JPH07219091A - Silver halide photographic sensitive material having transparent magnetic recording layer - Google Patents

Abstract

PURPOSE:To provide a photosensitive material having a transparent magnetic recording layer free from any error in magnetic output and input and causing no uneven drying due to repelling of a development processing solution and superior in photographic performance, such as slidability and scratch resistance, at the time of using it in a small type photographic cartridge. CONSTITUTION:The photosensitive material has at least one silver halide emulsion layer on, at least, one side of a support and at least one transparent magnetic recording layer on the reverse side of the magnetic recording layer, and contains, at least, one kind of specified sliding agent in the recording layer side of the material and this photosensitive material is packed into the small cartridge system.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a transparent magnetic recording layer. The present invention relates to a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material) which has good image quality and good photographic properties.

[0002]

2. Description of the Related Art Conventionally, silver halide photographic light-sensitive materials (hereinafter abbreviated as light-sensitive materials) have been used for various information (for example,
It was almost impossible to input the shooting date, weather, enlargement ratio, number of prints, etc., and it was only possible to input the shooting date slightly optically. Further, even at the time of printing, it is impossible to input information to the photosensitive material itself, which is a major obstacle to high speed and cost reduction. Inputting various kinds of information to the sensitive material is a very important means for improving the operability and further simplifying the camera in the future.
The magnetic recording method as the information input means is important because it can perform arbitrary input / output and is inexpensive, and has been studied in the past. By giving a magnetic recording layer to the sensitive material, it becomes possible to incorporate various kinds of information, which were difficult in the past, into the sensitive material. It has become possible to input / output conditions, the number of reprints, a portion to be zoomed, development of a message, conditions for printing, and the like to the magnetic recording layer of the photosensitive material. Furthermore, it has the potential of being applicable as a signal input / output means in the case of outputting an image directly from a sensitive material to a television / video image.

A photosensitive material having a transparent magnetic recording layer has a transparency necessary for a photosensitive material at the time of photographing by appropriately selecting, for example, the amount and size of magnetic particles contained in the magnetic recording layer. A magnetic recording layer that does not adversely affect the granularity,
It is made by providing it on the back surface of a light-sensitive material having a transparent support. Specifically, U.S. Pat.
79945, 4302523, etc. Also,
The signal input method to this magnetic recording layer is the international publication 90-04205.
No. 90-04212 and the like. However, in handling the photosensitive material provided with this magnetic recording layer, a major problem at the time of inputting / outputting thereof is that an input / output error occurs. The main causes of this are the slip agent applied to the back surface (the surface on which the emulsion layer is not applied), the abrasion powder of the magnetic recording layer, the dirt attached during the development process, the hand marks on the film, and the atmosphere. This is because dust or the like adheres to the surface of the magnetic head when the film is running, resulting in a space loss between the film and the magnetic head and a magnetic input / output error. In normal audio / video tapes, non-magnetic metal particles are added to the magnetic recording layer in order to prevent input / output errors caused by slip agents, abrasion powder of the magnetic recording layer, and dust in the atmosphere. When this is used on the back side of photographic film, there is a problem with the usual addition amount in terms of graininess, sharpness, optical density, etc., and dust is liable to adhere during development processing, and it is often directly touched. The effect was not sufficient for the stains on the photographic film in.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to have a transparent magnetic recording layer, to prevent magnetic recording input / output errors even after raw and development processing, to prevent stains during development processing and to improve photographic properties. To provide a silver halide photographic light-sensitive material which does not deteriorate.

[0005]

It has been found that the above object can be achieved by the following constitution. A silver halide photograph having at least one photosensitive silver halide emulsion layer on one side of a support and at least one transparent magnetic recording layer having a coercive force of 400 Oe or more on the side opposite to the photosensitive layer of the support. A silver halide photographic light-sensitive material characterized by containing at least a compound represented by the following general formula (1) and / or (2) on the magnetic recording layer side of the light-sensitive material. General formula (1) R ¹ X ¹ R ² General formula (2) R ³ X ² R ⁴ X ³ R ^{5 In} general formula (1), R ¹ and R ² each represent an aliphatic hydrocarbon group. However, in at least one of R ¹ or R ^2, having at least one polar substituent, R ^1, the total number of carbon atoms of the total R ² is 25 or more 120 or less. X ¹ represents a divalent linking group. In the general formula (2), R ³ and R ⁵ each represent an aliphatic hydrocarbon group, and R ⁴ represents a divalent aliphatic hydrocarbon group. Provided that at least one of R ³ , R ⁴ and R ⁵ has at least one polar substituent, and R ³ , R ⁴ and
The total total carbon number of R ⁵ is 30 or more and 150 or less. X
² and X ³ each represent a divalent linking group.

The layer containing the compound represented by the general formula (1) and / or (2) on the magnetic recording layer side of the photosensitive material contains the compound represented by the following general formula (3). The achievement degree is further enhanced by the silver halide photographic light-sensitive material characterized by the above. General formula (3) R ⁶ YBD R ⁶ represents an aliphatic hydrocarbon group having 25 or more and 70 or less carbon atoms. Y represents a divalent linking group. The _{B - (CH 2 CH 2 O} )
_a −, − (CH ₂ CH (OH) CH ₂ O) _b −, − ((CH ₂ ) _c CH (R) CH ₂
O] _d − or − (CH ₂ CH ₂ O) _e − [CH ₂ CH (OH) CH ₂ O
] _F - _{[(CH 2) c CH (R} ) CH 2 O ] _g - consists either units, a is 3 to 40, b, d each 3-30,
c represents 1 to 3, e represents 0 to 40, f and g each represent an integer of 0 to 30, and e + f + g is 3 to 40. Here, R represents H, CH ₃ , or a phenyl group. D is H or has 8 carbon atoms
The following hydrocarbon groups are shown.

Furthermore, the magnetic recording layer side of the light-sensitive material contains the compound represented by the general formula (1) and / or (2) and at least one compound of the general formula (3). The degree of achievement is further enhanced by a silver halide photographic light-sensitive material characterized by containing a binder in the layer. Further, the layer containing the compound represented by the general formula (1) and / or (2) on the magnetic recording layer side of the photosensitive material contains a compound represented by the following general formula (4). The degree of achievement is further enhanced by the silver halide photographic light-sensitive material. Furthermore, the presence of a binder in this layer is further enhanced. General formula (4) R ⁷ ZEM ^{1 In the} general formula (4), R ⁷ represents an aromatic or aliphatic hydrocarbon group. Z represents a divalent linking group. E is -OS
Represents O ₃ − or —SO ₃ −. M ¹ represents a cation.

First, the transparent magnetic recording layer used in the present invention will be described. The magnetic particles used in the present invention are γ
Ferromagnetic iron oxides such as Fe ₂ O ₃ (FeOx, 4/3 <x ≦
3/2), Co-deposited γFe ₂ O ₃ , Co-deposited ferromagnetic iron oxide (FeOx, 4/3 <x ≦ 3/2), Co-deposited magnetite, other Co-containing ferromagnetic iron oxide, Co Containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metals, ferromagnetic alloys, and other ferrites such as hexagonal Ba
Ferrite, Sr ferrite, Pb ferrite, Ca ferrite, or a solid solution or ion substitution product of these can be used. As an example of the ferromagnetic alloy, the metal content is 75 wt% or more, and 80 wt% or more of the metal content is at least one kind of ferromagnetic metal or alloy (Fe, C
o, Ni, Fe-Co, Fe-Ni, Co-Ni, Co
-Fe-Ni, etc.) and other components (Al, Si, S, Sc, Ti, V, Cr, M) at 20 wt% or less of the metal content.
n, Cu, Zn, Y, Mo, Rh, Pd, Ag, Sn,
Sb, B, Ba, Ta, W, Re, Au, Hg, Pd,
P, La, Ce, Pr, Nd, Te, Bi, etc.) can be mentioned. Further, the ferromagnetic metal component may contain a small amount of water, hydroxide or oxide. The manufacturing method of these ferromagnetic powders is known, and the ferromagnetic material used in the present invention can also be manufactured according to the known method.

The shape and size of the ferromagnetic material will be described.
The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape, etc., but needle shape is preferable in terms of electromagnetic conversion characteristics. The particle size and specific surface area are not particularly limited, but the specific surface area is S
_{The BET} is preferably 20 m ² / g or more, particularly preferably 30 m ² / g or more. When the particle size is needle-like, the major axis is 0.01 to
0.8 μm, the minor axis is 0.005 to 0.4 μm, the ratio of the major axis to the minor axis is preferably 100 to 2, and the major axis is 0.04 to
More preferably, 0.4 μm, the short axis is 0.01 to 0.1 μm, and the ratio of the long axis to the short axis is 100 to 3. When the magnetic particles are plate-like such as barium ferrite, the plate-like maximum length is 0.05 to 0.8 μm and the thickness thereof is 0.005 to 0.005 μm.
0.4 μm is preferable, and more preferably, the maximum length of the plate is 0.05 to 0.4 μm and its thickness is 0.05 to 0.
2 μm. At this time, the plate-shaped maximum length-thickness ratio (so-called aspect ratio) is preferably 2 to 100, and more preferably 4 to 30. The particle size distribution of the magnetic material is preferably as sharp as possible.

The larger the saturation magnetization (σ _S ) of the ferromagnetic material, the more preferable it is 50 emu / g or more, and more preferable 70 emu / g or more. In addition, the squareness ratio (σ _r / σ _s ) of the ferromagnetic material is 4
0% or more, and further preferably 45% or more. If the coercive force (Hc) is too small, it tends to be erased, and if it is too large, it becomes impossible to write depending on the system.

These ferromagnetic particles are disclosed in, for example, Japanese Patent Laid-Open No.
It may be surface-treated with silica and / or alumina, such as 9-23505 and those described in JP-A-4-096052. Further, JP-A-4-195726 and JP-A-4-19526
Surface treatment with an inorganic and / or organic material such as those described in 2116, 4-259911, and 5-081652 may be performed. Further, these ferromagnetic particles may be treated with a silane coupling agent or a titanium coupling agent on the surface thereof. As the coupling agent, known materials such as those described in JP-B-1-261469 can be used, but the following compounds can also be used.

Compound Example [1] -1. Vinyltrichlorosilane 〃 [1] -2. Vinyltriethoxysilane 〃 [1] -3. γ-methacryloxypropyltrimethoxysilane 〃 [1] -4. γ-glycidoxypropyltrimethoxysilane 〃 [1] -5. N-β (aminoethyl) γ-aminopropyl methyldimethoxysilane 〃 [1] -6. N-phenyl-γ-aminopropyl trimethoxysilane [1] -7. Vinyloctyltrimethoxysilane 〃 [1] -8. 10- (Vinyloxycarbonyl) nonyltrimethoxysilane 〃 [1] -9. p-Vinylphenyl triisopropylsilane 〃 [1] -10.3- (glycidyloxy) propyl triethoxysilane 〃 [1] -11.3- (acryloyl) propyl trimethoxysilane 〃 [1] -12.11- (methacryloyl) ) Undecyl trimethoxysilane 〃 [1] -13.3-aminopropyl trimethoxysilane 〃 [1] -14.3-phenylaminopropyl trimethoxysilane 〃 [1] -15.3-N, N-dibutylaminopropyl trimethoxy Silane 〃 [1] -16.3-Trimethylammoniopropyl trimethoxysilane iodide 〃 [1] -17.3-Mercaptopropyl trimethoxysilane 〃 [1] -18.3-Isocyanylpropyl methyldimethoxysilane 〃 [1 ] -19.3- (Poly (heavy Degree 10) oxyethynyl) oxypropyl trimethoxysilane 〃 [1] -20.3-methoxy (poly (polymerization degree 6) oxyethynyl) oxypropyl trimethoxysilane 〃 [1] -21. Decyltrimethoxysilane

Compound Example [2] -1. Isopropyltriisostearoyl titanate 〃 [2] -2. Isopropyl tridodecylbenzene sulfonyl titanate [2] -3. Isopropyl tris (dioctyl pyrophosphate) titanate 〃 [2] -4. Tetraisopropyl bis (dioctyl phosphite) titanate [2] -5. Tetraoctyl bis (ditridecyl phosphite) titanate 〃 [2] -6. Tetra (2,2'-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate 〃 [2] -7. Bis (dioctyl pyrophosphate oxyacetate titanate 〃 [2] -8. Bis (dioctyl pyrophosphate) ethylene titanate 〃 [2] -9. Isopropyltrioctanoyl titanate 〃 [2] -10 isopropyldimethacrylisostearoyl titanate 〃 [2] -11. Isopropylisostearoyl diacrylic titanate 〃 [2] -12. Isopropyltri (dioctyl phosphate) titanate 〃 [2] -13. Isopropyltricumylphenyl titanate 〃 [2] -14. Isopropyltritanate (N-amidoethylaminoethyl) titanate 〃 [2] -15. Dicumylphenyloxyacetate titanate 〃 [2] -16. Diisostearoyl ethylene titanate

The addition amount of these silane coupling agent and titanium coupling agent to the magnetic particles is 1.0 to 2
00 wt% is preferable, and if it is less than this, the liquid stability is inferior, and if it is too much, the liquid stability is also poor. It is more preferably 1 to 75 wt%, and even more preferably 2 to 50 wt%. The addition of the silane coupling agent and the titanium coupling agent of the present invention is carried out by a generally known method, and the surface thereof can be modified to impart the stability of the coating liquid of the magnetic material. That is, the coupling agent is processed by a direct processing method for magnetic particles and an integral blending method. The direct method is roughly classified into a dry method, a slurry method and a spray method. The magnetic material obtained by the direct treatment method is excellent in that it can be added to the binder to surely modify the surface of the magnetic particles with the coupling agent. Among them, the dry method is generally performed by uniformly dispersing magnetic particles in an alcohol aqueous solution, an organic solvent or an aqueous solution of a silane coupling agent and then drying the magnetic particles. The stirrer is preferably a Henschel mixer, super mixer, ready mixer, V-type blender, open kneader, or the like. Among these stirrers, the open kneader is particularly preferable. It is more preferable that magnetic particles and a small amount of water, or an organic solvent containing water and a coupling agent are mixed and stirred with an open kneader to remove water, and then finely dispersed. Further, the slurry method adds a coupling agent to the slurry when there is a step of making magnetic particles into a slurry in the production of a magnetic material, and has an advantage that it can be processed in the production step. The spray method adds a coupling agent to the magnetic particles in the drying step of the magnetic material, and has an advantage that it can be processed in the manufacturing step, but has a problem in uniformity of processing. The integral blending method is a method in which a coupling agent is added to magnetic particles and a binder, and it is a simple method that requires good kneading.

