JPH07253634A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material having a magnetic recording layer having a good magnetic recording characteristic and hardly exercising an evil influence on the photographic property. CONSTITUTION:This silver halide photographic sensitive material has at least one silver halide emulsion layer on a transparent substrate and a transparent magnetic recording layer over the whole image plane on the opposite side of the substrate. The magnetic recording layer has 1.5-7.0emu/m<2> saturation magnetization, >=55% squareness ratio and 750-1200Oe coercive force, and the increase in the transmission density due to the setting of the magnetic recording layer is controlled to <=0.15 status A blue filter density measured with an X-rite densitometer.

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, and particularly to a silver halide containing a magnetic recording layer having excellent magnetic characteristics and excellent optical performance. The present invention relates to a photographic light-sensitive material.

[0002]

2. Description of the Related Art Conventionally, a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material) has only provided image information at the time of photographing or printing.
Alternatively, as disclosed in Japanese Patent Application Laid-Open No. 4-73737, by providing a transparent magnetic recording layer on the entire surface of a light-sensitive material, in addition to the image, the shooting date and time, the shooting condition such as the reduction / enlargement ratio, and the reproduction Number of prints, place to zoom, message,
In addition, development and printing conditions can be input to the sensitive material, and can also be input to video equipment such as TV / video.

However, when the magnetic recording layer is provided on the entire screen as described above, the influence of the magnetic recording layer on the photographic image quality becomes a problem. In particular, the increase in color density due to the magnetic particles in the magnetic recording layer significantly deteriorates the performance as a photographic light-sensitive material. On the other hand, there is a dilemma that if the coating amount of the ferromagnetic material is reduced so much that the photographic property is prioritized, the magnetic output is lowered, and necessary information cannot be input / output. In addition, if the coercive force of the magnetic layer is too low, the magnetic output is reduced, and it is easily erased by another magnetic material such as a magnet. Magnetic recording requires a lot of power and a special magnetic head, which is disadvantageous in terms of cost. Further, in order to maximize the above-mentioned magnetic recording performance, it has been desired to remove the influence of dust due to charging, improve the slidability of the film, and eliminate the influence of curl.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material having a magnetic recording layer which has good magnetic recording characteristics and has little adverse effect on photographic properties.

[0005]

The object of the present invention is to provide at least one silver halide emulsion layer on a transparent support and to the opposite side of the transparent support to the silver halide emulsion layer. In a silver halide photographic light-sensitive material having a transparent magnetic recording layer on the entire screen, the saturation magnetization of the magnetic recording layer is 1.5.
~ 7.0emu / m ² , squareness ratio 55% or more, coercive force 750
It was achieved by a silver halide photographic light-sensitive material characterized in that the increase in transmission density by installing the magnetic recording layer was 0.15 or less in terms of blue filter density. Here, the concentration measurement is X manufactured by X-rite.
-The status A of the rite densitometer shall be used.

When the saturation magnetization is 1.5 emu / m ² or less, it is difficult to input / output necessary information at a sufficiently low error rate, and when it is set to 7.0 emu / m ² or more, the magnetic recording layer is installed. As a result, the transmission density is greatly increased and the performance as a photographic light-sensitive material is significantly reduced. The permissible amount of increase in transmission density as a photographic light-sensitive material is, for example, X-rit.
The density of the status A blue filter of the X-rite densitometer manufactured by e. is 0.15 or less. More preferably 0
It is 0.15. At this time, the higher the squareness ratio, the better, but an effective output cannot be obtained unless it is 55% or more. Further, when the coercive force is 750 Oe or less, it is easily erased by another magnetic recording material, so that the storage stability of the magnetic performance is deteriorated. On the other hand, the coercive force is 1200
If it exceeds Oe, it is not preferable because the permalloy head, which is low in cost, cannot write, and the battery consumption becomes great for recording with a small camera.

The details of the present invention will be described below. The magnetic particles used in the present invention include ferromagnetic iron oxides such as γFe ₂ O ₃ (FeOx, 4/3 <x ≦ 3/2), Co-deposited γF.
Co-coated ferromagnetic iron oxide such as e ₂ O ₃ (FeOx, 4/3
<X ≦ 3/2), Co-deposited magnetite, other Co-containing ferromagnetic iron oxide, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, and other ferrites such as hexagonal Ba Ferrite, Sr ferrite, Pb ferrite, Ca ferrite or their solid solutions or ion-substituted products can be used, but Co
Coated ferromagnetic iron oxide such as γFe ₂ O ₃ with Fe
^{A 2 +} / Fe3 ⁺ ratio of 0 to 10% is preferable from the viewpoint of transmission density. 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. When the particle size is needle-like, the major axis is 0.01 to 0.8 μm,
The major axis / minor axis ratio is preferably 2 to 100, and the major axis is 0.
More preferably, it is 05 to 0.3 μm, and the major axis / minor axis ratio is 4 to 15. Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The larger the saturation magnetization (σ s) of the ferromagnetic material, the more preferable it is, but 50 emu / g or more, more preferably 70 em.
u / g or more, and practically 100 emu / g or less. The squareness ratio (σr / σs) of the ferromagnetic material is preferably 40% or more, more preferably 45% or more. If the coercive force (Hc) is too small, it will be easily erased, and if it is too large, it will not be possible to write depending on the system, so an appropriate value is preferable.
e or more and 3000 Oe or less, preferably 500 Oe or more 2
000 Oe or less, more preferably 650 Oe or more and 95
It is 0 Oe or less.

