanese Patent Publication No. 58-32699, Belgian Patent No. 825,726, Japanese Patent Publication No. 60-225148, Japanese Patent Publication No. 51-126125, Japanese Patent Publication No. 58-50699, Japanese Patent Publication No. 52-54427. The carboxyl group-activating type hardeners described in Japanese Patent Publication No. 3,321,313 and the like can also be mentioned.

Hardeners are typically 0.
It is used in an amount of 01 to 30% by weight, preferably 0.05 to 20% by weight.

The magnetic powder is dispersed in the binder using a solvent if necessary to form a coating liquid. A ball mill, homomixer, sand mill, or the like can be used to disperse the magnetic powder. In this case, it is preferable to disperse the magnetic particles one by one as much as possible without damaging the magnetic particles.

When forming an optically transparent magnetic recording layer, the binder is preferably used in an amount of 1 to 50 parts by weight per 1 part by weight of the magnetic powder. More preferably, magnetic powder
It is 2 to 30 parts by weight with respect to 1 part by weight. Further, the solvent is used in such an amount that the coating can be easily performed.

As the method for providing the magnetic recording layer on the support, air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, A spray coat can be used. In order to perform multi-stripe coating, these coating heads may be arranged in multiple rows. Specific methods of stripe coating include, for example, JP-A-48-25503, JP-A-48-25504, JP-A-48-98803, and JP-A-50-13803.
7, gazette 52-15533 gazette, gazette 51-3208 gazette, gazette 51-6
No. 239, No. 51-65606, No. 51-140703, Japanese Patent Publication No. 29-4221, U.S. Pat.No. 3,062,181, the same.
The description in the specification of 3,227,165 can be referred to.

A support having a magnetic recording layer may be prepared by co-casting a solution of a binder in which magnetic particles are dispersed and a solution of a polymer for forming the support. in this case,
The binder that disperses the magnetic particles is preferably substantially the same as the polymer for forming the support. The support on which the magnetic recording layer is formed by co-casting may be stretched in order to satisfy mechanical strength, dimensional stability and the like.

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

The thickness of the magnetic recording layer is preferably 0.05 to 10 μm, more preferably 0.1 to 5 μm, and even more preferably 0.1.
It is 5 to 3 μm.

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to provide the magnetic recording layer with functions such as imparting lubricity, preventing electrification, preventing adhesion, and improving friction and abrasion characteristics. Various additives such as agents can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and for preventing clogging of the magnetic head. Abrasives can be added. The above-mentioned functions such as lubricity, antistatic, adhesion prevention, friction / abrasive property improvement, and magnetic head clogging prevention may be provided by providing these functional layers separately from the magnetic recording layer. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance. When the magnetic recording layer is provided in a stripe shape, a transparent polymer layer containing no magnetic material may be provided thereon to eliminate the step due to the magnetic recording layer.
In this case, the transparent polymer layer may have various functions described above.

Examples of lubricants include silicone oils such as polysiloxane, fine plastic powders such as polyethylene and polytetrafluoroethylene, higher fatty acids, higher fatty acid esters, and fluorocarbons.
These may be used alone or in combination.
These may be added in an amount of 0.2 to 20 parts by weight with respect to 100 parts by weight of the binder.

Examples of the abrasive include non-magnetic inorganic powders having a Mohs hardness of 5 or more, preferably 6 or more. Specifically, aluminum oxides (α-alumina, γ-alumina, corundum, etc.), Examples thereof include chromium oxide (Cr ₂ O ₃ ), iron oxide (α-Fe ₂ O ₃ ), oxides such as silicon dioxide and titanium dioxide, carbides such as silicon carbide and titanium carbide, and fine powder such as diamond. The average particle diameter of these is preferably 0.05 to 1.0 μm, and can be added in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the magnetic powder.

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

In the present invention, various supports can be used as the support. As the support that can be used, a film of polyester such as polyethylene terephthalate or polyethylene naphthalate, a cellulose triacetate film, a cellulose diacetate film, a polycarbonate film, a polystyrene film, a polyolefin film, a reaction of pyromellitic acid or its anhydride with a diamine, etc. The obtained polyimide film, polyethylene laminated paper, etc. can be mentioned.