Next, the binder in which the magnetic particles of the present invention are preferably used will be described. The binder used in the present invention is a known thermoplastic resin conventionally used as a binder for magnetic recording media, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, A natural product polymer (cellulose derivative, sugar derivative, etc.) or a mixture thereof can be used. The preferable glass transition temperature of the above resin is −40 ° C. to 300.
C., the weight average molecular weight is 20,000 to 1,000,000, and more preferably 5,000 to 300,000. Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymers, vinyl chloride, copolymers of vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / vinyl chloride. Vinyl-based copolymers such as acrylonitrile copolymer, ethylene-vinyl acetate copolymer,
Cellulose derivatives such as nitrocellulose, cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate, cellulose dodecanoate resin, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin Examples include rubber-based resins such as polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, and butadiene acrylonitrile resin, silicone resin, and fluorine resin.

The above-mentioned thermosetting resin or reactive resin has an extremely large molecular weight when heated, and includes, for example, phenol resin, phenoxy resin, epoxy resin,
Curable polyurethane resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic reaction resin, epoxy-polyamide resin, nitrocellulose melamine resin, mixture of high molecular weight polyester resin and isocyanate prepolymer, urea formaldehyde resin, low molecular weight glycol / High molecular weight diols / polyisocyanates mixtures, polyamine resins and mixtures thereof. 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 thermoplastic resin is used. Preferred functional groups include an acryloyl group and a methacryloyl group. Among these binders, cellulose diacetate is preferred. In the binders listed above, polar groups (epoxy group, CO ₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M, O
SO ₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , wherein M is hydrogen, an alkali metal or ammonium, and when there are a plurality of Ms in one group, R may be hydrogen or Alkyl group, X is halogen)
Introduced is preferable in terms of dispersibility and durability of the magnetic material.
The content of polar groups is from 10 ^-7 per gram of polymer.
10 ^-3 equivalent is preferable, and 10 ^-6 to 10 ^-4 equivalent is more preferable range.

The binders listed above may be used alone or as a mixture of several kinds, and a known crosslinking agent of epoxy type, aziridine type, isocyanate type and / or a radiation curable vinyl type monomer may be added for curing treatment. it can.
Two isocyanate groups are used as an isocyanate cross-linking agent.
Polyisocyanate compounds having more than one, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate,
Isocyanates such as xylylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane diisocyanate, reaction products of these isocyanates with polyalcohols (for example, 3 mol of tolylene diisocyanate and Examples include trimethylolpropane (1 mol reaction product) and polyisocyanates produced by condensation of these isocyanates. The radiation-curable vinyl-based monomer is a compound that can be polymerized by irradiation with radiation and has one or more carbon-carbon unsaturated bonds in the molecule,
(Meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl esters, vinyl esters, vinyl heterocyclic compounds, N-vinyl compounds, styrene, (meth) acrylic acid, crotonic acid, itaconic acid, Examples thereof include olefinic acid. Of these, preferred are (meth) acrylates of polyethylene glycol such as diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate having two or more (meth) acryloyl groups, trimethylolpropane tri (meth) acrylate, and the like. ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a reaction product of a polyisocyanate and a hydroxy (meth) acrylate compound, and the like. These cross-linking agents are preferably 5 to 45 wt% with respect to the whole binder containing the cross-linking agents.

A hydrophilic binder can also be used in the magnetic recording layer of the present invention. As the hydrophilic binder to be used, Research Disclosure No. 17643, 2
6 and pp. 651, No. 18716, water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. are exemplified.
As the water-soluble polymer, gelatin, gelatin derivatives,
Examples thereof include casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer and the like, and examples of the cellulose ester include carboxymethyl cellulose and hydroxyethyl cellulose. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. The most preferred of these is gelatin. Gelatin is a so-called alkali-treated (lime-treated) gelatin that is immersed in an alkaline bath before extraction of gelatin, an acid-treated gelatin that is immersed in an acid bath, and a double-dipped gelatin that has undergone both treatments and an enzyme treatment in the manufacturing process. Any of gelatin may be used. If necessary, a portion thereof may be colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose and other cellulose derivatives, agar, sodium alginate, starch derivatives, dextran and other sugar derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N.
-Vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates,
A gelatin derivative or the like may be used in combination with gelatin.

It is preferable to harden a magnetic recording material containing gelatin. Examples of hardeners that can be used in the magnetic recording layer 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 and others U.S. Pat. No. 3,288,
No. 775, No. 2,732,303, British Patent No. 97
4,723, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine In addition, compounds having reactive olefins described in U.S. Pat. Nos. 3,635,718, 3,232,763, and British Patent 994,869, N-hydroxymethylphthalimide, and other United States N-methylol compounds described in US Pat. Nos. 2,732,316 and 2,586,168, isocyanates described in US Pat. No. 3,103,437, US Pat. , 017,
280, 2,983,611 and the like, aziridine compounds, US Pat. No. 2,725,294.
No. 2,725,295, etc., acid derivatives described in US Pat. No. 3,091,537, halogen carboxaldehydes such as mucochloric acid. You can Alternatively, as an inorganic compound hardening agent, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-3269.
9, Belgian Patent No. 825,726, JP-A-60-2.
No. 25148, JP-A-51-126125, and JP-B-5.
Examples thereof include carboxyl group-active type hardeners described in JP-A No. 8-50699, JP-A No. 52-54427, US Pat. No. 3,321,313 and the like. The amount of hardener used is usually 0.01 to 30 wt% with respect to dry gelatin,
It is preferably 0.05 to 20 wt%.

As the method for dispersing the above-mentioned magnetic material in the binder, for example, Japanese Patent Application No. 4-189652 and various known means can be used. A combined use of a kneader and a pin type mill or a kneader and an annular type mill is also preferable. As the kneader, there are open type, closed type, continuous type and the like, and kneaders such as a three-roll mill and Labo Plastomill are also used. Further, at the time of dispersion, the dispersant described in JP-A-5-088283 and other known dispersants can be used.

The thickness of the magnetic recording layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, and particularly preferably 0.3 to 3 μm. The weight ratio of the magnetic particles to the binder is preferably 0.005 to 0.6, more preferably 0.01 to 0.3. The coating amount as a magnetic material is 0.
005-3 g / m ² is preferable, and more preferably 0.01-
2 g / m ^2, more preferably is 0.02 to 0.5 g / m ^2. The coercive force of the film provided with the magnetic recording layer is 4
00 Oe or more and 3000 Oe or less are preferable, and 800 Oe or more and 1500 Oe or less are more preferable. The increase in color density due to the addition of the magnetic recording layer needs to be suppressed as low as possible.
The following is preferable, and 0.2 or less is more preferable.

The magnetic recording layer of the present invention can be formed on the entire back surface of the photographic support by coating or printing or in the form of stripes. Alternatively, a support having a magnetic recording layer can be prepared by co-casting a solution of a binder in which magnetic particles are dispersed and a solution of a binder for preparing a support on the entire surface or in a stripe shape. In this case, the compositions of the two kinds of polymers may be different, but it is preferable that they are the same.
The method for applying this magnetic recording layer includes air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat, dip coat, bar coat. , Extrusion coat, etc. can be used, and other methods are also possible, and detailed explanations of these are described in detail in “Coating Engineering”, pages 253 to 277 (published by Showa 46. 3.20.), Published by Asakura Shoten. Has been done. By such a method, the magnetic recording layer coated on the support is subjected to a treatment for orienting the magnetic material in the layer while immediately drying it, if necessary, and then the formed magnetic recording layer is dried. The transport speed of the support at this time is usually 2 to 500 m.
/ Min, and the drying temperature is controlled at 20 to 250 ° C.
There is a method of using a permanent magnet or a solenoid coil to orient the magnetic body. The strength of the permanent magnet is preferably 2000 Oe or more, particularly preferably 3000 Oe or more. In the case of a solenoid, it may be 500 Oe or more. As described in Japanese Patent Application No. 5-005822, the timing of orientation during drying is preferably at a point where the residual solvent in the magnetic recording layer is 5 to 70%. Also, if necessary, surface smoothing is applied,
The magnetic recording layer of the present invention is provided. These are disclosed, for example, in JP-B-40-23625 and JP-B-39-28368.
No. 3,473,960, and the like. The method disclosed in Japanese Patent Publication No. 41-13181 is considered to be a basic and important technique in this field.

The magnetic recording layer has improved lubricity, curl adjustment,
Functions such as antistatic, adhesion prevention, and head polishing may also be provided, or another functional layer may be provided to impart these functions. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance. For example,
Inorganic and organic fine particles (eg, silica, SiO ₂ , Sn)
O ₂ , Al ₂ O ₃ , TiO ₂ , cross-linked polymethylmethacrylate, barium carbonate, silicone fine particles, etc.) are preferably added.

Additives (matting agent, etc.) to the magnetic recording layer
By incorporating a projection on the back layer surface of 0.8 μm or less, magnetic output error due to dust on the magnetic input / output can be prevented, and S / N, which is one of the magnetic characteristics, is not deteriorated and photographed. There are methods that do not affect sex. For this purpose, as a method of imparting surface protrusions to the back surface, there is a method of adding particles (matting agent etc.) to the back surface, causing brushing during coating and drying, or intentionally generating a Benard cell, It is preferable to add particles to the back surface in the sense that the shape of surface protrusions can be freely controlled.

The particles to which the matting agent or the like is added are insoluble in the developing solution, and the raw materials are inorganic fine particles, polymer particles,
Crosslinked polymer particles and the like can be used. As an example of the particles of the present invention, as the inorganic particles, fine particles of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide, further synthetic silica obtained by, for example, a wet method or gelation of silicic acid. Examples include silicon dioxide such as titanium dioxide and titanium dioxide (rutile type or anatase type) produced by titanium slag and sulfuric acid. Further, those obtained by crushing from an inorganic material having a relatively large particle size, for example, 20 μm or more, and then classifying (vibrating filtration, air classification) are also used. Further, as the polymer compound, there are polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch and the like, and pulverized and classified products thereof are also included. In addition, acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, phthalic acid diester, styrene derivative, vinyl ester, acrylamides, vinyl ethers, allyl compounds, vinyl ketones, vinyl heterocyclic compounds , Allyl compound, acrylonitrile, methacrylonitrile, polyfunctional monomers, three-dimensional siloxane polymer, benzoguanamine / formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, etc. The polymer compound which is a polymer of one kind or more may be formed into particles by various means, for example, a suspension polymerization method, a spray drying method, or a dispersion method. The average particle size of the particles is preferably 0.1 to 1 μm so that the photographic property is not deteriorated, and the coating amount is 1
˜100 mg / m ² is preferred.

It is more preferable that at least one kind of the particles is a non-spherical inorganic particle having a Mohs hardness of 5 or more because it has an effect of cleaning dirt attached to the magnetic head (effect as an abrasive). The composition of the non-spherical inorganic particles as an abrasive includes aluminum oxide (α-alumina,
γ-alumina, corundum, etc.), chromium oxide (Cr
₂ O ₃ ), iron oxide (α-Fe ₂ O ₃ ), oxides such as silicon dioxide, titanium dioxide and silicon carbide (SiC), carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. Aluminum oxide and chromium oxide are more preferable. The non-spherical inorganic particles may be added to the magnetic recording layer or may be overcoated on the magnetic recording layer. As the binder used at this time, the binder described in the binder for the magnetic recording layer can be used, and preferably the same binder as the binder for the magnetic recording layer is used. The above-mentioned abrasives preferably have an average particle size of 0.1 to 1 μm, and the coating amount is 0.1 to 5 μm.
0 mg / m ² is preferred. The above matting agents, abrasives and the like are used under severe conditions of the photosensitive material [high temperature (80 ° C. or higher): curl characteristic, low humidity (30 RH% or more): antistatic property, high humidity (80
RH% or more): anti-adhesion property], and is particularly effectively used for curl control, antistatic, anti-adhesion, etc.

As another method of preventing a magnetic output error caused by dust during magnetic input / output, not deteriorating S / N which is one of magnetic characteristics, and not affecting photographic properties, a melting point on the magnetic recording layer side is used. It is also effective to add a lubricant insoluble in a developer having a (pour point) of 10 ° C. or less. This effect is due to the effect of making it difficult for the slip agent used for the magnetic recording surface and the wear pieces of the magnetic recording layer to adhere to the magnetic head. The melting point (pour point) of the present lubricant may be 10 ° C. or lower, and the most preferable one is −50 ° C. or higher and 10 ° C. or lower. Further, since the present lubricating oil is dried at a high temperature after being applied, the present lubricant is preferably a non-volatile one, and preferably one having a boiling point of 200 ° C. or higher at room temperature. Any material can be used as the lubricant material as long as it satisfies the above-mentioned conditions, such as mineral oils such as spindle oil, machine oil, gear oil and synthetic hydrocarbons, polyalkylene glycols, alkyl diesters, phosphate esters, silicate esters, silicones. , And synthetic oils such as fluorocarbons. Specific examples are shown below, but the present invention is not limited to these.

Compound Example [3] -1 Andecan (pour point = −27 ° C.) 〃 [3] -2 Tetradecane (pour point = 6 ° C.) C ₈ H ₁₇ OCOCH (CH ₃ ) (CH ₃ ) ₃ COO-C ₈ H ₁₇ (pour point = -32 ° C) 〃 [3] -3 Liquid paraffin (pour point = -5 ° C or less) 〃 [3] -4 Dimethylsiloxane (pour point = -5 ° C or less) 100 mg / m ² is good. Further, the present oil may be added not only to the outermost lubricant layer on the magnetic recording layer side but also to the lower layer of the lubricant layer. Further, it is more effective and preferable to use the above-mentioned surface protrusion in combination. In this case, the coating amount of the lubricating oil used is 1 to 100 mg / m ² , more preferably 1 to 50 mg / m ² .