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. In addition, JP-A-4-195726 and 4-1.
92116, 4-259911, 5-081652.
A surface treatment with an inorganic and / or organic material as described may be applied. Furthermore, these ferromagnetic particles may be treated on their surface with a silane coupling agent or a titanium coupling agent. 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 trimethoxysilane 〃 [1] -16. 3-Trimethylammoniopropyl trimethoxysilan iodide 〃 [1] -18. 3-Isocyanylpropyl methyldimethoxysilane 〃 [1] -19. 3- (Poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane 〃 [1] -20. 3-methoxy (poly (degree of polymerization 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 Isopropyl dimethacryl isostearoyl titanate 〃 [2] -11. Isopropylisostearoyldiacrylic titanate 〃 [2] -12 Isopropyltri (dioctylphosphate) titanate 〃 [2] -13 Isopropyltricumylphenyl titanate 〃 [2] -14 isopropyltri (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. Preferably 1
˜75% by weight, more preferably 2 to 50% by weight. Further, the addition of these silane coupling agent and titanium coupling agent of the present invention is applied to the magnetic particles of the present invention by a generally known method to modify the surface of the magnetic particles and impart the coating solution stability of the magnetic material. be able to. 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. It is preferable to use a stirrer such as a Henschel mixer, a super mixer, a ready mixer, a V-type blender and an open kneader. Among these stirrers, the open kneader is particularly preferable. It is 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 treated 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 necessary to knead well and is a simple method.

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, Natural product polymer (cellulose derivative, sugar derivative, etc.)
And mixtures of these can be used. The Tg of the above resin is preferably -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000, preferably 50,000 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. Acrylonitrol copolymer, vinyl-based copolymers such as ethylene / vinyl acetate copolymer, nitrocellulose,
Cellulose diacetate, cellulose triacetate,
Cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate, cellulose derivatives such as cellulose dodecanoate resin,
Acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, Silicone resin and fluorine resin can be mentioned. The thermosetting resin or the reactive resin whose molecular weight becomes extremely large by heating, for example, phenol resin, phenoxy resin, epoxy resin, curable polyurethane resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic resin. System reaction resin, epoxy-polyamide resin, nitrocellulose melamine resin, a mixture of high molecular weight polyester resin and isocyanate prepolymer,
Included are urea formaldehyde resins, low molecular weight glycol / high molecular weight diol / polyisocyanate 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, OSO
₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , wherein M is hydrogen, an alkali metal or ammonium, and when there are plural M in one group, R may be different from each other, R is hydrogen or alkyl It is preferable to introduce (a base) from the viewpoint of dispersibility and durability of the magnetic material. The polar group content is in the range of preferably 10 ^-7 to 10 ^-3 equivalents, and more preferably 10 ^-6 to 10 ^-4 equivalents per gram of the polymer.

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. . The isocyanate-based crosslinking agent is a polyisocyanate compound having two or more isocyanate groups, such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5.
-Isocyanates such as diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane) , And polyisocyanates produced by condensation of these isocyanates. Radiation-curable vinyl monomers include
A compound that can be polymerized by irradiation with a carbon-
It is a compound having one or more carbon unsaturated bonds in the molecule, and is (meth) acrylic acid ester, (meth) acrylamide, allyl compound, vinyl ester, vinyl ester, vinyl heterocyclic compound, N-vinyl. Examples thereof include compounds, styrene, (meth) acrylic acid, crotonic acid, itaconic acid, olefinic acid and the like. 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 total 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. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. As the latex polymer, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer,
Examples thereof include acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. The most preferred of these is gelatin. Gelatin is a so-called alkali-processed (lime-processed) gelatin that is immersed in an alkali bath before extraction of gelatin, an acid-processed gelatin that is immersed in an acid bath, and a double-immersed gelatin that has been subjected to both of these processes in the manufacturing process. Any of gelatin may be used. If necessary, a portion of colloidal albumin, casein,
Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer,
Polyacrylamide or derivatives thereof, partial hydrolysates, gelatin derivatives and the like may be used in combination with gelatin.

It is preferable to harden the magnetic recording material containing gelatin. As a hardener that can be used in the magnetic recording layer,
For example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,3.
5-triazine and others U.S. Pat. No. 3,288,77
5, 2,732,303, British Patent 974,7
23, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others. US Patent No. 3,
Compounds having a reactive olefin described in 635,718, 3,232,763, British Patent 994,869, etc., N-hydroxymethylphthalimide, and other U.S. Pat. No. 2,732,316. Issue 2
N-methylol compounds described in US Pat. No. 586,168, isocyanates described in US Pat. No. 3,103,437, US Pat. No. 3,017,28.
0, 2,983,611 and the like, aziridine compounds, US Pat. Nos. 2,725,294 and 2,725,295 and the like, acid derivatives,
Examples thereof include epoxy compounds described in US Pat. No. 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Alternatively, as an inorganic compound hardening agent, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699.
No., Belgian Patent No. 825,726, JP-A-60-22
5148, JP-A-51-126125, JP-B-58
Examples include carboxyl group-activating type hardeners described in JP-A-50699, JP-A-52-54427, US Pat. No. 3,321,313 and the like. The amount of the hardener used is usually 0.01 to 30% by weight based on dry gelatin,
It is preferably 0.05 to 20% by weight.

As the method for dispersing the above-mentioned magnetic material in the binder, various known means other than, for example, Japanese Patent Application No. 4-189652 can be used. A kneader, a pin type mill, an annular type mill or the like 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 0.1 μ to 10 μ, preferably 0.2 μ to 5 μ, more preferably 0.3 μ to 3 μ.
is μ. The weight ratio of the magnetic particles to the binder is preferably 0.5: 100 to 60: 100, more preferably 1: 100 to 30: 100. The coating amount of the magnetic substance is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² .
m ² , more preferably 0.02 to 0.5 g / m ² .