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

In particular, from the curl and curl recovery after development processing, JP-A 1-244446, 1-291248, 1-298350, 2-89045, 2-93641, Ibid 2-181749
It is preferable to use a polyester having a high water content as shown in JP-A Nos. 2-214852 and 2-291135.

These polyesters may have a polar group and other substituents.

When a polyimide film is used as the support, the polyimide is colored and therefore it is necessary to make it thinner to obtain the required light transmission amount.

As the support in the present invention, cellulose triacetate, polyethylene terephthalate, polyethylene naphthalate and polyimide are preferable.

The above polyester has an area ratio in order to satisfy the mechanical strength and dimensional stability of the film support.
Stretching is preferably performed in the range of 4 to 16 times.

The support of the present invention includes a matting agent, an antistatic agent, a lubricant, a surfactant, a stabilizer, a dispersant, a plasticizer, an ultraviolet absorber, a conductive substance, a tackifier, a softening agent and a fluidity. Additives, thickeners, antioxidants and the like can be added.

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

The type of dye used is not particularly limited, but when a polyester film is used as a support,
In the film forming process, those having excellent heat resistance are preferable, for example,
Examples include anthraquinone-based chemical dyes. Also, as the color tone, if the purpose is to prevent light piping,
Gray dyeing is preferable as seen in general light-sensitive materials. As the dye, one kind or a mixture of two or more kinds may be used. The target can be achieved by using dyes such as Diaresin manufactured by Mitsubishi Kasei Co., Ltd. and MACROLEX manufactured by Bayer Co. alone or in an appropriate mixture.

Next, the anionic fluorochemical surfactant and the cationic fluorochemical surfactant used in the present invention will be described.

First, the anionic fluorine-based surfactant used in the present invention will be described. The anionic fluorosurfactant used in the present invention may be any one and is not particularly limited, but as the anionic fluorosurfactant preferably used in the present invention, the following general formula [F
A-1] can be mentioned.

[0063]

[Chemical 1] [In the formula, Cf has fluorine as a substituent, and at least 2
Represents a valent group containing C carbon atoms, Y is —COOM,
-SO ₃ M, -ΟSО ₃ M or -O-P (= O) ( OM) 2
(M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt). a is l or 2
Represents ] A more preferable anionic fluorine-based surfactant is a compound represented by the following general formula [FA-2].

[0064]

[Chemical 2] [In the formula, Rf represents a fluorine-substituted hydrocarbon group having 3 to 30 carbon atoms. D is -O-, -COO-, -COO-, -CO
N (R ₁₎ - or _{-SО 2 N (R 1) -} (R 1 represents an alkyl group having 1 to 5 carbon atoms.) At least a composed bond
1 represents a divalent group having 1 to 12 carbon atoms, and t represents 1 or 2. Y is -COO M, -S O ₃ M, -OSO ₃ M
Alternatively, it represents -OP (= O) (ΟM) ₂ (M represents a hydrogen atom or a cation such as an alkali metal or a quaternary ammonium salt). ] Of these, particularly preferred is −
An anionic fluorine-based surfactant having at least one bond of SO ₂ N (R ₁ )-.

Next, specific examples of the anionic fluorochemical surfactant used in the present invention will be given, but the anionic fluorochemical surfactant of the present invention is not limited to these.

[0066]

[Chemical 3]

[0067]

[Chemical 4]

[0068]

[Chemical 5]

[0069]

[Chemical 6]

[0070]

[Chemical 7]

[0071]

[Chemical 8]

Next, the cationic fluorine-based surfactant used in the present invention will be described. The cationic fluorosurfactant used in the present invention may be any one and is not particularly limited, but as the cationic fluorosurfactant preferably used in the present invention, the following general formula [F
K] can be mentioned.

[0073]

[Chemical 9] [In the formula, Rh represents a hydrocarbon group having 1 to 20 carbon atoms, and at least one hydrogen atom therein is substituted with a fluorine atom. T represents a chemical bond or a divalent group. (X) represents a cationic group, and Z represents a counter anion. ] Examples of the Rh _{is, C n F 2n + 1 -} (n represents 1 to 10, particularly preferably _{3~12.), HC m F 2m} -, H 2 C m F
_{2m-1 -, H 3 C} 3m F 6m-1 - (m represents 1-4.), And the like.