Next, the slip agent in the present invention will be described in detail. The compounds represented by the general formulas (1) and (2) have sufficient slipperiness and scratch resistance before and after development. General formula (1) R ¹ X ¹ R ² General formula (2) R ³ X ² R ⁴ X ³ R ^{5 In} this general formula (1), R ¹ and R ² each represent an aliphatic hydrocarbon group. Total carbon number of this compound is 25 or more 12
It must be 0 or less. The total number of carbons needs to be 25 or more in order to obtain sufficient slipperiness. Also, the total carbon number is 12
When it is more than 0, the solubility in an organic solvent is poor and it becomes difficult to apply it by dispersion or coating. The total carbon number is more preferably 30 or more and 100 or less, further preferably 40 or more and 80 or less. Further, R ¹ and R ² are sufficient scratch resistance,
Also, in order to suppress deterioration of slipperiness under various use conditions, it is preferable that each is an aliphatic hydrocarbon group having 10 to 70 carbon atoms. When the carbon number is 10 or less, the scratch resistance is deteriorated, and the sliding property is deteriorated by the transfer of the lubricant under various use conditions. Further, one-terminal functionalized aliphatic compounds having 70 or more carbon atoms are not generally known. This aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable from the viewpoint of scratch resistance. The carbon number of R ¹ and R ² is more preferably 15 or more and 50 or less. Further, at least one of R ¹ and R ² has at least one polar substituent. The polar substituent here means a group capable of forming a hydrogen bond or an ionic dissociative group. The polar substituent is not particularly limited,
_{-OH, -COOH, -COOM, -NH 2} , -NR 3
⁺ A ⁻ , —CONH _{2 and the} like are preferable. Here, M is a cation such as an alkali metal, alkaline earth metal or quaternary ammonium salt, R is H or a hydrocarbon group having 8 or less carbon atoms, A
^- is an anion such as a halogen atom. Moreover, among these groups, —OH is particularly preferable. This polar substituent is
Any number of them may fit in one molecule.

In the general formula (2), R ³ , R ⁴ and R ⁵ each represent an aliphatic hydrocarbon group. The total carbon number of this compound must be 30 or more and 150 or less. The total carbon number needs to be 30 or more in order to obtain sufficient slipperiness. If the total number of carbon atoms is more than 150, the solubility in organic solvents is poor and it becomes difficult to disperse or apply by coating. The total carbon number is more preferably 40 or more and 130 or less, still more preferably 50 or more and 120 or less. In addition, R ³ and R ⁵ are each an aliphatic hydrocarbon group having a carbon number of 10 or more and 70 or less, and R ⁴ is a carbon number of 10 or more in order to prevent sufficient scratch resistance and deterioration of slipperiness under various use conditions. It is preferably 50 or less aliphatic hydrocarbon groups. Regarding R ³ and R ⁵ , when the carbon number is 10 or less, the scratch resistance is deteriorated, and the sliding property is deteriorated by the transfer of the lubricant under various use conditions. Further, an aliphatic compound having a carbon number of 70 or more and having one end functionalized is not generally known. This aliphatic hydrocarbon group may have a linear structure, may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable from the viewpoint of scratch resistance. The number of carbon atoms of R ³ and R ⁵ is particularly preferably 15 or more and 50 or less. When R ⁴ has 10 or less carbon atoms, the scratch resistance is deteriorated, and the slipperiness is deteriorated due to the transfer of the lubricant under various use conditions. Further, an aliphatic compound having a carbon number of 50 or more and having both ends functionalized is not generally known. The aliphatic hydrocarbon group may also have a linear structure,
It may contain an unsaturated bond, may partially have a substituent, or may have a branched structure. Of these, the linear structure is particularly preferable from the viewpoint of scratch resistance.
The carbon number of R ⁴ is preferably 10 or more and 30 or less. Particularly preferred is 12 or more and 25 or less.

Further, at least one of R ³ , R ⁴ and R ⁵ has at least a polar substituent. The polar substituent here means a group capable of forming a hydrogen bond or an ionic dissociative group. The polar substituent is not particularly limited, -OH, -COOH, -COOM, -NH 2, -
NR ₃ ⁺ A ⁻ , —CONH _{2 and the} like are preferable. Where M
Is a cation such as an alkali metal, an alkaline earth metal or a quaternary ammonium salt, R is H or a hydrocarbon group having 8 or less carbon atoms, and A ⁻ is an anion such as a halogen atom. Moreover, among these groups, —OH is particularly preferable. Any number of the polar substituents may be contained in one molecule. Further, in the general formulas (1) and (2), X ¹ , X ² and X ³ represent a divalent linking group. Specifically, -C (O) O-, -C (O) NR-, -SO _3- , -OS
O _3- , -SO ₂ NR-, -O-, -S-, -NR-, -OC (O) NR- and the like are shown (R represents H or an alkyl group having 8 or less carbon atoms).

The amount of the slip agent represented by the general formulas (1) and (2) of the present invention is not particularly limited, but its content is 0.001 to 0.001 in order to exhibit sufficient slip and scratch resistance. 0.
1 g / m ² is preferable, more preferably 0.005-0.0
It is 5 g / m ² . Specific examples will be given below, but the present invention is not limited thereto.

[0033]

[Chemical 1]

[0034]

[Chemical 2]

The polyether-containing compound used in the present invention as described above is obtained, for example, by sequentially adding ethylene oxide to a corresponding higher alcohol by a conventional method or by adding the higher alcohol polyether to a corresponding dicarboxylic acid. It can be easily synthesized by dehydration condensation of the product or condensation of a higher carboxylic acid with the higher alcohol polyether adduct. In addition to the above-mentioned lubricants of the general formula (1) and / or (2) of the present invention, other lubricants can be used within the range in which the effects of the compound of the present invention can be obtained. As another slip agent used in the present invention, for example, polyorganosiloxane as disclosed in Japanese Patent Publication No. 53-292, US Pat.
Higher fatty acid amides as disclosed in 5, 14, Japanese Patent Publication No. 58-33541 and British Patent No. 92.
Higher fatty acid ester (ester of fatty acid having 10 to 24 carbon atoms and alcohol having 10 to 24 carbon atoms) as disclosed in JP-A-7-446 or JP-A-55-126238 and JP-A-58-90633. And higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, and JP-A-58-50534.
Known are esters of linear higher fatty acids and linear higher alcohols, higher fatty acid-higher alcohol esters containing a branched alkyl group as disclosed in WO 90108115.8, and the like. Among these, as polyorganosiloxanes, there are generally known polyalkylsiloxanes such as polydimethylsiloxane polydiethylsiloxane, polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, and Japanese Patent Publication No. 53-292. , Japanese Examined Sho 55-
49294, JP-A-60-140341, etc., organopolysiloxane having an alkyl group having 5 or more carbon atoms, alkylpolysiloxane having a polyoxyalkylene group in the side chain, alkoxy, hydroxy in the side chain,
A modified polysiloxane such as an organopolysiloxane having a hydrogen, carboxyl, amino or mercapto group may be used, or a block copolymer having a siloxane unit or a siloxane unit as disclosed in JP-A-60-191240 may be used. It is also possible to use a graft copolymer having a chain. Further, as higher fatty acid and its derivative, higher alcohol and its derivative,
Higher fatty acids, metal salts of higher fatty acids, higher fatty acid esters, higher fatty acid amides, polyhydric alcohol esters of higher fatty acids, etc., higher aliphatic alcohols, monoalkyl phosphites, dialkyl phosphites, trialkyl phosphites of higher aliphatic alcohols It is possible to use phyto, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, its amide compound or its salt.

Since the compounds of the above-mentioned general formula are highly hydrophobic, they often have poor solubility in solvents. Therefore, a method of dissolving in a non-polar organic solvent such as toluene or xylene,
Alternatively, there is a method of dispersing in a coating liquid, but a non-polar organic solvent is difficult to handle, and thus a method of dispersing is preferable. At this time, any dispersant may be used as long as it does not deteriorate slipperiness and scratch resistance, but a preferable dispersant is represented by the following general formula (3).
And those described in. In the general formula (3) R ⁶ YBD general formula (3), R ⁶ represents an aliphatic hydrocarbon group having 25 to 70 carbon atoms. This hydrocarbon group may contain an unsaturated bond, may be substituted with various substituents, and may contain a branched structure. A straight-chain aliphatic hydrocarbon group is particularly preferable in terms of slipperiness and scratch resistance. The carbon number of this hydrocarbon group is in the range of 25 or more and 70 or less. A hydrocarbon group having 25 or less carbon atoms causes problems such as sufficient slippage, scratch resistance not being exhibited, and deterioration of slipperiness after treatment. As a hydrocarbon compound having a carbon number of 70 or less and having one end functionalized, a long-chain linear or branched aliphatic alcohol or the like is known.
Compounds having 0 or more hydrocarbon groups are generally unknown. Particularly preferred as carbon number is 3
It is 0 or more and 60 or less. Y represents a divalent linking group. Specifically, -C (O) O-, -OCO-, -C (O) NR'-, -NR'CO-,-
SO ₂ NR'-, -NR'SO _2- , -O-, -S-, -NR-, -OCOR''COO-, -O
COR "O-, etc. can be mentioned (R 'is H or carbon number
Shows 8 or less hydrocarbon groups. In addition, R '' has 0 to 8 carbon atoms.
Up to hydrocarbon groups). In addition, B is-(CH ₂ CH ₂ O) _a
-, Or-(CH ₂ CH (OH) CH ₂ O) _b- , or-((CH ₂ ) _c CH (R) C
H ₂ O) _d- , or-(CH ₂ CH ₂ O) _e- (CH ₂ CH (OH) CH ₂ O) _f -((CH ₂ ) _c
CH (R) CH ₂ O) _g- , where a is 3 to
40, b and d are 3 to 30, respectively, c is 1 to 3 and e is 0 to 4
0, f, and g each represent an integer of 0 to 30, and e + f + g is 3 to
40 and R are H, CH ₃ , and a phenyl group. If the length of these nonionic groups is too short, sufficient solubility of the slip agent cannot be obtained, or sufficient dispersion stability cannot be obtained when dispersed. On the other hand, if it is too long, problems such as sufficient slippage, scratch resistance not being exhibited, and deterioration of slipperiness over time after treatment occur. Particularly preferred among the above nonionic group _{- (CH 2 CH 2 O)} a - a and, a is preferably 5 to
Thirty. D represents H or a hydrocarbon group having 8 or less carbon atoms. The use ratio of the general formula (3) to the slip agent (1) and / or (2) is preferably 1/9 to 9/1, more preferably 2/8 to 6/4. The method of dispersing the slip agent will be described later. Specific examples of the compound represented by the general formula (3) are shown below.

[0037]

[Chemical 3]

The use of a binder capable of forming a film in the layer containing the compound represented by the general formula (1) and / or (2) improves the surface condition of the lubricant and improves the film strength of the lubricant layer. Particularly preferred. As such a polymer, a known thermoplastic resin, thermosetting resin, radiation curable resin, reactive resin, a mixture thereof, or a hydrophilic binder such as gelatin can be used. It is further preferred to use such a binder together with the compound of the general formula (1) and / or (2) and the general formula (3). Specific examples of the thermoplastic resin include cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyacetyl cellulose phthalate, cellulose long chain alkyl ester, nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate. Cellulose derivatives such as resins, vinyl chloride / vinyl acetate copolymers, vinyl chloride, vinyl acetate / vinyl alcohol, copolymers of maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / acrylonitrile Copolymer, vinyl-based copolymer such as ethylene / vinyl acetate copolymer, acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane Fat, polyether polyurethane, polycarbonate polyurethane resins, polyester resins, polyether resins, polyamide resins, amino resins, styrene butadiene resins, rubber resins such as butadiene acrylonitrile resins, silicone resins, fluorine-based resin. As the radiation curable resin, the above-mentioned thermoplastic resin to which a group having a carbon-carbon unsaturated bond is bonded as a radiation curable functional group is used. Preferred functional groups include an acryloyl group and a methacryloyl group. In the binding molecules listed above, polar groups (epoxy groups,
CO ₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M, OSO
₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , provided that M is hydrogen, alkali metal or ammonium, and when there are a plurality of Ms in one group, they may be different from each other. R is hydrogen or an alkyl group and X is halogen. ) May be introduced. The polymer binders listed above may be used alone or as a mixture of several kinds, and a known isocyanate-based crosslinking agent and / or a radiation-curable vinyl-based monomer may be added for curing treatment.

As the hydrophilic binder, Research Disclosure No. 17643, page 26, and the same No. 18716, page 651, and examples include water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, and the like. Examples of the water-soluble polymer include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymer, maleic anhydride copolymer, and the like, and cellulose ester includes carboxymethyl cellulose and hydroxyethyl cellulose. Is. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene anhydride-containing copolymers, acrylic ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Of these, gelatin is the most preferable. Further, a gelatin derivative or the like may be used in combination with gelatin. The protective layer containing the hydrophilic binder can be hardened. Examples of the hardener 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, other compounds having reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, compounds having reactive olefin, N-hydroxymethyl Mention may be made of phthalimides, N-methylol compounds, isocyanates, aziridine compounds, acid derivatives, epoxy compounds, halogen carboxaldehydes such as mucochloric acid. Alternatively, as the inorganic compound hardening agent, chromium alum, zirconium sulfate and the like can be mentioned. Further, a carboxyl group-activating type hardener and the like can also be used. Of these binders, the most desirable one is
The binder molecule contains a polar substituent. As the polar substituent, for example, -OH, -COO
_{H, -COOM, -NH 3, -NR} 4 +, - CONH 2, -
_{SH, -OSO 3 M, -SO 3} M , and the like. Specifically, particularly preferable ones are cellulose esters such as acetyl cellulose.