The magnetic recording layer of the present invention can be provided on the entire back surface of the photographic support by coating or printing, or in the form of stripes. It is also preferable to co-cast a solution of a binder in which magnetic particles are dispersed and a solution of a binder for preparing a support in the form of an entire surface or stripes to prepare a support having a magnetic recording layer. In this case, the compositions of the two kinds of polymers may be different, but it is preferable that they are the same. This magnetic recording layer can be applied by air doctor coating, blade coating, air knife coating, squeeze coating, impregnation coating, reverse roll coating, transfer roll coating, gravure coating, kiss coating, cast coating, spray coating, dip coating, bar coating. , Extrusion coat, etc. can be used, and other methods are also possible. For a detailed explanation of these, refer to “Coating Engineering”, pages 253 to 277 (published by 4.3.20 of Showa) published by Asakura Shoten. Have been described. 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 m / min to 5
It is performed at 00 m / min, and the drying speed is 20 ° C to 250 ° C.
Controlled by. 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 2
000 Oe or more is preferable, and 3000 Oe or more is particularly preferable. In the case of a solenoid, it may be 500 Oe or more.
The timing of orientation during drying is described in Japanese Patent Application No. 5-0058.
As described in No. 22, the point where the residual solvent in the magnetic recording layer is 5% to 70% is desirable. If necessary, the surface is smoothed to produce the magnetic recording layer of the present invention. These are disclosed, for example, in JP-B-40-23625, JP-B-39-28368, and US Pat. No. 347.
No. 3960, etc. In addition, Japanese Patent Sho 41
The method disclosed in Japanese Patent No. 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 be provided together, 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 or organic fine particles (eg, silica, SiO ₂ , SnO)
₂ , Al ₂ O ₃ , TiO ₂ , crosslinked polymethylmethacrylate, barium carbonate, fine silicone particles, etc.) are preferably added.

For example, by incorporating an additive in the magnetic recording layer,
By providing protrusions of 0.8μ or less on the back layer surface, magnetic output errors due to dust during magnetic input / output can be prevented, S / N, which is one of the magnetic characteristics, is not deteriorated, and photographic properties are affected. There is a way not to give. As a method of giving surface protrusions to the back surface, there are methods of adding particles to the back surface, causing brushing at the time of coating and drying, and intentionally generating Benard cells, but it means that the shape of the surface protrusions can be freely controlled. Therefore, it is preferable to add particles to the back surface.

The added particles are insoluble in the developing solution,
As the material, 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. 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.). 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. Further, acrylic acid esters, methacrylic acid esters, itaconic acid diesters, crotonic acid esters, maleic acid diesters, phthalic acid diesters, styrene derivatives, vinyl esters, 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. In order not to deteriorate the photographic property, the average particle size of the particles is preferably 0.1 μm to 1 μm, and the coating amount thereof is preferably 1 to 100 mg / m ² .

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 the dirt attached to the magnetic head.
The composition of the non-spherical inorganic particles is aluminum oxide (α
-Alumina, γ-alumina, corundum, etc.), chromium oxide (Cr ₂ O ₃ ), iron oxide (α-Fe ₂ O ₃ ), silicon dioxide, titanium dioxide, oxides such as silicon carbide (SiC),
Carbides such as silicon carbide and titanium carbide, fine powders such as diamond are preferable, and more preferably aluminum oxide,
Chromium oxide (Cr ₂ O ₃ ) is good. The non-spherical inorganic particles may be added to the magnet layer or may be overcoated on the magnet layer. As the binder used at this time, the binder described in the above-mentioned magnet layer binder can be used, and preferably the same binder as the binder for the magnet layer.

Next, the polyethylene aromatic dicarboxylate type polyester support which is the support of the present invention will be described. The polyester of the present invention is formed with a diol and an aromatic dicarboxylic acid as essential components, but as a dibasic acid that can be often used as a mixture with other dicarboxylic acids,
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 Acid, 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, 1,4-dicarboxymethylphenol, 1,3-dicarboxy-5
Phenylphenol, sodium 3-sulfoisophthalate

And the like. The essential 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 are used. 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol,
Examples thereof include 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. The polyester of the present invention may be salicylic acid or the like, which may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule.

Among these diols and dicarboxylic acid monomers, preferred aromatic dicarboxylic acids are 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), Paraphenylenedicarboxylic acid (PP
DC), as diol, (poly) ethylene glycol (PEG or EG)), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), and hydroxycarboxylic acid as a copolymerization component. Examples of the acid include those obtained by copolymerizing para-hydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA).

Of these, preferred polymers are polyethylene terephthalate, polyethylene naphthalate, homopolymers such as polycyclohexanedimethanol terephthalate (PCT), and terephthalic acid.
Copolymer of naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is preferably between 0.9: 0.1 and 0.1: 0.9, 0.8: 0.2-0. 2: 0.8 is more preferable), a copolymer of terephthalic acid, ethylene glycol and bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, Further, 0.5: 0.5 to 0: 0.9 is preferable.), Isophthalic acid, para-phenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; para-phenylenedicarboxylic acid is used in a molar ratio of terephthalic acid). 1 is 0.1 to 0.
5, 0.1 to 0.5, and more preferably 0.2
.About.0.3, 0.2 to 0.3 are preferable), terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.7: 0.3). Preferably, 0.9: 0.1 to 0.6: 0.4) terephthalic acid, a copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is 0:
1.0 to 0.8: 0.2 is preferable, and 0.1: 0.9 to 0.7: 0.3 is more preferable. ), Parahydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of parahydroxybenzoic acid and ethylene glycol is preferably 1: 0 to 0.1: 0.9, more preferably 0.9: 0.1). .About.0.2: 0.8) and the like are preferable. Among these, polyesters containing 2,6-naphthalenedicarboxylic acid are particularly preferable. Specifically, it is a polyester containing 0.1-1.0 of 2,6-naphthalenedicarboxylic acid. 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 for these polyesters is about 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.