As an example of T, -SO₂N (R ')
-(CH₂)_p-, -CONR '-(CH₂)_p-, -O-
A'-SΟ₂NR '-(CH₂)_p-, -OA-CON
R '-(CH₂)_p-, -O-A'-O- (CH₂)_p-, -O
-A '-(CH₂)_p-, -O- (CH₂CH₂O)_q-(CH₂)
_p-, -O- (CH₂)_p-, -NR '-(CH₂)_p-, -S
O₂N (-R ')-(CH₂)_p-O-, -CONR '-(CH
₂)_p-O-, -OA-SO₂NR '-(C (-R')
H )_p-OA'-, (R 'is a hydrogen atom, having 1 to 6 carbon atoms
Represents alkyl, the alkyl group having an -OH group,
Good. p represents 0-6. A'is an alkylene group, ant
Represents a len group. q represents 1 to 20. ) Etc.
be able to.

As an example of the above (X),

[0076]

[Chemical 10] And so on.

As an example of Z,

[0078]

[Chemical 11] And so on.

Specific examples of the cationic fluorinated surfactant used in the present invention are shown below, but the cationic fluorinated surfactant of the present invention is not limited to these.

[0080]

[Chemical 12]

[0081]

[Chemical 13]

[0082]

[Chemical 14]

In the present invention, it is particularly preferable to use a poorly soluble sulfonamide type cationic fluorosurfactant in the same layer together with an anionic fluorosurfactant. The term “poorly soluble” refers to the one in which 2 g of the above surfactant was added to 100 cc of water at 23 ° C., the mixture was stirred for 1 hour and left at 23 ° C. for 24 hours to form a precipitate or a floating substance was observed. Whether it is poorly soluble can be easily determined by the above test. Of the above specific examples, FK-1, F
K-8, FK-15, FK-16 and the like are poorly soluble.

Examples of the anionic fluorine-based surfactant or the cationic fluorine-based surfactant used in the present invention include, in addition to the above specific examples, for example, US Pat. Nos. 2,559,751 and 2,567,0ll, and No. 2,732,398, the same
2,764,602, 2,806,866, 2,809,99
No. 8, No. 2,9l5,376, No. 2,915,528, No. 2,934,450, No. 2,937,098, No. 2,
957,031 specification, 3,472,894 specification, 3,555,089
No. 2,918,501, British Patent No. 1,143,927, No. 1, l30,822, Japanese Patent Publication No. 45-37304, Japanese Patent Publication No. 47-9613, No. 50-l21243. , 50-1
No. 17705, No. 49-134614, No. 50-117727, No. 52-41182, No. 51-12392, British Chemical Society (J. Chem. Soc.) L950, page 2789, the same. 1957 p. 2574 and 2640, American Chemical Society Journal (J. Amer. Chem. Soc.) Vol. 79, p. 2549 (1957), Oil Chemistry (J. Japan. Oil Chemists S
oc.) Vol. 12, p. 653, Journal of Organic Chemistry (J.0rg. Chem.) No. 30
The compounds described in Volume 3524 (l965) and the like can be mentioned.

Some of the anionic fluorine-based surfactants and the cationic fluorine-based surfactants used in the present invention are commercially available, and these commercially available products can also be used. Commercially available products include, for example, Megafac F from Dainippon Ink and Chemicals, Fluorad FC from Minnesota Mining and Manufacturing Company, Monflor and Ei DuPont from Imperial Chemical Industries. EIDupont) You can use Zonyls from Nemeras and Company or Licowet VPF from Farbeberke Hoechst.

The total content of the cationic fluorochemical surfactant and the anionic fluorochemical surfactant used in the present invention is usually 0.1 to 1,000 mg per 1 m ² , and preferably 1 to 300 mg. , And more preferably 4 to 100 mg.

Further, in the present invention, two or more kinds of the cationic fluorosurfactant and the anionic fluorosurfactant may be used in combination. In addition, a nonionic fluorine-based surfactant, a betaine fluorine-based surfactant, and a hydrocarbon-based surfactant can be used in combination.

In the present invention, the addition ratio of the anionic fluorine-based surfactant to the cationic fluorine-based surfactant is preferably 1:10 to 10: 1 and more preferably 3: 7 to 7: 3 is preferred.

In the present invention, the fluorine-based anionic surfactant and the fluorine-based cationic surfactant are present on the side where the magnetic recording layer is present, and more preferably on the outermost layer. In order to make it exist in the outermost layer, it may be added to the coating solution for forming the outermost layer and then coated, or the outermost layer may be overcoated with this compound.