Some additives may be added to the above-mentioned lubricant layer in order to impart other functions. For example, a surfactant having a sulfonic acid or sulfuric acid ester as a hydrophilic part may be added as an additive in order to improve repellency caused by a hydrophobic slip agent, and examples thereof include compounds represented by the following general formula (4). General formula (4) R ⁷ ZEM ^{1 In} general formula (4), R ⁷ is an aromatic or aliphatic hydrocarbon group. The hydrocarbon group is not particularly limited, but specifically, straight chain alkyl, branched alkyl, substituted or unsubstituted phenyl group, naphthalene group, succinic acid ester of alkyl group, ester of phosphoric acid, etc. can give. Z is a divalent linking group. This linking group may be omitted. The linking group is not particularly limited, but specifically includes -R-, -OR-, -COOR-, -OCOR-, etc., and R is an alkyl group having 0 to 10 carbon atoms, a polyoxyethylene group, A polyoxypropylene group and the like. Also, E is -OSO
₃ − and −SO ₃ −. M ¹ is H or an alkali metal,
It is a cation such as an alkaline earth metal or a quaternary ammonium salt. Specific examples of the compound represented by the general formula (4) are shown below.

[0041]

[Chemical 4]

The amount of the additive represented by the general formula (4) of the present invention is preferably 0.001 g / m ² or more and up to the solid content of the slip agent, and from 0.005 g / m ² An amount up to 1/2 of the solid content of the agent is more preferable. It is more preferable to use the compound of the general formula (1) and / or (2), the compound of the general formula (3), the above-mentioned binder and the compound of the general formula (4). The above-mentioned slipping agent is coated with a coating liquid prepared by dissolving or dispersing it in a suitable water or organic solvent on a support or a support having another layer on the back surface, or at the time of coating an emulsion, and then dried. It can be formed by As a method of dispersing the slip agent, a generally known emulsification / dispersion method can be used. Specifically, there are a method of dissolving in an organic solvent and emulsifying in water, a method of melting a lubricant at a high temperature and emulsifying in water, a solid dispersion method using a ball mill, a sand grinder, and the like. For such an emulsification and dispersion method, "Handbook of Emulsification and Dispersion Technology Application" (Science Forum version)
Etc. are described in the book.

As the slip agent used in the present invention, various methods in which it is dispersed in an organic solvent can be used. As a method for dispersing in an organic solvent, a generally known method can be used. As a preferred method, specifically, a method in which a lubricant is solid-dispersed by a ball mill, a sand grinder or the like in an organic solvent, a lubricant is heated and dissolved in an organic solvent, and cooling precipitation is performed with stirring. Dispersion method, or a method in which a lubricant is dissolved in an organic solvent by heating and then added to an organic solvent at room temperature or in a cooled state to disperse by cooling and precipitation, and mutually compatible. Not emulsifying with organic solvents. Among these, a preferred method is a method in which the slipping agent is dissolved in an organic solvent by heating, and this is added to an organic solvent at room temperature or in a cooled state, cooled, precipitated and dispersed. The organic solvent used for this dispersion is not particularly limited, but a solvent having a high polarity is preferable as the cooling medium to which the lubricant solution is added. A particularly preferred method is a method in which the lubricant is heated and dissolved at 60 to 150 ° C. and dispersed as a cooling medium in a solvent in which the solubility of the lubricant at room temperature is 1% or less. Among the solvents in which the solubility of the lubricant at room temperature is 1% or less, ketones and alcohols are particularly preferable because of good dispersibility. Further, as the disperser used in this dispersion, an ordinary stirrer can be used, but an ultrasonic disperser and a homogenizer are particularly preferable.

As the diluting solvent used for coating, any solvent may be used as long as it does not deteriorate the dispersion stability or the solubility of the lubricant, for example, water, water containing various surfactants, alcohols (methanol, ethanol). , Isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, and other methyl, ethyl, propyl, butyl esters, etc.), hydrocarbons ( Hexane, cyclohexane, etc.) Halogenated hydrocarbons (methylene chloride, chloroform, carbon tetrachloride, etc.), aromatic hydrocarbons (benzene, toluene, xylene, benzyl alcohol, benzoic acid, anisole, etc.), amides (dimethylformamide, Dimethylacetamide, n-meth Pyrrolidone, etc.), ethers (diethyl ether, dioxane, tetrahydrofuran, etc.), ether alcohols such as propylene glycol monomethyl ether, glycerol, diethylene glycol, dimethyl sulfoxide and the like. Among them, water for handling, water containing various surfactants, alcohols,
Ketones and esters are preferred.

The sliding performance is preferably a coefficient of static friction of 0.25 or less. After conditioning the sample at 25 ° C. and 60% RH for 2 hours,
The HEIDON-10 static friction coefficient measuring device can be used to measure with a 5 mmφ stainless steel ball, and the smaller the value, the better the slipperiness. The coefficient of static friction of the film before and after the development treatment is preferably 0.25 or less, more preferably 0.20 or less, still more preferably 0.16 or less, and particularly preferably 0.12 or less. At this time, it is preferable that both the emulsion surface and the back surface are small, but the smaller the back surface is, the better. The developed static friction coefficient of the present invention is 0.2
To reduce the number to 5 or less, a lubricant may be added to the emulsion layer and the back layer of the film, and it is particularly preferable to add a lubricant to the outermost layers on both sides. The method for containing the slipping agent can be achieved by containing it in a coating solution and applying it, or it may be attached after the film is formed. There is also a means using a spin coating method or the like.

Next, the antistatic agent preferably used in the light-sensitive material of the present invention will be described. In the present invention, the conductive material preferably used is crystalline metal oxide particles, and those containing oxygen vacancies and those containing a small amount of different atoms forming a donor with respect to the metal oxide used are not included. Generally, it is particularly preferable because it has high conductivity, and the latter is particularly preferable because it does not cause fog in the silver halide emulsion. Examples of metal oxides include ZnO, TiO ₂ , SnO ₂ , and Al _2.
O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO
₃ , V ₂ O _5, etc., or composite oxides of these are good,
Particularly, ZnO, TiO ₂ , and SnO ₂ are preferable. Examples of containing a different atom include Al for ZnO,
Addition of In, etc., addition of Sb, Nb, P, halogen elements, etc. to SnO ₂ , and addition of Nb, T to TiO ₂ .
It is effective to add a or the like. The addition amount of these hetero atoms is preferably in the range of 0.01 to 30 mol%,
It is particularly preferably 1 to 10 mol%. Furthermore, in order to improve the dispersibility of fine particles and the transparency, a silicon compound may be added during the formation of fine particles.

The metal oxide fine particles of the present invention have conductivity, and their volume resistivity is 10 ⁷ Ωcm or less, particularly 10 ⁵
Ωcm or less. Regarding these oxides, JP-A-56
-143431, 56-120519, 58-
No. 62647 and the like. Furthermore, as described in JP-B-59-6235, a conductive material in which the above-mentioned metal oxide is attached to other crystalline metal oxide particles or fibrous material (for example, titanium oxide) may be used. . Available primary particle size is 0.0001-1 μm
However, when it is 0.001 to 0.5 μm, the stability after dispersion is good and it is easy to use. Further, it is very preferable to use the conductive particles of 0.001 to 0.3 μm in order to reduce the light scattering property as much as possible because a transparent photosensitive material can be formed. These particles are usually a secondary aggregate in which several or more primary particles are aggregated in the dispersion liquid and the coating film, and the particle size is 0.01 to 0.3 μm, preferably 0.03. Is about 0.2 μm. When the conductive material is needle-like or fibrous, the length is preferably 30 μm or less and the diameter is 1 μm or less, and particularly preferably, the length is 10 μm or less and the diameter is 0.3 μm or less. Is 3 or more.

These conductive metal oxides of the present invention may be coated from a coating solution without a binder, and the preferable coating amount is 1 g / m ² , more preferably 0.000.
9-0.5 g / m ² , particularly preferably 0.0012-0.3
It is g / m ² . In that case, it is preferable to further apply a binder thereon. Further, the metal oxide of the present invention is more preferably applied together with a binder. The binder is not particularly limited, but it is also possible to use the above-mentioned binder, for example, gelatin or dextran,
It may be a water-soluble binder such as polyacrylamide, starch or polyvinyl alcohol, or poly (meth) acrylic acid ester, polyvinyl acetate, polyurethane, polyvinyl chloride, polyvinylidene chloride, styrene / butadiene copolymer, polystyrene, polyester, Synthetic polymeric binders such as polyethylene, polyethylene oxide, polypropylene, polycarbonate, etc. may be used in the organic solvent and further these polymeric binders may be used in the form of aqueous dispersions. Further, these metal oxides may be used as a mixture of spherical and fibrous ones. The content of the metal oxide of the present invention is 0.0005 g / m ²
Or more, more preferably 0.0009 to 0.5 g /
m ² and particularly preferably 0.0012 to 0.3 g / m ² .
Further, a heat-resistant agent, a weather-resistant agent, inorganic particles, a water-soluble resin, an emulsion, etc. may be added to the layer made of the metal oxide of the present invention for matting and improving the film quality within a range that does not impair the effects of the present invention. good. For example, inorganic fine particles may be added to the layer made of the metal oxide of the present invention. Examples of inorganic fine particles to be added, silica, colloidal silica, alumina,
Alumina sol, kaolin, talc, mica, calcium carbonate and the like can be mentioned. The fine particles have an average particle size of 0.
01 to 10 μm is preferable, and more preferably 0.01 to
5 μm, weight ratio to solid content of the coating agent is 0.05 to
10 parts is preferable, and 0.1 to 5 parts is particularly preferable.

Further, various organic or inorganic curing agents may be added to the coating agent of these conductive agents. These curing agents may be low molecular weight compounds or high molecular weight compounds, and these may be used alone or in combination. Examples of the low molecular weight curing agent include, for example, T.H.
"The Theory of." By TH James
The Theory of the Photographic Process
Photographic Process) ", 4th edition, pp. 77-88, and among these, those having a vinyl sulfonic acid, an aziridine group, an epoxy group, or a triazine ring are preferable, and JP-A No. 53-4122
No. 1 and low molecular weight compounds described in JP-A-60-225143 are preferable. The polymer curing agent is preferably a compound having a molecular weight of 2000 or more and having at least two groups that react with a hydrophilic colloid such as gelatin in the same molecule, and as a group that reacts with a hydrophilic colloid such as gelatin. Examples thereof include aldehyde groups, epoxy groups, active halides (dichlorotriazine, chloromethylstyryl groups, chloroethylsulfonyl groups, etc.), active vinyl groups, active ester groups and the like. Examples of the polymer curing agent used in the present invention include polymers having an aldehyde group such as dialdecit starch, polyacrolein and acrolein copolymers described in US Pat. No. 3,396,029, and US Pat. No. 3,623. No. 878, a polymer having an epoxy group, a polymer having a dichlorotriazine group described in Research Disclosure Magazine 17333 (1978), and the like, JP-A-56-66841.
Polymers having an active ester group described in
JP-A-56-142524, US Pat. No. 4,161,
No. 407, JP-A-54-65033, Research Disclosure Magazine 16725 (1978) and the like, and polymers having an active vinyl group or a group serving as a precursor thereof are preferable, and JP-A-56-14252 is particularly preferable.
It is preferable that the active vinyl group, or a group which is a precursor thereof, is bonded to the polymer main chain by a long spacer as described in No. 4.

Next, the conductive polymer or latex preferably used in the invention will be described. The conductive polymer used is not particularly limited, and may be any of ionic (anionic, cationic, etc.), betaine and nonionic, and among them, ionic (anionic, cationic) is preferable. More preferred are anionic sulfonic acid-based, carboxylic acid-based, and phosphoric acid-based polymers or latices, and tertiary amine-based, quaternary ammonium-based, and phosphonium-based polymers. Examples of these conductive polymers include anionic polymers or latexes described in JP-B-52-25251, JP-A-51-29923 and JP-B-60-48024, and JP-B-57.
-18176, 57-56059, 58-56
Examples thereof include cationic polymers or latexes described in US Pat. No. 856, US Pat. No. 4,118,231 and the like. Specific examples of these conductive polymers or latices will be described below, but the present invention is not limited thereto.

[0051]

[Chemical 5]

These conductive polymers or latices of the present invention may be coated from a coating solution without a binder, in which case it is preferable to further coat a binder thereon. Also, the conductive polymer or latex of the present technology may be co-coated with a binder. The content of the conductive polymer or terax of the present invention is 0.005 to 5 g / m ² , and preferably 0.1.
It is 01 to 3 g / m ² , and more preferably 0.02 to 1 g / m ² . The binder is 0.005~5g / m ^2, preferably, 0.01 to 3 g / m ^2, particularly preferably 0.01
~ ² g / m ² . The weight ratio of the conductive polymer or latex to the binder is 99: 1 to 10:90, preferably 95: 5 to 15:85, and particularly preferably 90:10 to 20:80.

The conductive metal oxide, polymer and latex additive layers used in the present invention are not particularly limited,
Examples thereof include a protective layer, an intermediate layer, an emulsion layer, a UV layer, an antihalation layer, an undercoat layer, a back layer and a back protective layer. Among these, a protective layer, an intermediate layer, an antihalation layer, an undercoat layer, a back layer, and a back protective layer are preferable, and an undercoat layer is particularly preferable.
It is a back layer, an intermediate layer, and an antihalation layer. The conductivity of the antistatic layer produced as described above is preferably as low as possible, and its electrical resistance is 1 at 25 ° C. and 10% RH.
It is 0 ¹² or less, more preferably 10 ¹¹ or less, and particularly preferably 10 ¹⁰ or less.

It is needless to say that this conductivity is preferably provided before the developing treatment of the light-sensitive material, but it is desirable that the conductivity can be maintained even after the developing treatment. From this viewpoint, a conductive metal oxide is more preferable. Further, the antistatic agent as described above can particularly improve the effects of the present invention under conditions where static electricity is easily generated (for example, low humidity conditions, 30% RH or less). When static electricity is generated, a magnetic input / output error occurs, and static electricity causes static marks on the image.