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: [terephthalic acid (TPA) / ethylene glycol (EG)) (100/100)] (PET) Tg = 80 ° C. P-1: [2,6-naphthalenedicarboxylic acid (NDCA) / Ethylene glycol (EG) (100/100)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: [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 = 112C P-7: TPA / EG / BPA (100/50/50) Tg = 105C 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: IPA / PPDC / TPA / 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: PHBA / EG / TPA (200/100/100) Tg = 125 ° C. P-14: PEN / PET (60/40) Tg = 95 ° C. P-15: PEN / PET (80/20) Tg = 104 ° C. P-16: PAr / PEN (50/50) Tg = 142 ° C. P-17: PAr / PCT (50/50) Tg = 118 ° C P-18: PAr / PET (60/40) Tg = 101 ° C P-19: PEN / PET / PAr (50/25/25) Tg = 108 ° C P-20: TPA / 5-sulfoi Phthalic acid (SIP) / EG (95/5/100) Tg = 65 ℃ P-21: PEN / SIP / EG (99/1/100) Tg = 115 ℃

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 have 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.
T and PEN, with which TAC is 122 μm
The required film thickness can be reduced to 105 μm or less. Next, the polyester support of the present invention is characterized by being heat-treated, and in that case, it is necessary to perform the treatment 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, if the heat treatment temperature exceeds the glass transition temperature, the film tends to be curled. 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 performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1 to −5 ° C./hour. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours 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 curl, a heat treatment is performed at a temperature higher than Tg and lower than the melting point (melting temperature determined by DSC) before the heat treatment to erase the heat history of the support. The reheat treatment may be performed at a temperature of 40 ° C. or higher and lower than Tg. In the present invention, this heat treatment is referred to as "preheat treatment".
The heat treatment at 40 ° C. or higher and lower than Tg described in the preceding paragraph is called a “post heat treatment” to distinguish them. The preheat treatment temperature is Tg or higher and lower than the melting point, and more preferably Tg + 20 ° C. or higher and crystallization temperature (crystallization temperature determined by DSC) or lower.
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 1500
The time is less than or equal to the hour, more preferably 1 minute or more and less than 1 hour. If it is less than 0.1 minutes, a sufficient effect cannot be obtained,
When 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 −0.1 to Tg−20 ° C. A post-heat treatment is preferably performed while cooling at -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, it may be carried out by any of a method of heat-treating the roll from room temperature in a constant temperature bath, and a method of winding and heat-treating the roll in a constant temperature during web conveyance. Good. Although the method of (1) requires a long time for raising and lowering the temperature, it has an advantage of requiring less equipment investment. The method of (1) requires winding equipment at high temperature, but has an advantage that the heating time can be omitted. In the heat treatment in the roll form, the surface shrinkage such as wrinkles due to winding tightness and the cutout of the core portion is likely to occur due to the heat shrinkage stress generated during the heat treatment. For this reason, 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 in the form of a web, a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the form of a roll. Among these heat treatment methods, it is preferable that the pre-heat treatment is performed in a web shape and the post-heat treatment is performed in a roll shape. This is because if the pre-heat treatment is carried out in the form of a web, planar defects are less likely to occur as compared with the case of performing it in the form of a roll, and the post-heat treatment requires a relatively long time.

These heat treatments are carried out after film formation on the support, after glow discharge treatment, and after coating the back layer (antistatic agent, slip agent, etc.),
It may be carried out at any stage after the application of the undercoat. 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 more 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 glass fiber-containing resin.

Next, in order to further enhance the function of the polyester of the present invention as a photographic support, it is preferable to coexist various additives. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the addition amount thereof is usually 0.01% by weight to 20% by weight, preferably 0.05% by weight based on the weight of the polyester film.
It is about 10% by weight to 10% by weight. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. 2,4-dihydroxybenzophenone as an ultraviolet absorber,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenone-based compounds such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'
Examples thereof include benzotriazole-based UV absorbers such as -di-t-butyl-5'-methylphenyl) benzotriazole and salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

The refractive index of the preferred aromatic polyester of the present invention is as high as 1.6 to 1.7, whereas the refractive index of gelatin which is the main component of the photosensitive layer coated thereon is 1. The value is 50 to 1.55, which is smaller than this value. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of incorporating inert inorganic particles and the like into a support, a method of adding a dye, and the like are known. The preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase film haze. At this time, the dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film. Further, those having excellent compatibility with polyester are preferable. From the above viewpoints, as the dye, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, the color density in the visible light region was measured with a color densitometer manufactured by Macbeth Co. and at least 0.
It must be 01 or more. More preferably 0.
It is 03 or more.

The polyester film according to the present invention can be imparted with slipperiness depending on the application, and the slipperiness imparting means is not particularly limited.
The kneading of an inert inorganic compound or the coating of a surfactant is used as a general method. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC.
Examples are O ₃ , talc, kaolin and the like. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for a support for a photographic light-sensitive material. Therefore, in the slipperiness imparting means, the external particle system is a polyester film. It is desirable to select SiO ₂ having a refractive index relatively close to that, or an internal particle system capable of relatively reducing the precipitated particle size. Further, in the case of imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

When any of these polyester films is used as a support, since each of these polyester supports has a hydrophobic surface, a photographic layer (for example, a photosensitive halogen) containing a protective colloid mainly containing gelatin is provided on the support. It is very difficult to firmly bond the silver halide emulsion layer, the intermediate layer, the filter layer, etc.). The conventional techniques used to overcome such difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
After surface activation treatment such as laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a method of directly applying a photographic emulsion to obtain an adhesive force, and (2) after performing these surface treatments once,
Alternatively, there are two methods: a method of providing an undercoat layer without surface treatment and coating a photographic emulsion layer on the undercoat layer. (For example, U.S. Pat. Nos. 2,698,241, 2,764,520, 2,864,755, 3,462,335, 3,475,193, 3,143,421. No. 3,501,301, No. 3,460,944, No. 3,674,531, British Patent No. 788,365,
No. 804,005, No. 891,469, Japanese Patent Publication No. 48
-43122, 51-446, etc.).