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

Any silver halide can be used as the silver halide of the silver halide emulsion, for example, silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide. , Silver chloroiodobromide, which is appropriately selected depending on the required performance, but silver bromide and silver iodobromide are preferred from the viewpoint of obtaining high sensitivity.

The silver halide grain contained in the silver halide photographic emulsion to be used may be a grain in which a latent image is mainly formed on the surface, or a grain in which a latent image is mainly formed inside the grain. .

The silver halide grains may have a regular crystal form such as a cube, octahedron or tetradecahedron,
It may have an irregular crystal shape such as a sphere or a plate. In these particles, (100) plane and (111) plane
Any surface ratio can be used. Further, it may have a composite form of these crystal forms, and grains of various crystal forms may be mixed, but twin silver halide grains having two parallel twin planes facing each other are preferable. .

A twin is a silver halide crystal having one or more twin planes in one grain. The morphology of twins is classified by Klein and Moiser in the report Photographiesche Correspondents. (Photographishe Korrespondenz)
Volume 99, page 99, volume 100, page 57.

In the present invention, when tabular silver halide grains are used, the average ratio of the diameter to the thickness of tabular grains (also referred to as aspect ratio) is preferably less than 5, but more preferably 1.1 or more. Less than 4.5, particularly preferably
It is 1.2 or more and less than 4. This average value is obtained by averaging the ratio of diameter to thickness of all tabular grains.

The diameter of the silver halide grain is indicated by the circle equivalent diameter of the projected area of the silver halide grain (the diameter of the circle having the same projected area as the silver halide grain),
The thickness is preferably 5.0 μm, more preferably 0.2 to 4.0 μm, and particularly preferably 0.3 to 3.0 μm.

As the silver halide photographic emulsion, any one such as a polydisperse emulsion having a wide grain size distribution and a monodisperse emulsion having a narrow grain size distribution can be used, but a monodisperse emulsion is preferable.

As the monodisperse silver halide emulsion,
It is preferable that the weight of silver halide contained in the grain size range of ± 20% around the average grain size r is 60% or more, more preferably 70% or more, and still more preferably the weight of all silver halide grains. 80% or more.

[0099] Here, the average particle diameter r is the product ni × ri ³ of the frequency ni and ri ³ particles having a particle size ri is defined as the particle size ri when the maximum.

Particle size r here i is a silver halide grain
Convert the projected image of the silver halide grains of the child into a circular image of the same area.
It is the diameter when

Particle size r i is, for example, an electron microscope of the particles.
The image is magnified 10,000 to 70,000 times, and the particles are printed directly on the print.
It can be obtained by measuring the diameter or the area at the time of projection.
Yes (the number of particles measured must be 1,000 or more indiscriminately)
And ).

Particularly preferred highly monodisperse emulsions of the present invention are:

[0103]

[Equation 1] When the breadth of distribution is defined by, the breadth of the distribution is 20%
It is the following, and more preferably 15% or less.

The average particle size and standard deviation are obtained from the particle size ri defined above.

In the present invention, when silver iodobromide is used as the silver halide, the content of the silver iodide is 4 mol% or more and 15 mol or more as an average silver iodide content in the entire silver halide grains. % Or less, more preferably 5 mol% or more and 12 mol% or less, and particularly preferably 6 mol% or more and 10 mol% or less.

The silver halide grains contained in the silver halide photographic emulsion are preferably so-called core / shell type grains in which silver iodide is concentrated.

The core / shell type particle is a particle composed of a core serving as a core and a shell covering the core, and the shell is formed of one layer or more layers. The silver iodide contents of the core and the shell are preferably different from each other, and it is particularly preferable that the silver iodide contents of the core portions are maximized.

The silver iodide content of the above core is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 25 mol% or more. The silver iodide content of the outermost shell of the above shells, that is, the shell usually forming the outermost surface layer is preferably 5 mol% or less, more preferably 0 to 2 mol%. The proportion of the core is preferably 2 to 60% of the total volume of the particles, and more preferably 5 to 50%.