The support used in the present invention, its heat treatment and surface treatment will be described below. The cellulose derivative (mainly cellulose triacetate) used in the current photographic light-sensitive material is used in this magnetic recording property-imparting photographic light-sensitive material, and polyester having a glass transition temperature of 50 ° C. to 200 ° C. can also be used. The glass transition temperature (Tg) of polyester is preferably 50 to 200 ° C, and 90 to 200 ° C.
Is more preferable.

The polyester of the present invention is preferably formed by using a diol and an aromatic dicarboxylic acid as components,
Dibasic acids that can often be used in combination with other dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid,
Phthalic anhydride, naphthalenedicarboxylic acid (2,6-,
1,5-, 1,4-, 2,7-), diphenylene p,
p'-dicarboxylic acid, tetrachlorophthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride,
3,6-endomethylenetetrahydrophthalic anhydride,
1,4-cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1,1-dicarboxy-2-phenyl ethylene,
Examples thereof include 1,4-dicarboxymethylphenol, 1,3-dicarboxy-5phenylphenol, and sodium 3-sulfoisophthalate. The aromatic dicarboxylic acid is one having at least one benzene nucleus among the above-mentioned dicarboxylic acids.

Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1 Examples thereof include cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, p-hydroxyethyloxybenzene, and bisphenol A.

If desired, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. Further, the polyester of the present invention may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule, and examples thereof include salicylic acid.

As the monomers of these diols and dicarboxylic acids, first, preferable aromatic dicarboxylic acids are 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), Paraphenylenedicarboxylic acid (PP
DCA), as diol, (poly) ethylene glycol (PEG or EG), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), hydroxycarboxylic acid as a copolymerization component Examples thereof include parahydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA).

Among these polymers, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycyclohexanedimethanol terephthalate (PCT), polyarylate (PAr) are preferable.
And homopolymers thereof, and copolymers of terephthalic acid, naphthalenedicarboxylic acid and ethylene glycol (the mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is 90:
It is preferably 10 to 10:90, and 80:20 to 20:
80 is more preferable. ), A copolymer of terephthalic acid, ethylene glycol and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is 60: 40-
It is preferably between 0: 100, more preferably 50:50 to 10 :.
90 is more preferable. ), Isophthalic acid, para-phenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; the molar ratio of para-phenylenedicarboxylic acid is 10-50 when terephthalic acid is 100, respectively, more preferably, respectively, Two
0-30, preferably 20-30), terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (mole ratio of neopentyl glycol and ethylene glycol is preferably 100: 0 to 70:30, more preferably 90:10). -60: 40) terephthalic acid, a copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is 0: 100-8)
0:20 is preferable, and more preferably 10:90 to 7
It is 0:30. ), Para-hydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of para-hydroxybenzoic acid, terephthalic acid, ethylene glycol is preferably 100: 0 to 10:90:90,
More preferably 90:10:10 to 20:80:80)
And the like are preferable. Among these, polyesters containing 2,6-naphthalenedicarboxylic acid are particularly preferable. Specifically, it is a polyester containing 2,6-naphthalenedicarboxylic acid in an amount of 10 to 100 mol% of the acid content.
Among them, polyethylene 2,6-naphthalate is particularly preferable.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, it can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103-136.
Page, "Synthetic Polymer V" (Asakura Shoten, 1971), 18th
It can be performed with reference to the descriptions on pages 7 to 286.

The preferred average molecular weight range of these polyesters is 5,000 to 200,000. Furthermore, in order to improve the adhesiveness with other polyesters, these polyesters may be partially blended with another polyester, or the monomers constituting the other polyester may be copolymerized, or these polyesters may be copolymerized. A monomer having an unsaturated bond can be copolymerized therein to radically crosslink. A polymer blend obtained by mixing two or more kinds of the obtained polymers is disclosed in JP-A-49
-5482, 64-4325 and JP-A-3-19271.
8. Research Disclosure 283,739-4
1, the same 284, 779-82, the same 294, 807-14
It can be easily formed according to the method described in 1.

The polyester of the present invention has a Tg of 50 ° C.
As described above, the conditions of use are not generally handled with sufficient caution, and the temperature is often exposed to 40 ° C. especially in the midsummer outdoors. From this viewpoint, the Tg of the present invention is safe. The temperature is preferably 55 ° C or higher. More preferably, Tg is 60 ° C. or higher, and particularly preferably 70 ° C. or higher. Further, it is preferable that Tg is 90 ° C. or higher in order to complete the treatment. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used by general users, that is, the temperature in summer exceeds 40 ° C. Polyesters having a glass transition temperature above the temperature are preferred. On the other hand, there is no general-purpose polyester film which is transparent and has a temperature higher than 200 ° C. Therefore, the Tg temperature of the polyester used in the present invention needs to be 50 ° C. or higher and 200 ° C. or lower.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Polyester compound example P-0: PET; [Terephthalic acid (TPA) / ethylene glycol (EG) (100/100)] Tg = 80 ° C. P-1: PEN; [2,6-naphthalenedicarboxylic acid (NDCA) / ( EG) (100/100)] Tg = 119 ° C. P-2: PCT; [(TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: PAr; [TPA / bisphenol A (BPA) (100/100)] Tg = 192 ° C

P-4: 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C P-7: TPA / EG / BPA (100/50/50) Tg = 105 ° C P -8: TPA / EG / BPA (100/25/75) Tg = 135 ° C. P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C. P-10: TPA / PPDCA / IPA / EG (20/50/30/100) Tg = 95 ° C. P-11: NDCA / NPG / EG (100/70/30) Tg = 105 ° C. P-12: TPA / EG / BP (100/20 / 80 Tg = 115 ° C. P-13: TPA / EG / PHBA (50/50/50) Tg = 125 ° C. P-14: TPA / 5-sulfoisophthalic acid (SIPA) / EG (95/5/100) Tg = 65 ° C P-15: NDCA / SIPA / EG (99/1/100) Tg = 115 ° C

P-16: PEN / PET (60/40) Tg = 95 ° C. P-17: PEN / PET (80/20) Tg = 104 ° C. P-18: PAr / PEN (50/50) Tg = 142 ° C P-19: PAr / PCT (50/50) Tg = 118 ° C P-20: PAr / PET (60/40) Tg = 101 ° C P-21: PEN / PET / PAr (50/25/25) Tg = 108 ° C

These supports of the present invention have a thickness of 50 μm or more and 300 μm or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying, whereas if it exceeds 300 μm, it is inconsistent with the purpose of reducing the thickness for compactness. More preferably from the strength of the waist, the thicker one is preferably 50 to 200 μm,
Furthermore, 80 to 115 μm is preferable, and 8 is particularly preferable.
It is 5 to 105 μm. All of the polyesters of the present invention as described above had a flexural modulus higher than that of TAC, and it was possible to realize the original thinning of the film. However, PE has strong bending elasticity among these.
N, PET and using this, TAC is 122 μm
The required film thickness can be reduced to 105 μm or less.

Next, a heat treatment method for improving the winding tendency will be described. The polyester support of the present invention is preferably subjected to a heat treatment, especially under severe conditions (for example, 8
It is particularly preferably used to prevent a marked curl when stored at 0 ° C or higher). In that case, it is necessary to carry out at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours. This effect progresses faster as the heat treatment temperature increases. However, when the heat treatment temperature exceeds the glass transition temperature, the effect is lost. Therefore, this heat treatment needs to be performed at a temperature not higher than the glass transition temperature.

The heat treatment temperature is 40 ° C. or higher and lower than Tg, more preferably Tg-20 ° C. or higher and lower than Tg. Four
If the temperature is lower than 0 ° C., it takes a long time to obtain a sufficient curling effect, resulting in poor industrial productivity. The heat treatment may be carried out at a constant temperature within this temperature range, or may be carried out while cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1 to −5 ° C./hour. The heat treatment time is 0.1 hour or more and 1500 hours or less, more preferably 0.5 hour or more and 200 hours or less.
If the time is less than 0.1 hours, a sufficient effect cannot be obtained, and 1
When the time is 500 hours or more, the effect is saturated, but the support is likely to be colored or brittle.

In order to further increase the effect of eliminating the curling habit, heat treatment ("preheat treatment") is performed beforehand at a temperature of Tg or higher and lower than the melting point (melting temperature determined by DSC) to erase the heat history of the support. After that, heat treatment (“post heat treatment”) may be performed at a temperature of 40 ° C. or higher and lower than Tg. Pre-heat treatment temperature is T
It is preferable to carry out at a temperature not lower than g and lower than the melting point, more preferably not lower than Tg + 20 ° C. and not higher than the crystallization temperature (crystallization temperature determined by DSC). When the pre-heat treatment is performed at a temperature equal to or higher than the melting point, the elasticity of the support is remarkably reduced, which causes problems in surface condition and transportability. The pre-heat treatment may be carried out within this temperature range at a constant temperature (constant temperature pre-heat treatment), may be carried out while lowering the temperature (pre-heat treatment before cooling), or may be carried out while raising the temperature (rise of temperature). Pre-heat treatment). Pre-heat treatment time is 0.1 minutes or more 1
It is 500 hours or less, more preferably 1 minute or more and 1 hour or less. If it is 0.1 minutes or less, a sufficient effect cannot be obtained, and if it is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. After this pre-heat treatment, a post-heat treatment is carried out, but it may be rapidly cooled from the pre-heat treatment end temperature to the post-heat treatment start temperature, or may be gradually cooled to the post-heat treatment start temperature across Tg. Alternatively, the temperature may be once cooled to room temperature and then raised to the post-heat treatment temperature.

Although there are several combinations of these pre-heat treatment and post-heat treatment methods, after the constant temperature pre-heat treatment at Tg + 20 ° C. or higher and the crystallization temperature or lower, a cooling rate of −0. A post-heat treatment is preferably performed while cooling at 1 to -5 ° C / hour.

The heat treatment of such a support may be carried out in the form of a roll or may be carried out while being conveyed in the form of a web. In the case of heat treatment in the form of a roll, either of 1) a method of heat-treating the roll from room temperature in a constant temperature bath, or 2) a method of heat-treating the roll in a roll shape after the temperature is kept at a predetermined value during web conveyance. May be carried out in. The method 1) takes time to raise and lower the temperature, but has the advantage of requiring less equipment investment. The method 2) requires winding equipment at high temperature, but has the advantage that the heating time can be omitted. In the roll-shaped heat treatment, due to the heat shrinkage stress generated during the heat treatment, wrinkles due to winding tightness and surface defects such as cut-outs of the core portion are likely to occur. Therefore, unevenness is imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ are applied) to reduce creaking between the supports to prevent wrinkles due to winding tightening, and It is desirable to make a contrivance such that a knurl is provided on the end of the core and the end of the core is slightly raised to prevent the cut end of the winding core from appearing. On the other hand, when the heat treatment is carried out while the web is conveyed, a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the roll-shaped heat treatment. Among these heat treatment methods, it is preferable that the pre-heat treatment is performed during the web conveyance and the post-heat treatment is performed in a roll shape. This is because if the pre-heat treatment is carried out while the web is being conveyed, planar defects are less likely to occur as compared with the case where the pre-heat treatment is carried out, and the post-heat treatment requires a relatively long time.

These heat treatments may be carried out at any stage after the film formation on the support, after the surface treatment such as glow discharge treatment, after the coating of the back layer (antistatic agent, slipping agent, etc.), and after the undercoat coating. Preferred is after the antistatic agent is applied. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment. Furthermore, in the method for heat treating the polyester of the present invention, in order to shorten the time,
It is preferable to preliminarily heat to Tg or higher for a short time (preferably, perform Tg treatment at 20 ° C. or higher and 100 ° C. or lower for 5 minutes to 3 hours). Further, the roll core used in the heat treatment is preferably one having a built-in electric heater or a structure capable of flowing a high-temperature liquid so that it can be hollow or heated for efficient temperature propagation to the film.
The material of the roll winding core is not particularly limited, but it is preferably one that does not undergo strength reduction or deformation due to heat, and examples thereof include stainless steel and resin containing glass fiber.

For the surface treatment of the support, ultraviolet irradiation treatment,
Any of glow discharge treatment, corona discharge treatment, and flame treatment can be used. Glow discharge treatment is described in U.S. Pat. Nos. 3,462,335, 3,761,299, 4,072,769 and British Patent 891,469.

The composition of the discharge atmosphere gas at the time of glow discharge treatment may be only the gas species generated in the container by the discharge treatment of the support itself after the start of discharge as described in JP-A-59-556430. However, Japanese Patent Application No. 5-199
It is preferable to carry out the glow discharge treatment in the presence of water vapor described in No. 704. Water vapor partial pressure is 10% or more and 100%
The following is preferable, and 40% or more and 90% or less is more preferable. The gas other than water vapor is air composed of oxygen, nitrogen and the like. The method of quantitatively introducing water vapor into the glow discharge treatment atmosphere is as follows. Can be achieved by quantifying.

When the glow discharge treatment is carried out in a state where the support to be surface-treated is preheated, the adhesion can be improved in a short time and the yellowing of the support can be greatly reduced. The preheating temperature is preferably 50 ° C. or higher and Tg or lower, and 70
C. or higher and Tg or lower are more preferable, and 90.degree. C. or higher and Tg or lower are even more preferable. Specific methods for raising the polymer surface temperature in vacuum include heating with an infrared heater and heating with contact with a hot roll. The glow discharge treatment is preferably performed using the discharge electrode and the discharge treatment device described in Japanese Patent Application No. 147864/1993. The degree of vacuum during glow discharge treatment is preferably 0.005 to 20 Torr, more preferably 0.02 to 2 Torr. The voltage is 500-
It is preferably between 5,000 V and more preferably 500-3.
It is 000V. The discharge frequency used is DC to several 1
000 MHz, more preferably 50 Hz to 20 MHz,
More preferably, it is 1 KHz to 1 MHz. Discharge intensity is 0.01 KV · A · min / m ^{2 to 5} KV · A · min /
m ² is preferable, more preferably 0.15 KV · A · min /
m ^{2 to 1} KV · A · min / m ² . It is preferable that the temperature of the support subjected to the glow discharge treatment is immediately lowered by using a cooling roll by the method described in JP-A-3-39106.