In all of these surface treatments, an essentially co-polar group is formed on the surface of the support which is originally hydrophobic,
This is probably due to an increase in the cross-linking density of the surface.As a result, the affinity of the components contained in the undercoating liquid with polar groups may increase, or the fastness of the adhesive surface may increase. To be Furthermore, an adhesion mechanism due to generation of radicals is also considered. In addition, various ideas have been made for the constitution of the undercoat layer, and a layer that adheres well to the support (hereinafter referred to as the undercoat first layer) is provided as the first layer.
A so-called multi-layering method in which a hydrophilic resin layer (hereinafter, abbreviated as the second undercoat layer) that adheres well to the photographic layer as a second layer is applied thereon, and a resin containing both a hydrophobic group and a hydrophilic group There is a single layer method in which only one layer is applied.

Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. First, the ultraviolet irradiation treatment will be described below. These are Japanese Examined Patent Publication Nos. 43-2603, 43-2604, and 4
It is preferably carried out by the treatment method described in No. 5-3828. The mercury lamp is a high-pressure mercury lamp composed of a quartz tube, and it is preferable that the wavelength of ultraviolet rays is between 180 and 320 nm. The UV irradiation may be performed in the stretching step of the support, at the time of heat setting, or after heat setting. Regarding 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 rises 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 treated light, as the amount of treated light increases, the adhesive force between the support and the layer to be adhered improves, but as the amount of light increases, the support becomes colored,
In addition, the problem that the support becomes brittle occurs. Therefore,
For ordinary plastic films such as polyester and polyolefin, a high-pressure mercury lamp having a main wavelength of 365 nm is used, and the irradiation light amount is preferably ^{20 to} 10000 (mJ / cm ² ), more preferably 50 to 2000 (mJ / cm ² ). is there. 254nm
In the case of a low-pressure mercury lamp whose main wavelength is
00 to 10,000 (mJ / cm ² ) is preferable, and more preferably 3
It is from 00 to 1500 (mJ / cm ² ). Next, the corona discharge treatment will be described in any conventionally known method, for example, JP-B-48-5043, JP-A-47-51905, JP-A-47-28067, JP-A-49-83767, and JP-A-51-51.
41770, 51-131576 and the like. Discharge frequency is 50H
z to 5000 KHz, preferably 5 KHz to several 100 K
Hz is suitable, and particularly preferably 10 Hz to 30 KHz
Is. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable.
If the frequency is too high, a special device for impedance matching is required, which increases the price of the device.
Not preferable. Regarding the treatment strength of the object to be treated, it is usually 0.001 KV · A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.01 KV · A · min / m ^{2 to 1} KV · A · min /
m ² is suitable. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0.
mm is suitable. As the corona discharge treatment machine, a solid state corona treatment machine 6KVA model manufactured by Pillar can be used. Further, as the flame treatment, natural gas, liquefied propane gas, etc. can be used, and the mixing ratio with air is important. A preferable gas / air mixing ratio is a volume ratio of 1/14 to 1/22 for propane, more preferably 1/16 to 1
/ 19. For natural gas, it is 1/6 to 1/10, and more preferably 1/7 to 1/9. Flame treatment amount is 1 to 5
0 Kcal / m ² , more preferably 3 to 20 Kcal / m ^2.
Is. The distance between the tip of the internal flame of the burner and the support is 4
It is more effective to make it less than cm. As the processing device, a frame processing machine manufactured by Kasuga Electric Co., Ltd. can be used. The backup roller that supports the support during the treatment is preferably a hollow roll, and it is preferable that a cooling liquid is passed through the roll to maintain a constant temperature.

The glow discharge treatment, which is an effective surface treatment, can be performed by any conventionally known method, for example, Japanese Patent Publication No.
5-7578, 36-10336, 45-22
No. 004, No. 45-22005, No. 45-24040.
No. 46-43480, U.S. Pat. No. 3,057,79.
No. 2, No. 3,057,795, No. 3,179,482
Issue 3, Issue 3,288,638, Issue 3,309,299
Issue No. 3,424,735 Issue No. 3,462,335
Issue 3, Issue 3,475,307, Issue 3,761,299
No., British Patent No. 997,093, JP-A-53-1292.
No. 62 or the like can be used. In particular, it was found that the glow treatment is particularly effective as a surface treatment which simultaneously satisfies the requirements of adhesion, yellowing suppression and blocking prevention required for a polyester support having a Tg of 90 ° C. or higher and 200 ° C. or lower, which is preferable in the present invention. . There is a method of introducing various gases such as oxygen, nitrogen, helium or argon into the atmosphere of glow discharge treatment, but in the case of the polyester support of the present invention, even if a special gas is introduced, the effect of significantly adhering is achieved. Is not found, the price of gas is expensive, and it is not industrially suitable. On the other hand, when the water vapor is introduced, it has an adhesive effect equal to or higher than that of the case of introducing the special gas, and the price is significantly low, which is an industrially excellent method.

The steam partial pressure of the present invention for performing glow discharge treatment in the presence of steam is preferably 10% or more and 100% or less, and more preferably 40% or more and 90% or less.
If it is less than 10%, it becomes difficult to obtain sufficient adhesiveness.
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. Further, when the film to be surface-treated is subjected to vacuum glow discharge treatment in a preheated state, the adhesiveness is improved in a shorter time than that at room temperature,
It has been found that yellowing can be significantly reduced. The preheating described here is different from the heat treatment for improving the rolling behavior which will be described later. The preheating temperature is preferably 50 ° C. or higher and Tg or lower, more preferably 70 ° C. or higher and Tg or lower, and further preferably 90 ° C. or higher and Tg or lower. If it is preheated at a temperature of Tg or higher, the adhesion will be slightly deteriorated. Specific methods for raising the polymer surface temperature in vacuum include heating with an infrared heater and heating with contact with a hot roll.
For example, if you want to preheat the film surface to 115 ℃, 115
It is sufficient to contact the film with a hot roll at 0 ° C. for at most 1 second. The heating method is not limited to the above-mentioned method, and widely known heating methods can be used.