The silver halide grains contained in the silver halide photographic emulsion are prepared by preliminarily allowing an aqueous solution containing a protective colloid such as gelatin and seed particles to be present in a reaction vessel and, if necessary, silver ions, halogen ions or silver halide fine grains. Can be obtained by growing the seed particles to grow crystals. Here, the seed particles can be prepared by a single jet method or a controlled double jet method well known in the art. The halogen composition of the seed grains is arbitrary and may be any of silver bromide, silver iodide, silver chloride, silver iodobromide, silver chlorobromide, silver chloroiodide and silver chloroiodobromide. Silver bromide and silver iodobromide are preferred.

When seed grains are used for preparing a silver halide emulsion, the seed grains may have a regular crystal form such as a cube, octahedron or tetradecahedron, or may have a spherical or plate shape. It may have an irregular crystal form. In these particles, any ratio of (100) plane to (111) plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed,
It is preferable to use the monodisperse spherical seed particles described in Japanese Patent Application No. 2-408178.

The silver halide photographic emulsion can be produced by any of the acidic method, the neutral method and the ammonia method.

In the production of silver halide photographic emulsion,
The halide ion and the silver ion may be mixed at the same time, or the other may be mixed in the presence of either one. Also,
It may be grown by adding halide ions and silver ions successively or simultaneously while controlling the pH and pAg in the mixing vessel while taking into consideration the critical growth rate of silver halide crystals. The conversion method may be used to change the silver halide composition of the grains at any step of the silver halide formation. Further, halide ions and silver ions may be supplied as fine silver halide particles into the mixing vessel.

In the production of silver halide photographic emulsion,
Known silver halide solvents such as ammonia, thioether, thiourea and the like can be present.

The silver halide grains contained in the silver halide photographic emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), Rhodium salt (including complex salt)
And at least one selected from iron salts (including complex salts) can be used to add a metal ion so that these metal elements can be contained inside and / or on the surface of the particles, and the particles are placed in a suitable reducing atmosphere. By this, reduction sensitization nuclei can be imparted to the inside of the grain and / or the surface of the grain.

In the silver halide photographic emulsion, unnecessary soluble salts may be removed after the completion of the growth of silver halide grains, or may be contained. When removing the salts, Research Disclosure (Research D
isclosure, hereinafter abbreviated as RD. ) It can be carried out based on the method described in No. 17643, Section II.

Conditions other than those mentioned above in the production of the silver halide photographic emulsion according to the present invention are described in JP-A-61-6643.
No. 61, No. 61-14630, No. 61-112142, No. 62-
No. 157024, No. 62-18556, No. 63-92942,
63-151618, 63-l63451, 63-220238.
The optimum conditions can be selected with reference to known methods such as Japanese Patent Publication No. 63-311244 and Japanese Patent Publication No. 63-311244.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are RD No.17643, RD No. 18716 and RD No.
No. 308119 (Respectively RDl7643, RDl8716 and RD308
Abbreviated as 119. )It is described in. Table 1 shows the locations.

[0118]

[Table 1] When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, photographic additives that can be used are described in the above RD. Table 2 shows the relevant locations.

[0119]

[Table 2] The hardener is used in an amount of 1 to 20% by weight, preferably 2 to 10% by weight, based on dry-processed gelatin.

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used, specific examples of which are described in the following RDl7643 and RD308119. Table 3 shows the related description.

[0121]

[Table 3]

Further, these additives are described in RD308119 page 1007.
It can be added to the photographic photosensitive layer by the dispersion method described in the section XIV.

For the color photographic light-sensitive material, the above-mentioned RD308119 is used.
An auxiliary layer such as a filter layer or an intermediate layer described in the section VII-K can be provided.

When the color photographic light-sensitive material is constituted, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned RD308119 VII-K can be adopted.

An undercoat layer may be provided on the support in order to firmly adhere the light-sensitive silver halide emulsion layer, the filter layer and the conductive layer to the support. Surface activation treatment such as mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment and ozone oxidation treatment may be performed. Further, an undercoat layer may be provided after the surface activation treatment, and a photographic emulsion layer or the like may be coated thereon.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James, Theory of the Photographic Process 4th Edition (Th
e Theory of The Photografic Process Forth Editio
n) Pages 291-334 and the Journal of the American Chemical Society (JournaI of the Ame
rican Chemical Society) Vol. 73, p. 3,100 (1951)
The developers known per se described in 1) can be used. The color photographic light-sensitive material is RD1764 described above.
3 Development can be carried out by a usual method described on pages 28 to 29, RDl 8716 page 615 and RD308119 XIX.