The ultraviolet irradiation treatment is conducted in Japanese Examined Patent Publication No. 43-2603.
It is preferable to use the processing methods described in JP-B No. 43-2604 and JP-B No. 45-3828. The mercury lamp is a high pressure mercury lamp consisting of a quartz tube and has an ultraviolet wavelength of 220.
Those between ˜380 nm are preferred. The UV irradiation may be performed in the stretching step of the support, at the time of heat setting, or after the heat setting.

With respect to the method of ultraviolet irradiation, a high-pressure mercury lamp having a main wavelength of 365 nm can be used as the light source if there is no problem in the performance of the support that the surface temperature of the support will rise to around 150 ° C. . When low temperature treatment is required, a low pressure mercury lamp having a dominant wavelength of 254 nm is preferable. It is also possible to use an ozone-less type high pressure mercury lamp and a low pressure mercury lamp. Regarding the amount of light to be treated, the larger the amount of treatment is, the more the adhesive force between the support and the layer to be adhered is improved. Therefore, for ordinary polyester, polyolefin and other plastic films, a high pressure mercury lamp with a main wavelength of 365 nm
Irradiation dose 20~10000mJ / cm ² C., more preferably 50~2000mJ / cm ^2. In the case of a low pressure mercury lamp having a main wavelength of 254 nm, the irradiation light amount is 100 to 10
000 mJ / cm ² is preferable, more preferably 300 to 1500
It is mJ / cm ² .

For corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar can be used. The discharge frequency during the treatment is 5 to 40 KHz, more preferably 10 to 30 KHz. The waveform is preferably an AC sine wave. The gap clearance between the electrode and the dielectric roll is 1 to 2 mm, more preferably 1.4 to 1.6 mm. Further, the treatment amount is 0.3 to 0.4 KV · A · min / m ² , and more preferably 0.34 to 0.38 KV · A · min / m ² .

The flame treatment method may be either natural gas or liquefied propane gas, but the mixing ratio with air is important. In the case of propane gas, the preferable mixing ratio of propane gas / air is 1/22 to 1/14, preferably 1/19 to 1/16 by volume. In the case of natural gas, it is 1/10 to 1/6, preferably 1/9 to 1/7.
The amount of flame treatment is 1 to 50 Kcal / m ² , more preferably 3 to ²
It is recommended to do it in the range of 0 Kcal / m ² . It is more effective if the distance between the tip of the internal flame of the burner and the support is less than 4 cm. A frame processing device manufactured by Kasuga Electric Co., Ltd. can be used as the processing device. Further, the backup roll that supports the support during the flame treatment is a hollow roll, and it is preferable that the backup roll is water-cooled by cooling water and always treated at a constant temperature.

Next, the silver halide photographic light-sensitive layer of the present invention will be described in detail. The light-sensitive material of the present invention comprises a silver halide emulsion layer, a back layer, a protective layer, an intermediate layer, an antihalation layer and the like, and these are mainly used in the hydrophilic colloid layer. In that case, the binder of the hydrophilic colloid layer includes, 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 thereof include polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives and partial hydrolysates thereof, dextran, polyvinyl acetate, polyacrylic acid ester, rosin and the like, if necessary. Mixtures of two or more of these colloids may be used.

The most used of these is gelatin or its derivative, and the gelatin mentioned here means so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin. 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 hardeners (single or in combination). In the present invention, an anion, a nonion, a cation, and a betaine fluorine-containing surfactant can be used in combination. These fluorine-containing surfactants are disclosed in JP-A-49-10.
No. 722, British Patent No. 1,330,356, JP-A-5
3-84712, 54-14224, 50-1
13221, U.S. Pat. Nos. 4,335,201, 4,347,308, and British Patent 1,417,915.
No. 52/26687 / 57-26719
No. 59-38573, JP-A-55-149938.
No. 54, No. 54-48520, No. 54-14224, No. 58-200235, No. 57-146248, No. 5
8-196544, British Patent No. 1,439,402
No., etc. Specific examples of these fluorine-containing surfactants will be described.

[0083]

[Chemical 6]

In the present invention, a nonionic surfactant may be used. Specific examples of the nonionic surfactant preferably used in the present invention are described below.

[0085]

[Chemical 7]

The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material. For example, a surface protective layer, an emulsion layer, an intermediate layer, Examples thereof include an undercoat layer and a back layer. The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention may be 0.0001 to 1 g per 1 square meter of the photographic light-sensitive material,
It is more preferably 0.0005 to 0.5 g, and particularly preferably 0.0005 to 0.2 g. Further, two or more kinds of these surfactants of the present invention may be mixed. Also,
Ethylene glycol, propylene glycol, 1,1,
1-Trimethylolpropane etc. JP-A-54-89626
A polyol compound as shown in No. 1 can be added to the protective layer or other layers of the present invention. Other known surfactants may be added to the photographic constituent layers of the present invention alone or in combination. Although they are used as coating aids, sometimes they have other purposes, such as emulsion dispersion,
It is also applied for sensitization and other improvement of photographic characteristics.
Further, in the present invention, a lubricating composition, for example, US Pat. Nos. 3,079,837 and 3,080,317
No. 3,4,535,970, No. 3,294,53
No. 7, and modified silicones as disclosed in JP-A No. 52-129520 can be contained in the photographic constituent layers.
For example, US Pat. Nos. 4,275,146 and 3,93
No. 3,516, Japanese Patent Publication No. 58-33541, British Patent No. 927,446, and Japanese Patent Laid-Open Nos. 55-126238 and 5;
No. 8-90633 and the like. These compounds may be used in combination with the slip agent of the present invention.

The photographic light-sensitive material of the present invention has US Pat.
And polymer latexes described in JP-B-45-5331 and the like. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene anhydride-containing copolymers, acrylic ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. Of these, gelatin is the most preferable. Further, a gelatin derivative or the like may be used in combination with gelatin. The protective layer containing gelatin can be hardened. Examples of the hardener 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 and other compounds having reactive halogen, divinyl sulfone, 5-acetyl-1,3
-Diacryloyl hexahydro-1,3,5-triazine, compounds having reactive olefin, N-hydroxymethylphthalimide, N-methylol compound, isocyanates, aziridine compounds, acid derivatives, epoxy compounds, Mention may be made of halogen carboxaldehydes such as mucochloric acid. Alternatively, as the inorganic compound hardening agent, chromium alum, zirconium sulfate and the like can be mentioned. Further, a carboxyl group-activating type hardener and the like can also be used.

In the present invention, in order to improve the adhesion failure under high temperature and high humidity, it is preferable to give unevenness to the surface of the photosensitive material. Therefore, in the present invention, the average height of the protrusions on the emulsion-side and / or back-side surface is 0.02 to 10 μm, preferably 0.05 to 5 μm. Also, it is preferable that the number of protrusions on the surface is large, but if there are more protrusions than necessary, the haze becomes large, which is a problem. Preferred protrusions may any number as long as it has an average height of the protrusions of the present invention, for example spherical, its content when forming a projection in the irregular matting agent in 0.5~600mg / m ² Yes, more preferably 1 to 400 mg / m ² . The matting agent used for this purpose is not particularly limited in its composition, and may be an inorganic material or an organic material, and two or more kinds may be used.

The particles used in the present invention may be particles that remain in the light-sensitive material even after the development processing or may be dissolved in the processing solution. In that case, it is desirable to contain a group capable of being dissolved in alkaline. Examples of the inorganic compound and the organic compound of the matting agent of the present invention include fine powders of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide. Examples thereof include silicon dioxide such as synthetic silica obtained by chemical conversion, and titanium dioxide (rutile type or anatase type) generated by titanium slag and sulfuric acid. It can also be obtained by pulverizing from an inorganic material having a relatively large particle size, for example, 20 μm or more, and then classifying (vibrating filtration, air classification, etc.). In addition, pulverized and classified products of organic polymer compounds such as polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate and starch are also included. Alternatively, a polymer compound synthesized by a suspension polymerization method, a polymer compound spherically formed by a spray drying method or a dispersion method, or an inorganic compound can be used. Further, a polymer compound, which is a polymer of one or more of the following monomer compounds, may be formed into particles by various means. The polymer may be polymerized from a single monomer or may be particles copolymerized from a plurality of monomers. As the monomer, acrylic acid esters, methacrylic acid esters, vinyl esters, styrenes and olefins are preferably used.

Further, in the present invention, JP-A-62-14647 is used.
Nos. 62-17744 and 62-17743 may be used, and particles having a fluorine atom or a silicon atom may be used. Among these, the particle composition preferably used is polystyrene, polymethyl (meth) acrylate, polyethyl acrylate, poly (methyl methacrylate / methacrylic acid = 95/5, or 50/50 (molar ratio), poly (styrene / styrene sulfonic acid). = 95/5, or 60/40 (molar ratio), polyacrylonitrile, poly (methyl methacrylate / ethyl acrylate / methacrylic acid = 50/40/10),
Examples thereof include silica.

Furthermore, the particles of the present invention are disclosed in JP-A-64-
It is also possible to use particles having reactive (especially gelatin) groups as described in EP 77052 and EP 307855. These matting agents are preferably 0.01 to
0.1 to 20 having an average particle size of 25 μm
μm is more preferable. The layer containing the matting agent is not particularly limited, but is preferably an emulsion protective layer, a back layer, or a back protective layer. Among them, the emulsion and the back protective layer are preferable, and the thickness of the protective layer is 0.05 to 6 μm, and more preferably 0.15 to 5 μm.

Particularly, representative examples of the silver halide color photographic light-sensitive material preferable in the present invention include a color reversal film and a color negative film. Particularly, a color negative film for general use is a preferable color photographic light-sensitive material. Description will be made below using a general-purpose color negative film. The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. The number of layers and the order of layers of the non-photosensitive layer are not particularly limited. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic light-sensitive material, it is generally a unit photosensitive layer. The arrangement is such that the red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are arranged in this order from the support side. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

Next, the film cartridge (or cartridge) used in the present invention will be described. The patrone used in the present invention is mainly made of synthetic plastic. In molding the plastics of the present invention, a plasticizer is mixed with the plastics as needed. Examples of the plasticizer include trioctyl phosphate, tributyl phosphate, dibutyl phthalate, diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone, di-n-octyl succinate, bromonaphthalene and butyl palmitate. It is a target.

Specific examples of the plastic material used in the present invention are shown below, but the invention is not limited thereto. Specific examples include polystyrene, polyethylene, polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, methylmethacryl resin, vinyl formal. Resin, vinyl butyral resin, polyethylene terephthalate, Teflon, nylon, phenol resin, melamine resin and the like.

Particularly preferred plastic materials for the present invention are polystyrene, polyethylene, polypropylene and the like. Further, the cartridge of the present invention may contain various antistatic agents. The antistatic agent is not particularly limited, but carbon black, metal oxide particles, nonion, anion,
Cation and betaine-based surfactants or polymers can be preferably used. As these antistatic patrones, JP-A-1-125537 and 1-3
No. 12538.

In particular, the resistance at 25 ° C. and 25% RH is 10 ¹²
Ω or less is preferable. Usually, Patrone is made of plastic in which carbon black, pigments, etc. are kneaded in order to impart a light-shielding property. The size of the cartridge may be the same as it is now, or if the diameter of the current cartridge of 25 mm is 22 mm or less, preferably 20 mm or less, 14 mm or more, it is effective for downsizing the camera.

The volume of the cartridge case is 30 cm ³ or less, preferably 25 cm ³ or less, more preferably 20 cm ³ or less. The weight of the plastic used in the cartridge and cartridge case is 1g to 25g.
It is preferably 5 g or more and 15 g or less. The ratio of the inner volume of the cartridge to the cartridge and the plastic used in the cartridge is 4 to 0.7, preferably 3
~ 1.

In the case of a patrone containing the preferred 135 color light-sensitive material of the present invention, the total weight of the plastic used in the patrone and the patrone case is usually 1 g.
It is 5 g or less and preferably 5 g or more and 15 g or less.
The patrone of the present invention is not particularly limited in its form.

Further, a cartridge used in the present invention to feed a film by rotating a spool will be described.
First, there is a photographic film cartridge that can be loaded into the camera without pulling out the tip of the photographic film from the main body of the cartridge in advance, and that the feeding mechanism on the camera side can be simplified. This photo film cartridge has a structure in which the leading end of the film is housed in the main body of the cartridge, and the spool is rotated in the film feeding direction to feed the leading end of the film from the port of the cartridge to the outside. In such a photographic film cartridge, U.S. Pat. No. 4,834,306 (Japanese Patent Laid-Open No. 1-33)
In the film cartridge disclosed in No. 06845), flanges are rotatably provided at both ends of a spool shaft around which the film is wound, and the outer periphery of these flanges is bulged inward. A tongue is provided. That is, the outermost circumference of the film is sandwiched between the tongue pieces provided on the flange, and the tongue pieces prevent the outermost circumference of the film from loosening. A wide opening protrusion for deforming the flange is provided at a position where the film faces the port opening so as to widen the space between the flanges. That is, near the port,
The wide-opening projections push the flanges apart at all times, and the outermost periphery of the film sandwiched between the tongue pieces provided on these flanges can escape from the tongue pieces. As a result, when the spool shaft is rotated in the film feeding direction, the leading end of the film is fed from the port portion to the outside of the cartridge.

The method of shielding the film outlet is arbitrary. A felt-shaped light-shielding member called "telemp" may be provided as in the conventional case, or the film outlet may be formed so as to be openable and closable and kept closed except when necessary. Further, the tip of the film does not necessarily have to be arranged in alignment with the tip of the film outlet, and may be stored inside the cartridge body.
It is desirable that it be stored in the film outlet.