The preheated support is subjected to glow discharge treatment. Important processing conditions to be suppressed other than the steam partial pressure and the preheating temperature of the support are vacuum degree, inter-electrode voltage, discharge frequency, etc. Can be mentioned. By controlling these treatment conditions, it becomes possible to carry out glow discharge treatment that achieves both adhesion and suppression of yellowing. The pressure during glow discharge treatment is preferably 0.005 to 20 Torr.
It is more preferably 0.02 to 2 Torr. If the pressure is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained. On the other hand, if the pressure is too high, stable discharge will not occur. The voltage is 500 to 500.
It is preferably between 0V. More preferably 500 to 3000
V. If the voltage is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained.
On the other hand, if the voltage is too high, the surface will be deteriorated, and conversely the adhesiveness will decrease. The discharge frequency used is, as seen in the prior art, from direct current to several 1000 MHz, preferably 50 Hz to 20 MHz, and more preferably 1 KHz.
~ 1 MHz. Discharge treatment intensity is 0.01 KV · A
Min / m ^{2 to 5} KV · A · min / m ² is preferable, and more preferably 0.15 KV · A · min / m ^{2 to 1} KV · A · min / m ² to obtain the desired adhesive performance.

It is preferable that the temperature of the support thus subjected to the glow discharge treatment is immediately lowered by using a cooling roll. The support is likely to be plastically deformed by an external force as the temperature rises, and the flatness of the support is impaired. Further, low-molecular weight substances (monomers, oligomers, etc.) may be deposited on the surface of the support, which may deteriorate transparency and blocking resistance. Next, regarding the undercoating method (2), all of these methods have been well researched. For example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid are used for the first undercoating layer in the multilayer method. , A lot of polymers such as polyethyleneimine, epoxy resin, grafted gelatin and nitrocellulose, including copolymers starting from a monomer selected from maleic anhydride, etc. Its properties have been investigated mainly for gelatin. In the single layer method, good adhesion is often achieved by swelling many supports and interfacially mixing with the hydrophilic undercoat polymer. Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. 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. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-dichloromethane. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on.

The subbing layer of the present invention includes SiO ₂ , Ti.
O ₂ and inorganic fine particles such as a matting agent or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. In addition to this, the undercoat liquid may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat. The undercoat liquid according to the present invention is a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method,
Gravure coating method or US Pat. No. 2,681,29
It can be applied by the extrusion coating method using the hopper described in No. 4 specification. If desired, US Pat. Nos. 2,761,791 and 3,508,
947, 2,941,898, and 3,52
No. 6,528, Yuji Harazaki, “Coating Engineering”, page 253 (1973, published by Asakura Shoten), etc., can be used to simultaneously coat two or more layers. In the present invention, the support is preferably polyethylene-2,6-naphthalenedicarboxylate at 100 ° C to
Heat treated for 24 hours between 115 ° C and the thickness of the support
85 μm to 105 μm, the surface of which is subjected to ultraviolet irradiation treatment or glow discharge treatment, and the non-photosensitive hydrophilic layer on the back side is a gelatin layer of 1 to 7 μm and the non-photosensitive hydrophilic layer. Is a cellulose binder of 0.5 to 5 μm. At this time, the weight ratio of the gelatin amount of the non-photosensitive hydrophilic layer of the back layer to the gelatin layer of the emulsion layer on the opposite side is preferably 0.1 to 0.5.

Next, the photographic layer of the photographic light-sensitive material of the present invention will be described. The silver halide emulsion layer may be any of black and white colors. Here, a color silver halide photographic light-sensitive material will be described. The light-sensitive material of the present invention may have at least one layer of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support, and a silver halide emulsion. There is no particular limitation on the number of layers and the order of layers of the non-photosensitive layer. 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 a color sensitivity to any of blue light, green light, and red light. 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 according to the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as an intermediate layer of each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. For the intermediate layer, JP-A Nos. 61-43748, 59-113438, 59-113440 and 6-61 are used.
The couplers and DIR compounds as described in 1-20037 and 61-20038 may be contained, and a color mixing inhibitor may be contained as is usually used. A plurality of silver halide emulsion layers constituting each unit photosensitive layer are described in West German Patent No. 1,121,470 or British Patent No. 923,045, JP-A-57-112751.
No. 62-200350, No. 62-206541.
No. 62-206543, No. 56-25738,
62-63936, 59-202464, JP-B-55-34932, and 49-15495.

The silver halide grains include those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal forms such as spheres and plates, twin planes and the like. It may have a crystal defect or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 1764.
3 (December 1978), pp. 22-23, "I. Emulsion preparation an
d types) "and ibid. No. 18716 (19).
(November 1979), p. 648, "The Physics and Chemistry of Photography" by Grafkeide, published by Paul Montel (P. Glafkide).
s, Chemie et Phisique Photo
ographique, Paul Montel, 19
67), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photograph.
ic Emulsion Chemistry (Foc
al Press, 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press, Inc. (V.L.
Zelikman et al. , Making and
Coating Photographic Emul
, Focal Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
The monodisperse emulsions described in JP-A No. 1989-2000 are also preferable. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described by Gatov, Photographic Science and Engineering (Gut
off, Photographic Science
and Engineering), Volume 14, 248
~ 257 (1970); U.S. Pat. No. 4,434,2.
No. 26, No. 4,414, 310, No. 4,433, 04
No. 8, 4,439,520 and British Patent No. 2,1.
It can be easily prepared by the method described in No. 12,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halide such as silver rhodanide and lead oxide. Also, a mixture of particles having various crystal forms may be used. Silver halide emulsion,
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. The efficiency of the present invention is particularly remarkable when an emulsion sensitized with a gold compound and a sulfur-containing compound is used. Additives used in such processes are Research Disclosure No. 17643 and No. 1871.
It is described in No. 6, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant portions are shown in the following table. (Additive type) (RD176439) (RD187169) 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to 24, page 648, right column, page 649, right Column 4 Whitening agent Page 24 5 Antifoggants and stabilizers 24 to 25 pages 649 Right column to 6 Light absorbers, filter dyes, UV absorbers 25 to 26 pages 649 Right column to 650 Left column 7 Stain prevention Agent page 25 right column page 650 left to right column 8 dye image stabilizer page 25 9 film hardening agent page 26 651 page left column 10 binder page 26 same as above 11 plasticizer, lubricant page 27 650 right column 12 coating aid, Surfactants, pages 26 to 27, page 650, right column Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, formaldehyde described in U.S. Pat. Nos. 4,411,987 and 4,435,503. React with, it is preferable to add a compound capable of immobilizing the photosensitive material.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG. . Examples of yellow couplers include U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961. issue,
Japanese Patent Publication No. 58-10739, British Patent No. 1,425,0
20, No. 1,476,760, and U.S. Pat. No. 3,9.
73,968, 4,314,023, 4,
Those described in 511, 649, European Patent No. 249,473A, etc. are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No., EP 73,636, US Pat. No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
, JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-.
No. 35730, No. 55-118034, No. 60-18.
5951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, W.
Those described in O (PCT) 88/04795 and the like are particularly preferable.