[0127]

EXAMPLES Specific examples of the present invention will be described below.
The embodiments of the present invention are not limited to these. Example 1 A triacetyl cellulose film (T having a base thickness of 110 μm)
The coating solution for the first layer below was applied to one surface of (AC) at 20 ml / m ² and dried at 80 ° C. for 5 minutes to form the first layer. <1st layer coating liquid>

[0128]

[Chemical 15] 35 g SiO ₂ fine particles (average particle size 3.0 μm) 0.1 g Ethylene glycol 270 ml Methanol 600 ml Acetone 4000 ml Further, the following composition for the second layer is acetone-on the first layer.
The coating solution dispersed in a mixed solvent of ethyl acetate (50:50) using a sand mill was applied to form a second layer.

<Composition for Second Layer> Magnetic powder Fe ₂ O ₃ (Hc: 330 Oe, BET: 32 m ² / g) 200 mg / m ² Diacetyl cellulose 800 mg / m ^{2 On} the second layer, the following third layer The coating composition prepared by dissolving the layer composition in a toluene-ethyl acetate (50:50) mixed solvent was applied to form a third layer. <Composition for the third layer> Fluorine-based surfactant (type and amount are listed in Table 4) Behenic acid (lubricant) 20 mg / m ² Then, opposite to the surface where the first to third layers are provided. After the corona discharge treatment, the following photographic constituent layers were sequentially formed on the surface of the side support to prepare multilayer silver halide color photographic light-sensitive materials (Samples 1 to 12).

Unless otherwise stated, the quantities shown in the photographic constituent layers shown below are expressed in quantities per 1 m ² . The silver halide emulsion and colloidal silver are shown in terms of silver.

<Photographic Constituent Layer> First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.15 g UV Absorber (UV-1) 0.20 g Colored Cyan Coupler (CC-1) 0.02 g High Boiling Solvent (Oil-1) ) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average grain size 0.3 μm) (Average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (Average grain size 0.4 μm) (Average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) ) Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR Objects (D-1) 0.006g DIR compound (D-2) 0.01g High-boiling solvent (Oil-1) 0.55g Gelatin 1.0g

Fourth layer: high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (average grain size 0.7 μm) (average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S- 1) 1.7 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ^-4 (mol / Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; intermediate Layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm) (Average iodine content 8.0 mol%) 0.6 g Iodobromide Silver emulsion (average grain size 0.3μ) (Average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-5) 0.8 × 10 ^-4 (model / Silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7g Gelatin 1.0g

Seventh layer: high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (average grain size 0.7 μm) (average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-7) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) ) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g 8th layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) ) 0.15 g Gelatin 1.0 g 9th layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm) (average iodine Content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average particle size 0.4 .mu.m) (average iodide content of 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 -4 ( mol / 1 mol of silver ) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g

Layer 10: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (average grain size 0.8 μm) (average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-11) 1.2 × 10 ^-4 (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High Boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorption Agent (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling point solvent (Oil-1) 0.07 g High boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g 12 layers; second protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethylmethacrylate (average particle size 3 μm) 0.02 g Methylme Acrylate: methacrylate: methacrylic acid = 3: 3: Copolymer of 4 (weight ratio) (average particle size 3 [mu] m) 0.13 g Gelatin 0.7g

-Preparation of silver iodobromide emulsion-The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

A silver iodobromide emulsion was prepared by the double jet method using monodisperse silver iodobromide grains having an average grain size of 0.33 μm (silver iodobromide content of 2 mol%) as seed crystals.

A solution (G-1) having the following composition was treated at a temperature of 70 ° C. and pA.
While maintaining g 7.8 and pH 7.0, 0.34 mol equivalent of seed emulsion was added while stirring well. (Formation of internal high iodine phase-core phase) After that, the solution (H-1) having the following composition and the solution (S-1) having the following composition were accelerated while maintaining a flow ratio of 1: 1. (The flow rate at the end was 3.6 times the initial flow rate) and was added over 86 minutes.