Further, the film cartridge disclosed in Japanese Patent Laid-Open No. 4-115251 (US Pat. No. 5,226,613) has flanges rotatably provided at both ends of the spool shaft and outer peripheries of these flanges. Of the tongue that is formed so as to project toward the inner side of the spool shaft and that prevents loosening of the outermost periphery of the film wound around the spool shaft, and that is provided inside the cartridge and that rotates the flange at an angle inclined with respect to the spool shaft. A first restricting rib that restricts the movement freely, and a second restricting rib that restricts the limit of the angle at which the flange inclines with respect to the spool shaft.
The width of the film tip is narrower than the distance between the tips of the tongues, and is formed so that the step between the side end of the film tip and the side end of the photographable portion becomes a gentle curve. When the film is fed out, this step comes into contact with the tongue piece to spread the flange. Further, a flange rotatably provided at both ends of the spool shaft, and a tongue piece that is formed to project toward the inner side of the outer periphery of these flanges and prevents loosening of the outermost periphery of the film wound around the spool shaft. And a wide-opening protrusion that is provided inside the cartridge when the film is in a position toward the port opening and that restricts the flange interval by widening the flange by abutting the tongue piece, and the flange at an angle inclined with respect to the spool shaft. This is provided with a regulation rib that rotatably regulates.

The photographic film used in the present invention may be a so-called raw film before development or a photographic film which has been subjected to development processing. Further, the raw film and the developed photographic film may be stored in the same new cartridge, or may be different cartridges. In particular, since the developed photographic film is stored for a long time, the storage container is larger and the spool can rotate more easily than the cartridge for storing the raw film, and the light-shielding mechanism (for example, teremp) is not required. In some cases, it is preferable that the new cartridge contains a sufficient amount of a slip agent and an antistatic agent. Also,
The developed photographic film may be stored in a new cartridge after applying a slipping agent or an antistatic agent by a final processing bath or a coating method (for example, spraying, transferring, coating method, etc.) during the developing processing.

[0103]

The present invention will be described in detail below with reference to specific examples, but the present invention is not limited thereto. (Example 1) 1) Preparation of support and heat treatment Polyethylene naphthalate (PEN) chips were melt extruded, and then longitudinally stretched 3.4 times and laterally 4 times, and biaxially stretched to a thickness of 90μ. A polyester support was formed into a film. The film is formed at an extrusion temperature of 300 ° C. and a longitudinal stretching temperature of 140.
C., transverse stretching temperature 130.degree. C., heat setting 250.degree. C. for 6 seconds. After the film formation, the support was heat-treated by winding it on a stainless air core having an outer diameter of 30 cm and heating at 110 ° C. for 24 hours.

2) Surface Treatment, Coating of Photosensitive Layer Side Adhesive Layer Both surfaces of the PEN support were subjected to ultraviolet irradiation treatment. The ultraviolet irradiation treatment was carried out in the same manner as the method shown in the example of JP-B-45-3828. Then, an adhesive layer liquid having the following formulation was applied to the photosensitive layer side at a coating amount of 10 ml / m ² and dried at 110 ° C. for 2 minutes. (Adhesive layer liquid formulation) Gelatin 1 part by weight Water 1 part by weight Acetic acid 1 part by weight Methanol 50 parts by weight Ethylene dichloride 50 parts by weight p-Chlorophenol 4 parts by weight

3) Coating of the first layer of the back The first layer of the back was applied with the same amount of the liquid having the same formulation as the above-mentioned adhesive layer.

4) Coating of second layer of back 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N sodium hydroxide aqueous solution was added dropwise to this solution until the pH of the solution became 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate. The reddish brown colloidal precipitate was separated by centrifugation.
To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. 200 parts by weight of the colloidal precipitate from which excess ions were removed was redispersed in 1500 parts by weight of water and sprayed in a baking furnace heated to 650 ° C., and the bluish average particle size was 0.005 μm.
Fine particles of stannic oxide antimony monoxide composite were obtained. The resistivity of this fine particle powder was 25 Ωcm. A mixed solution of 40 parts by weight of the above fine powder and 60 parts by weight of water was adjusted to pH 7.0, roughly dispersed by a stirrer, and then retained by a horizontal sand mill (Dynomill, manufactured by Willy A. Backfen AG) for a residence time of 30.
Dispersion was carried out until the total amount of the primary particles was partially agglomerated to prepare a dispersion having an average particle diameter of 0.08 μm.

A second layer coating solution was prepared according to the following formulation,
It was applied so that the dry film thickness was 0.3 μm, and dried at 110 ° C. for 30 seconds. (Second layer liquid formulation) The conductive fine particle dispersion liquid (SnO ₂ / Sb ₂ O ₅ , 0.15 μm) 10 parts by weight gelatin 1 part by weight water 27 parts by weight methanol 60 parts by weight resorcin 2 parts by weight poly (oxyethylene) (Polymerization degree 10) 0.01 parts by weight of nonyl phenyl ether

5) Coating of the third layer on the back Co-deposition-added 1100 parts by weight of the γFe ₂ O ₃ magnetic material to 220 parts by weight of water and 150 parts by weight of the silane coupling agent of compound example [1] -19 in the present text. And kneaded well in an open kneader for 3 hours. The roughly dispersed viscous liquid is heated to 70 ° C.
After being dried for 1 day and at room temperature to remove water, it was heated at 110 ° C. for 1 hour for treatment to prepare surface-treated magnetic particles. Further, the following formulation was used, and the mixture was kneaded again in an open kneader. The surface-treated magnetic particles 1000 parts by weight Diacetyl cellulose 17 parts by weight Methyl ethyl ketone 100 parts by weight Cyclohexanone 100 parts by weight Further, 200 by a sand mill (1 / 4G) with the following formulation.
Finely dispersed at 0 rpm for 4 hours. Kneaded product 100 parts by weight Diacetyl cellulose 60 parts by weight Methyl ethyl ketone 300 parts by weight Cyclohexanone 300 parts by weight Finally, the mixture was diluted with the following formulation. The above-prepared fine dispersion liquid 70 parts by weight Diacetyl cellulose 130 parts by weight Methyl ethyl ketone 1300 parts by weight Cyclohexanone 1300 parts by weight C ₂ H ₅ C (CH ₂ OCONHC ₆ H ₃ (CH ₃ ) NCO) ₃ (curing agent) 34 parts by weight Silica particles ( Particle size 0.3 μm (matting agent) 3 parts by weight Aluminum oxide (particle size 0.5 μm) (abrasive) 1 part by weight The diluted solution is filtered (filter diameter, 30 μm) in advance to form the third layer coating solution. did. The wire bar was applied within 10 days after filtration. The film thickness is 1.2 μm, the amount of magnetic material is 70 mg / m ² , and the matting agent and the polishing agent are each 30
It was adjusted to be mg / m ² , 10 mg / m ² . At the time of application, in order to further remove foreign matter, filtration (filter diameter, 10 μm) was performed immediately before the application portion, and the overflowed liquid was filtered (filter diameter, 30 μm) and then returned to the pipe.

6) Coating of Back Fourth Layer After coating of the above-mentioned third layer of back, a slipping agent was dispersed in the coating solution by the following method, and the solution was prepared to apply. First, a lubricant, a dispersant, etc. shown in Table 1 were added to a solvent according to the following formulation, and dissolved by heating at 105 ° C. Lubricants + dispersants and the like shown in Table 1 1 part by weight Xylene 4 parts by weight This solution was added to 15 parts by weight of isopropanol and precipitated with stirring. Furthermore, this slip agent dispersion,
Using a high-pressure homogenizer, the output was dispersed for a maximum of 10 minutes to obtain a slip agent dispersion stock solution. The coating solution for the fourth layer prepared from this undiluted solution of the slip agent was coated on the above-mentioned third layer of the wire bar with a wire bar. The coating amount was 10 ml / m ² . 3 at 110 ° C
A sample was prepared by drying for a minute to form a surface layer (at this time, it was confirmed that the temperature inside the casing of the conveying system and the substantial temperature of the conveying roller were 110 ° C). (4th layer coating liquid formulation) Acetone 240 parts by weight Cyclohexanone 170 parts by weight The above slip agent dispersion liquid 20 parts by weight Additive binder shown in Table 1 2 parts by weight As a comparative example, instead of the above lubricant, a comparative lubricant As the coating, coating was performed in the same manner as in the above example except that the one shown in Table 1 was used.

[0110]

[Table 1]

[0111]

[Chemical 8]

7) Coating of Photosensitive Layer On the support coated with an adhesive layer, each photosensitive layer having the composition shown below was multilayer-coated to prepare a multilayer silver halide color photosensitive material sample. (Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer. The layer structure is shown below.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth Layer (First Protective Layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 ExF-8 0.045 ExF-9 0.050 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 2.3 μm) 5.0 × 10 ^-2 B-2 (diameter 2.3 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-3, B-4 to B- may be used. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0128]

[Table 2]

In Table 2, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
was μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0132]

[Chemical 9]

[0133]

[Chemical 10]

[0134]

[Chemical 11]

[0135]

[Chemical 12]

[0136]

[Chemical 13]

[0137]

[Chemical 14]

[0138]

[Chemical 15]

[0139]

[Chemical 16]

[0140]

[Chemical 17]

[0141]

[Chemical 18]

[0142]

[Chemical 19]

[0143]

[Chemical 20]

[0144]

[Chemical 21]

[0145]

[Chemical formula 22]

[0146]

[Chemical formula 23]

[0147]

[Chemical formula 24]

8) Development processing of sample The prepared sample was developed by the following method.
As the developing machine, a cine type automatic developing machine FNCP-900 manufactured by Fuji Photo Film Co., Ltd. was used. The development processing time of these samples is as follows. Processing time Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Water washing 2 minutes 10 seconds Fixing 4 minutes 20 seconds Water washing 3 minutes 15 seconds Stability 1 minute 5 seconds The treatment liquid composition used in each step is as follows. It was on the street.

Color developer Diethylenetriamine pentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 g Hydroxylamine Sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino-2-methylaniline sulfate 4.5 g Water was added to bring the total amount to 1.0 liter pH 10.0

Bleaching Solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water was added to bring the total amount to 1.0 liter pH 10.0

Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 g Sodium bisulfite 4.6 g Water was added to a total volume of 1.0 liter pH 6.6

Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononyl ether (average degree of polymerization 10) 0.3 g Water was added to bring the total amount to 1.0 liter.

9) Processing of Samples Photographic film samples obtained by slitting each sample into a width of 35 mm and a width of 24 mm were loaded into the reverse feeding cartridge shown in FIG. 9 of JP-A-5-210202. At this time, the outer diameter of the cartridge is 20 mm, the inner diameter is 18 mm, and the spool diameter is 7 mm.
And the length of the loaded photographic film sample was 1.4 m.

10) Characteristic Evaluation Method The samples were evaluated as follows. (A) Evaluation of magnetic output error With the signal input method disclosed in the above-mentioned WO 90-04205, after magnetically input from the coated surface side of the magnetic recording layer in advance, development processing is performed, and the sensitive material is magnetized before and after that. The output operation was performed 1000 times with the head, and the number of output errors was shown. Evaluation is 25 ℃ 55%
It was conducted under the RH environment. (B) Evaluation of repellency unevenness after development processing 1.4 m of a sample processed to have a width of 35 mm was processed by a method generally called hanging in the photographic industry. That is, it is a method of suspending the sensitive material on a suspension jig and immersing it in a bath containing the above-mentioned developing solution. After completion of the development process, the repellency unevenness of the back surface of the sample was evaluated by three ranks of ◯ Δx. ○ indicates almost no unevenness, △
Indicates a state where liquid flow-like unevenness is visible, and × indicates a state where repellency unevenness is clearly visible. ○ and △ are acceptable in the photograph. (C) Measurement of Contact Angle The contact angle was measured on the sample after development, which was washed with running water for 2 minutes, dried, and conditioned at 25 ° C. and 60% RH for 2 hours or more. The measurement liquid used was a 0.3% aqueous solution of poly (oxyethylene) nonylphenol (n = 8.6). The temperature and humidity conditions at the time of measurement are 25 ° C. and 60% RH. For the measurement of the contact angle, the measurement liquid was dropped on the surface of the sample to which the slipping compound was applied, and the value obtained 2 minutes after the dropping was read.

(D) Surface Condition of Coating The surface condition of the sliding layer after the lubricant was applied was evaluated on a scale of 5 from A to E. Photographically, A and B are acceptable levels, C is photographicly acceptable but is visually unpleasant and barely permissible, and D and E are high in haze, which causes printing problems. (E) Measurement of dynamic friction coefficient After the sample was conditioned for 2 hours at a temperature of 25 ° C and a humidity of 60% RH,
EIDON-14 dynamic friction coefficient measuring machine, using 5mmφ stainless steel ball, load 100g, friction speed 60cm /
Measured in minutes. The smaller the value, the better the slipperiness. (F) Evaluation of scratch resistance After conditioning the sample at a temperature of 25 ° C. and a humidity of 60% RH for 2 hours, a diamond having a tip of 0.025 mmR was formed on the back surface (the surface not coated with the photosensitive material) before and after the development processing. Apply the needle vertically and apply a continuous load to the sample back surface at 60 cm /
Scratch at the speed of a minute. The sample after scratching was placed on Schaukasten, and the scratching strength was defined as the strength at which scratches began to be visible by permeation. The larger the value, the better the scratch resistance. Here, if the repellency unevenness is poor after the development processing, unevenness occurs in the print processed image. If the slipperiness and scratch resistance are poor, the back layer will be scratched during magnetic output, which will result in scratches on the printed image, which is unacceptable photographically.

11) Evaluation Results From the results shown in Table 3, the following was revealed. Samples 1-2 to 1-18 using the compound of the present invention all fall within the range in which the magnetic output error frequency is allowed, and the treatment liquid is excellent in repellency, surface state, slipperiness, and scratch strength, The performance was photographically acceptable. On the other hand, in Example 1-1 in which there was no slip agent, the number of magnetic output errors was large, and the slipperiness and scratch strength were extremely poor. In addition, 1-19, 20 and 1-22, 2 using a compound that does not contain a polar group
In No. 3, the magnetic output error frequently occurred and the repellency unevenness after the processing was bad. In addition, even with 1-21 in which a compound having a small total carbon number and a short alkyl chain length was used, a magnetic output error frequently occurred, and the slipperiness and scratch strength after the treatment deteriorated. In addition, Samples 1-5, 6, 14, 15 in which the compound represented by the general formula (3) is added to the compounds represented by the general formulas (1) and (2) of the present invention, the general formula (4) Samples 1-7, 8 and 16 to which the compound represented by the formula (1) was added had further improved repellency unevenness after the treatment. Furthermore, sample 1 using both
In Nos. 9 and 17 and Samples 1 to 10 and 18 to which a binder was added, the repellency unevenness after the treatment was further improved, and the magnetic output error was extremely close to zero, which was a great improvement. Further, from the result of measuring the contact angle of the above-mentioned sample, the sample having a contact angle of 45 degrees or less has an acceptable level of unevenness of the treatment liquid,
It became clear that the repellency of the treatment liquid is less likely to occur when the temperature is less than 10 degrees.