Examples of cyan couplers include phenol-type and naphthol-type couplers, and US Pat.
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No. 2,369,929, No. 2,801,171, No. 2,772,162, No. 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
No. 3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A, No. 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,753,871, No. 4,451,55
No. 9, No. 4,427, 767, No. 4, 690, 8
No. 89, No. 4,254,212, No. 4,296,
Those described in JP-A No. 199 and JP-A No. 61-42658 are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No.
17643, Section VII-G, U.S. Pat. No. 4,163,67
No. 0, Japanese Examined Patent Publication No. 57-39413, US Pat.
Those described in 4,929, 4,138,258 and British Patent 1,146,368 are preferable. Examples of couplers in which the color forming dye has excessive diffusibility include U.S. Pat. No. 4,366,237 and British Patent 2,125,57.
No. 0, European Patent No. 96,570, and West German Patent (Publication) No. 3,234,533 are preferable. Typical examples of polymerized dye-forming couplers are U.S. Pat. Nos. 3,451,820, 4,080,211, 4,367,282, and 4,409,320.
U.S. Pat. No. 4,576,910, British Patent 2,102,13.
No. 7, etc. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the aforementioned RD17643, VII to F patents, JP-A-57-151944, and JP-A-57-15423.
No. 4, No. 60-184248, No. 63-37346.
And U.S. Pat. No. 4,248,962 are preferred.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,092
7,140, 2,131,188, JP-A-59
Those described in Nos. 157638 and 59-170840 are preferable. Other couplers that can be used in the light-sensitive material of the present invention include U.S. Pat. No. 4,130,4.
Competitive couplers described in U.S. Pat. No. 27, US Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
-185950, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound described in JP-A-62-24252 and the like, and after separation as described in EP 173,302A Couplers that release dyes that recolor, R.I. D. No. 11449, 24
No. 241, bleaching accelerator releasing coupler described in JP-A No. 61-201247, and a ligand-releasing coupler described in US Pat. No. 4,553,477, JP-A-63-75.
Examples thereof include couplers releasing the leuco dye described in No. 747.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,222.
No. 027 and the like. Specific examples of the high boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, Examples thereof include alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives and hydrocarbons. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or higher, preferably 50 ° C. or higher and about 160 ° C. or lower can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2- Examples include ethoxyethyl acetate and dimethylformamide. The process of latex dispersion method, effects and specific examples of latex for impregnation are described in US Pat.
199,363, West German Patent Application (OLS) No. 2,54
No. 1,274 and No. 2,541,230.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is 28 μm or less,
And the film swelling speed T _^1/2 is preferably not more than 30 seconds. The film thickness means a film thickness measured at 25 ° C. 55% relative humidity (2 days), the film swelling rate T _^1/2 can be measured in accordance with a known method in the art. For example, A. Green et al., Photographic Science and Engineering (Pho
togr. Sci. Eng. ), Volume 19, Issue 2, 124
Can be measured by using a type of Swellometer described (swelling meter) pp ~129, T _^1/2 in the color developer 30
The maximum swollen film thickness reached when treated at 3 ° C for 15 minutes
0% to saturated film thickness, that time the definition of to reach the thickness of the T ^_1/2.

[0064] The film swelling speed T _^1/2 can be adjusted to gelatin as a binder by adding a hardening agent, or by changing the aging conditions after coating. The swelling rate is preferably 150 to 400%. The swelling rate is calculated from the maximum swollen film thickness under the above-mentioned conditions by the formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness. Further, in the present invention, materials used for various silver halide photographic light-sensitive materials can be used.

In the present invention, an antistatic agent is preferably used. The antistatic agent is not particularly limited, and examples of the anionic polymer electrolyte include polymers containing a carboxylic acid, a carboxylic acid salt, and a sulfonic acid salt.
159, JP-A-51-30725 and JP-A-51-1.
29216 and Japanese Patent Application Laid-Open No. 55-95942. Examples of the cationic polymer include JP-A-49-121523 and JP-A-48-911.
65 and Japanese Patent Publication No. 49-24582. In addition, ionic surfactants are also anionic and cationic. For example, JP-A-49-85826.
No. 49-33630, U.S. Pat. No. 2,99.
No. 2,108, U.S. Pat.
Examples thereof include compounds described in JP-A No. 8-87826, JP-B-49-11567, JP-B-49-11568, and JP-A-55-70837.