(Formation of External High Iodity Phase-Shell Phase) Subsequently, while maintaining pAg 10.1 and pH 6.0, (H-2) and (S
-2) and were added at a flow rate accelerated at a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles were formed, they were washed with water by a conventional flocculation method, and then gelatin was added and redispersed, and pH and pAg were adjusted to 5.8 and 8.0 at 40 ° C., respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Solution Ocein gelatin 100.0 g 10% by weight solution of -1 of the following compound in ethanol 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml Compound-1: polyiso Propyleneoxy / polyethyleneoxy / sodium disuccinate

<H-1> Solution Ocein gelatin 82.4 g Potassium bromide 151.6 g Potassium iodide 90.6 g Finish with water 1030.5 ml

<S-1> Solution Silver nitrate 309.2 g 28% aqueous ammonia solution Equivalent Finish with water 1030.5 ml

<H-2> Solution Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml

<S-2> Solution Silver nitrate 1133.0 g 28% aqueous ammonia solution Equivalent Finish with water 3776.8 ml

The silver iodobromide emulsions used in layers other than the 10th layer were also processed in the same manner as described above, so that the average grain size of seed crystals, temperature, pA
The emulsions having different average grain sizes and silver iodobromide contents were prepared by changing g, pH, flow rate, addition time and halide composition.

All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, sensitizing dye, 4-hydroxy-6.
-Methyl-1,3,3a, 7-tetrazaindene, 1-
Phenyl-5-mercaptotetrazole was added.

The above-mentioned light-sensitive material further comprises the compound SU.
-1, SU-2, viscosity modifier, hardener H-1, H-2,
Stabilizer ST-1, antifoggant AF-1, AF-2 (heavy
Weight average molecular weight of 10,000 and 1,100,000), dyeing
Material AI-1, AI-2 and DI-1 (9.4mg / m² ) Included
Have.

The compounds used above will be described later.

Each of the prepared samples was cut as shown in FIG. 1 and packed in a cartridge to prepare a film having a width of 35 mm and 24 shots.

In FIG. 1, 101 is perforation, C0 to C3, and F00 to F29 are tracks for recording magnetic information.

For each sample packed in the cartridge,
The reading error of the magnetic recording was evaluated according to the following. The results obtained are shown in Table 4.

(Evaluation of magnetic recording read error) Track C shown in FIG. 1 of the film packed in the cartridge.
Magnetic information was recorded on 0 to C3 by using the magnetic recording / reproducing apparatus of the format disclosed in US Pat. No. 5,021,820. After the development processing, the magnetic information recorded by the magnetic recording / reproducing apparatus was reproduced. When there was 30% or less of the reproduction output, it was determined that there was a read error.

With respect to each sample, five 24 film films each of which was packed in the patrone were prepared, and magnetic information was recorded and reproduced as described above on all 24 frames of each film. I checked the number of coma.

In the above evaluation, immediately after the film was developed, fingerprints and talc were applied to the entire surface of the film, and the surface on which the fingerprints and talc were applied was cleaned with a non-woven fabric three times, and those not treated. I went to both.

The results are shown in Table 4. In addition, in Table 4,
Fingerprints and talc were applied to the entire surface of the film, and the surface on which the fingerprints and talc were applied was cleaned three times with a non-woven fabric. It was

[0157]

[Table 4]

Example 2 100 parts by weight of dimethyl terephthalate, ethylene glycol 6
0.1 part by weight of calcium acetate hydrate was added to 4 parts by weight as a transesterification catalyst, and transesterification reaction was carried out by a conventional method.

The obtained product was added to 5-sodium sulfo-di (β-hydroxyethyl) isophthalic acid (abbreviation: S
An ethylene glycol solution (concentration: 35% by weight) of IP), 8.1 parts by weight of polyethylene glycol (abbreviation: PEG) (number average molecular weight = 3000), 0.05 part by weight of antimony trioxide, and 0.13 part by weight of trimethyl phosphate ester were added.
Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a copolyester.

These copolymerized polyesters were subjected to T at 290 ° C.
The film was melt extruded from a die and rapidly cooled and solidified on a cooling drum to obtain an unstretched film (thickness: 660 μm). This unstretched film is preheated at 80 ° C., stretched 3.2 times in the vertical direction, and further stretched 3.2 times in the horizontal direction at 90 ° C.
It was heat set at 30 ° C. for 30 seconds to obtain a biaxially stretched film having a thickness of 65 μm. The biaxially stretched film was used as a support.