[0157]

[Table 3]

Example 2 As shown in Table 4, Example 1
Instead of the ultraviolet irradiation treatment of Example 2, corona discharge treatment (Example 2
−1 to 3), glow discharge treatment (Examples 2-4 to 6), or flame treatment (Examples 2-7 to 9), and then immediately applied to the photosensitive layer-side adhesive layer and the back-side first layer. Examples 1-2 and 1 except that the layer coating method is changed to the method shown below
Table 5 shows the results of evaluation of the samples prepared in the same manner as in Examples 1-2, 10 and 16 (Examples 2-10 to 12) except that the samples prepared in the same manner as in Examples 0 and 16 were not subjected to surface treatment. It was As shown in Table 5, in Examples 2-10 to 12, sufficient adhesion cannot be obtained between the support and the coated photosensitive layer or back layer on both the emulsion surface and the back surface. It didn't make sense. However, in other embodiments 2-1 to 3,2-
In Nos. 4 to 6 and 2 to 7 to 9, the same effects as in Examples 1-2, 10 and 16 were obtained, excellent magnetic recording performance, no unevenness of repelling of the processing liquid occurred, and other photographic performances were also excellent. The wood was obtained.

[0159]

[Table 4]

[0160]

[Table 5]

The surface treatment used in this example and the method for applying the photosensitive layer side adhesive layer and the back side first layer applied immediately after the surface treatment will be described below. 12) Corona discharge treatment After performing corona discharge treatment on both sides of the support, an adhesive layer having the following formulation was formed on the photosensitive layer side and the same back layer was formed on the back layer side.
Layers were provided. The coating amount was 10 ml / m ² and the coating was dried at 115 ° C. for 6 minutes. For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. was used, and a 20 cm / 30 cm wide support was used.
Process in minutes. At this time, the object to be treated was treated at 0.375 kV · A · min / m ^{2 based} on the readings of current and voltage. The discharge frequency during the treatment was 9.6 kHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. (Adhesive layer formulation) Gelatin 300 parts by weight Distilled water 25000 parts by weight Sodium α-sulfodi-2-ethylhexyl succinate 5 parts by weight Formaldehyde 2 parts by weight

13) Glow Discharge Treatment Both sides of the support were subjected to a reduced pressure of 0.2 mmHg and an output of 250.
Glow discharge treatment was performed at 0 W with a treatment intensity of 0.5 kV · A · min / m ² . The photosensitive layer side of this support was coated with the adhesive layer liquid of the following formulation, and the back layer side was coated with the same liquid at 10 ml / m ² , and 1
It was dried at 15 ° C for 6 minutes. (Adhesive layer formulation) Gelatin 100 parts by weight Salicylic acid 30 parts by weight Resorcin 100 parts by weight Compound G 5 parts by weight Poly (oxyethylene) (polymerization degree 10) Nonyl phenyl ether 10 parts by weight Water 202 parts by weight Methanol 9553 parts by weight

[0163]

[Chemical 25]

14) Flame treatment As a flame treatment device, a flame treatment device manufactured by Kasuga Electric was used. The distance between the tip of the inner flame of the burner and the support was set to 2 cm, and the mixing ratio of propane gas / air was 1/18 by volume. The flame treatment amount was 5 Kcal / m ² . The backup roll supporting the support during the flame treatment was a hollow roll through which cooling water was passed, and the treatment was always performed at a constant temperature of 30 ° C. The adhesive layer liquid was prepared and applied with the same formulation as the sample subjected to the glow discharge treatment.

(Embodiment 3) In this embodiment, in consideration of a sample under severe conditions, the following curling habit evaluation and magnetic recording output error evaluation under severe conditions were performed. As shown in Tables 6 and 7, Example 3 was the same as Example 1-10.
-1 was produced. A sample (Example 3-2) produced in the same manner as in Example 3-1 except that the heat treatment that should be performed after film formation was not performed, and the back second layer liquid formulation was used in Example 3-1. Of which, 10 parts by weight of the conductive fine particle dispersion is mixed with 1 part of water.
Samples prepared in the same manner as in Example 3-1 except that coating was carried out by using 0 parts by weight and 1 part by weight of the dispersion liquid and 9 parts by weight of water to prepare (Examples 3-3 and 4). ) Furthermore, in Example 3-1, a sample (Example 3-5) prepared in the same manner as in Example 3-1 except that the matting agent to be added is not added to the back third layer (Example 3-5) and Example. Example 3-
In Example 1, the sample (Example 3-6) produced in the same manner as in Example 3-1 except that the abrasive to be added was not added to the back third layer was evaluated as follows. The results are shown in Table 7.

[0166]

[Table 6]

[0167]

[Table 7]

First, the evaluation method newly performed in the third embodiment will be described. (G) Core set and curl evaluation The sample loaded in the cartridge is heat-treated (core set) in an environment of 80 ° C. for 2 hours, then cooled, and then cooled at 25 ° C. and 55% RH.
The film sample was taken out from the cartridge under the temperature and humidity, the radius of the innermost peripheral portion was measured in units of meters, and the reciprocal thereof was used as the evaluation value of curl. The larger the number, the easier it is for the curl to occur. After this measurement, the film sample was developed. Those having a strong winding tendency were crushed by the nip rolls in the developing machine during the development processing, resulting in “back end folding”, and subsequent magnetic output error could not be evaluated due to conveyance failure. This core setting condition is a heat treatment condition assuming that the sensitive material will be placed in a car during the daytime in summer.

(H) Evaluation of magnetic recording output error under harsh conditions After magnetically input in the above-mentioned evaluation of magnetic recording output error, the core is set and the photosensitive material is output 1000 times by the magnetic head before and after the developing process. The output error count of the operation is shown. The evaluation was performed in an environment of 25 ° C. and 55% RH. Example 3-1
The sample of No. 2 had excellent performance even if core setting was performed under severe conditions (high temperature), the number of magnetic recording errors did not increase, and other performance did not deteriorate. The sample of Example 3-2 is
The winding tendency was strong and many magnetic recording errors occurred even before the development processing, and trailing edge folds occurred during the development processing, and reading was not possible after the processing. Therefore, it can be seen that the heat treatment can prevent a remarkable curl even when placed under high temperature conditions, and can improve the transportability and the magnetic recording performance.

There was no antistatic agent (Example 3-3; electric resistivity was 10 ¹⁵ Ωcm or more), or only an antistatic layer having an electric resistivity of more than 10 ¹² Ωcm was provided. In the sample (Example 3-4), a large amount of magnetic input / output error due to static electricity was generated, which was a problem. The electrical resistivity is a value under the condition of 25 ° C. and 10% RH. That is, under low humidity conditions, static electricity is generated,
It causes a large amount of magnetic input / output error, and further, the static electricity acts on the emulsion layer to cause a static error in the image. Therefore, by providing the antistatic layer having an electric resistivity of 10 ¹² Ωcm or less, the magnetic recording performance and the processed image could be made excellent even under the low humidity condition. Example 3 in which no matting agent was added
-5 and Example 3-6 in which no abrasive was added,
Under the high temperature treatment condition, it was found that the magnetic output error was relatively large as shown in Table 7. Therefore, as in the present invention, by containing a matting agent and an abrasive in the photosensitive material back layer, excellent magnetic recording performance could be exhibited even under high temperature conditions.

(Example 4) In Example 1, the emulsion layer was prepared in the same manner as Sample 101 of Example 1 of JP-A-2-854, which is a reverse color emulsion layer, and the developing treatment was performed. When the same evaluation as in Example 1 was carried out except that the development processing method for a color reversal light-sensitive material as shown in Example 1 of Example No. 854 was performed.
The same effect as was obtained. As described above, according to the present invention, it is possible to produce a photographic light-sensitive material having a transparent magnetic recording layer in which the occurrence of magnetic input / output errors is remarkably suppressed, unevenness in repelling of processing does not occur, and other excellent photographic performance. It was

[0172]

According to the present invention, after the development processing, the processing solution does not cause unevenness in drying due to repelling, and the processing solution does not remain. Therefore, the residual processing solution causes dust on the input / output of magnetic recording and the like. It is possible to provide a silver halide photographic light-sensitive material having a transparent magnetic recording layer having sufficient slipperiness and scratch resistance in addition to causing no magnetic recording input / output error.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 1/38 1/76 502 1/81 3/00 530 G03C 1/04 1/85 1/91

Claims (11)

[Claims] 1. A transparent magnetic recording layer having at least one photosensitive silver halide emulsion layer on one side of a support and having a coercive force of 400 Oe or more on the side opposite to the photosensitive layer of the support. The silver halide photographic light-sensitive material has a silver halide photographic light-sensitive material containing at least a compound represented by the following general formula (1) and / or (2) on the magnetic recording layer side of the light-sensitive material. material. General formula (1) R ¹ X ¹ R ² General formula (2) R ³ X ² R ⁴ X ³ R ^{5 In} general formula (1), R ¹ and R ² each represent an aliphatic hydrocarbon group. However, in at least one of R ¹ or R ^2, having at least one polar substituent, R ^1, the total number of carbon atoms of the total R ² is 25 or more 120 or less. X ¹ represents a divalent linking group. In the general formula (2), R ³ and R ⁵ each represent an aliphatic hydrocarbon group, and R ⁴ represents a divalent aliphatic hydrocarbon group. Provided that at least one of R ³ , R ⁴ and R ⁵ has at least one polar substituent, and R ³ , R ⁴ and
The total total carbon number of R ⁵ is 30 or more and 150 or less. X
² and X ³ each represent a divalent linking group. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the compounds represented by the general formulas (1) and (2) are compounds having the following characteristics.
In the compound represented by the general formula (1), R ¹ and R ² are each an aliphatic hydrocarbon group having 10 or more and 70 or less carbon atoms, and the polar substituent is -OH, -COOH, -COOM,
_{^{-NH 2, -NR 3 + A -}} , is -CONH _2. Here, M represents a cation, R represents H or a hydrocarbon group having 8 or less carbon atoms, and A ⁻ represents an anion. In the compound represented by the general formula (2), R ³ and R ⁵ are each an aliphatic hydrocarbon group having 10 to 70 carbon atoms, and R ⁴ is a divalent aliphatic hydrocarbon group having 5 to 50 carbon atoms. Represents a polar substituent
_{OH, -COOH, -COOM, -NH 2} , -NR 3 +
A ^-, it is -CONH _2. Where M is a cation and R
Represents H or a hydrocarbon group having 8 or less carbon atoms, and A ⁻ represents an anion. 3. A compound represented by the following general formula (3) is added to a layer containing the compound represented by the general formula (1) and / or (2) on the magnetic recording layer side of the photosensitive material. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the silver halide photographic light-sensitive material is contained. General formula (3) R ⁶ YBD R ⁶ represents an aliphatic hydrocarbon group having 25 or more and 70 or less carbon atoms. Y represents a divalent linking group. The _{B - (CH 2 CH 2 O} )
_a −, − (CH ₂ CH (OH) CH ₂ O) _b −, − ((CH ₂ ) _c CH (R) CH ₂
O] _d − or − (CH ₂ CH ₂ O) _e − [CH ₂ CH (OH) CH ₂ O
] _F - _{[(CH 2) c CH (R} ) CH 2 O ] _g - consists either units, a is 3 to 40, b, d each 3-30,
c represents 1 to 3, e represents 0 to 40, f and g each represent an integer of 0 to 30, and e + f + g is 3 to 40. Here, R represents H, CH ₃ , or a phenyl group. D is H or has 8 carbon atoms
The following hydrocarbon groups are shown. 4. A magnetic recording layer side of the photosensitive material, wherein the layer containing the compound represented by the general formula (1) and / or (2) contains a compound represented by the following general formula (4). The silver halide photographic light-sensitive material according to any one of claims 1 to 3, wherein General formula (4) R ⁷ ZEM ^{1 In the} general formula (4), R ⁷ represents an aromatic or aliphatic hydrocarbon group. Z represents a divalent linking group. E is -OS
Represents O ₃ − or —SO ₃ −. M ¹ represents a cation. 5. A binder is contained in a layer containing a compound represented by the general formula (1) and / or (2) on the magnetic recording layer side of the photosensitive material. 5. The silver halide photographic light-sensitive material as described in any one of 4 to 4. 6. The silver halide photographic light-sensitive material according to claim 5, wherein the binder comprises a cellulose ester. 7. The support of the photosensitive material is a polyester support, and the polyester support is surface-treated by ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment or flame treatment. 7. A silver halide photographic light-sensitive material according to any one of 1 to 6. 8. The support is polyester having a glass transition temperature of 90 ° C. or higher and 200 ° C. or lower, and the support is 40 ° C. or higher between the time after film formation and the coating of the photosensitive layer. 0.1 to 150 at a temperature below the glass transition point
The silver halide photographic light-sensitive material according to claim 7, which is heat-treated for 0 hours. 9. The silver halide photographic light-sensitive material according to claim 8, wherein the support is polyethylene naphthalate. 10. An antistatic agent (having an electric resistivity of 10 ¹² Ωcm or less at 25 ° C./10% RH) and / or a matting agent and / or an abrasive agent in at least one layer on the side opposite to the photosensitive layer. The silver halide photographic light-sensitive material according to any one of claims 1 to 9, wherein 11. A silver halide photograph in which the tip of the film wound on the spool is sent to the outside from the film outlet of the cartridge body by rotating a spool rotatably provided in the cartridge body in the film feeding direction. A patrone system for a light-sensitive material and claim 1.
A photographic product comprising the silver halide photographic light-sensitive material described in any one of 10 to 10.