Both sides of the support were subjected to a corona discharge treatment of 8 W / (m ² · min), and one side was coated with a subbing coating solution B-3 shown below so as to have a dry film thickness of 0.8 μm. Forming a subbing layer B-3 on the other surface of the support.
4 to a dry film thickness of 0.8 μm to form an undercoat layer B-4.
Was formed.

<Undercoating Coating Liquid B-3> Copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content). 30%) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml

<Undercoating Coating Liquid B-4> Copolymer latex liquid of butyl acrylate 40% by weight, styrene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexa Methylene-1,6-bis (ethylene urea) 0.8 g Finished with water 1000 ml Further, 8 W / (m ² on the undercoat layer B-3 and the undercoat layer B-4.
-Min) corona discharge is applied, and on the undercoat layer B-3,
The undercoat layer B-5 is formed by applying the following coating solution B-5 to a dry film thickness of 0.1 μm, and the undercoat layer B-4 is coated with the following coating solution B-6. The undercoat layer B-6 having an antistatic function was formed by coating so as to have a thickness of 0.8 μm.

<Coating Liquid B-5> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Finish with water 1000 ml <Coating liquid B-6> Water-soluble conductive polymer (UL-4) 60 g Lattex liquid containing compound (UL-5) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g Curing agent (UL-6) 12 g Polyethylene glycol (weight average molecular weight 600) 6g Finish with water 1000ml

Then, on the undercoat layer B-6, 8 W / (m ² · mi
n) is subjected to corona discharge to sequentially form a back layer consisting of the following two layers on the surface of the undercoat layer B-6, and 25 W / (m ² · min) on the undercoat layer B-5. Then, the first to twelfth layers of the photographic constituent layers described in Example 1 were sequentially formed to prepare multilayer color photographic light-sensitive materials (Samples 13 to 25).

Unless otherwise specified, the quantities shown in the bag layer and the photographic constituent layers shown below are expressed in quantities per 1 m ² . Also, silver halide and colloidal silver are shown in terms of silver.

<Back Layer> First Layer Gelatin 4.5 g Sodium-di- (2-ethylhexyl) -sulfosuccinate 1.0 g Sodium tripolyphosphate 76 mg Citric acid 16 mg Carboxyalkyl dextran sulfate 49 mg Vinyl sulfone type hardener 23 mg Second Layer Magnetic powder (Co deposition-magnetite Hc = 700Oe, BET = 36m²/ g, Fe²⁺/ Fe ³⁺ = 16.6%) 200 mg Gelatin 1.5 g Polymer beads (average particle size 3 μm, polymethylmethacrylate) 24 mg Sodium-di- (2-ethylhexyl) -sulfosuccinate 15 mg Carboxyalkyl dextran sulfate 12 mg Vinyl sulfone type hardener 30 mg Fluorine-based Surfactant (type and amount are listed in Table 5)

Each of the prepared samples was cut as shown in FIG. 1 and packed in a cartridge to prepare a film having a width of 35 mm and 24 shots. With respect to each sample packed in the cartridge, the reading error of magnetic recording was evaluated in the same manner as in Example 1. The results obtained are shown in Table 5.

[0169]

[Table 5]

[0170]

[Chemical 16]

[0171]

[Chemical 17]

[0172]

[Chemical 18]

[0173]

[Chemical 19]

[0174]

[Chemical 20]

[0175]

[Chemical 21]

[0176]

[Chemical formula 22]

[0177]

[Chemical formula 23]

[0178]

[Chemical formula 24]

[0179]

[Chemical 25]

[0180]

INDUSTRIAL APPLICABILITY The photographic light-sensitive material of the present invention prevents foreign matter from adhering to the surface of the photographic light-sensitive material, particularly the magnetic recording surface side, which may cause an error in writing and reading of magnetic information, and prevents the occurrence of magnetic signal. Read errors are prevented.

[Brief description of drawings]

FIG. 1 is an explanatory diagram illustrating a track on which magnetic information is recorded.

Claims (2)

[Claims] 1. A photographic light-sensitive material having at least one silver halide emulsion layer on one side of a support and a transparent magnetic recording layer on the other side, wherein an anionic fluorine is provided on the transparent magnetic recording layer side. A photographic light-sensitive material characterized in that a surfactant and a cationic fluorine-based surfactant are present. 2. The photographic light-sensitive material according to claim 1, wherein the support has a thickness of 40 to 115 μm.