The most preferable antistatic agent is Z
nO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ ,
At least one crystalline metal oxide selected from SiO ₂ , MgO, BaO, MoO ₃ , and V ₂ O ₅ or a composite oxide thereof (Sb, P, B, In, S, Si,
C) and further, sol-like metal oxides or fine particles of composite oxides thereof. The fine particles or acicular filler of the conductive crystalline oxide or its composite oxide used in the present invention has a volume resistivity of 10 ⁷ Ω-cm or less, more preferably 10 ⁵ Ω-cm or less. The particle size is 0.001 to 1.0 μm, especially 0.001
It is desirable to set the thickness to 0.3 μm. In order to give conductivity more efficiently, the primary fine particles are partially aggregated to 0.0
It is preferable to use fine particles or filler of a conductive crystalline oxide or a composite oxide thereof having a particle size of 1 to 0.2 μm.
Further, the electrical conductivity reached when producing an antistatic layer using these is preferably 10 ¹² Ω or less, more preferably 10 ¹⁰ Ω, both in the raw state and after the treatment.
Hereafter, it is particularly preferable that the electric resistance is 10 ^9.5 Ω or less. In that case, the content in the sensitive material is generally 5 to 50.
0 mg / m ² is preferable and 10 to 350 mg / m ² is particularly preferable. The amount of the binder is preferably from 1-500 mg / m ^2, in particular 5 to 300 mg / m ² is preferred. The ratio of the fine particles of the conductive crystalline oxide or the composite oxide thereof or the amount of the acicular filler to the binder is preferably 1/300 to 100/1, more preferably 1/100 to 100/5.

Next, the slip in the present invention will be described in detail. The light-sensitive material of the present invention preferably has slipperiness. The slipperiness is good on both the photosensitive layer surface and the back surface, but the back surface is more effective. This is because if the surface of the photosensitive material becomes slippery, the force applied to the radiation curable resin layer of the present invention is released and the scratch resistance is improved. The preferred sliding property is a dynamic friction coefficient of 0.25.
It is 0.01 or more below. The measurement at this time represents a value when the stainless steel ball having a diameter of 5 mm is moved at 60 cm / m ² . In this evaluation, even if the photosensitive material surface is replaced as the mating material, the values are almost the same. As a typical example of the measuring method, a value obtained by moving a stainless ball having a diameter of 5 mm at 60 cm / m ² is used below.

As the slip that can be 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 No. 6,
Japanese Patent Publication No. 58-33541, British Patent Nos. 927, 4
46 or higher fatty acid esters (fatty acids having 10 to 24 carbon atoms and 10 carbon atoms) as disclosed in JP-A-55-126238 and JP-A-58-90633.
.About.24 alcohol esters) and higher fatty acid metal salts as disclosed in U.S. Pat. No. 3,933,516, and direct fatty acid salts as disclosed in JP-A-58-50534. Esters of chain higher fatty acids and straight chain higher alcohols, higher fatty acid-higher alcohol esters containing a branched alkyl group as disclosed in WO 90108115.8 and the like are known.

Among these, as polyorganosiloxanes, there are generally known polyalkylsiloxanes such as polydimethylsiloxane polydiethylsiloxane, polyarylsiloxanes such as polydiphenylsiloxane and polymethylphenylsiloxane, and Japanese Patent Publication 53-
292, JP-B-55-49294, JP-A-60-140
341, etc., such as an organopolysiloxane having a C5 or higher alkyl group, an alkylpolysiloxane having a polyoxyalkylene group in its side chain, and an alkoxy, hydroxy, hydrogen, carboxyl, amino, or mercapto group in its side chain. It is also possible to use modified polysiloxanes such as organopolysiloxanes, block copolymers having siloxane units, and JP-A-60-1.
It is also possible to use a graft copolymer having a siloxane unit in the side chain as shown in 91240.

As the higher fatty acid and its derivative and the higher alcohol and its derivative, higher fatty acid, metal salt of higher fatty acid, higher fatty acid ester, higher fatty acid amide,
Polyhydric alcohol esters of higher fatty acids, etc., higher aliphatic alcohols, monoalkyl phosphites of higher aliphatic alcohols, dialkyl phosphites, trialkyl phosphites, monoalkyl phosphates, dialkyl phosphates, trialkyl phosphates, higher alkyls Aliphatic alkyl sulfonic acid, its amide compound, its salt, etc. can be used.

As represented by the general formulas (1) and (2),
The long-chain alkyl compound is preferable in that sufficient slip properties and scratch resistance can be obtained before and after the development treatment. General formula (1) R ¹ X ¹ R ² General formula (2) R ³ X ² R ⁴ X ³ R ⁵ General formula (3) R ⁶ YBD In this general formula (1), R ¹ and R ² are fats. It is a group hydrocarbon group. The total carbon number of this compound is 25 or more and 120
You need the following: The total number of carbons needs to be 25 or more in order to obtain sufficient slipperiness. Also, the total carbon number is 120
When the amount is larger, 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.

In the general formula (2), R³, R^Four, R^Five
Is an aliphatic hydrocarbon group. The total carbon number of this compound is 3
It must be 0 or more and 150 or less. Sufficient slip of total carbon
In order to obtain the property, 30 or more is required. Also, total charcoal
If the number of primes exceeds 150, the solubility in organic solvents
Poor, it becomes difficult to apply by dispersion or coating. Total carbon number and
And more preferably 40 or more and 130 or less, and more preferably
Or more than 50 and less than 120. Also, sufficient scratch resistance,
And to prevent deterioration of slipperiness under various usage conditions, R
³, R^FiveAre each aliphatic having 10 to 70 carbon atoms
Hydrocarbon group, R ^FourIs an aliphatic having 10 to 50 carbon atoms
It is preferably a hydrocarbon group. R³, R^Fiveabout
When the carbon number is 10 or less, the scratch resistance deteriorates, and
Under the conditions of use, the slippery transfer causes deterioration of slipperiness.
It In addition, a fat having a carbon number of 70 or more and functionalized at one end
Family compounds are generally unknown. This aliphatic carbonization
The hydrogen group may have a straight-chain structure or contain an unsaturated bond.
May have some substituents, may have a branched structure
You may have a structure. Among them, especially from the viewpoint of scratch resistance
A linear structure is preferred. R³, R^FiveOf carbon number
Particularly preferred is 15 or more and 50 or less. Well
R^FourFor, if the carbon number is 10 or less, scratch resistance
Is deteriorated, and the slipperiness due to the transfer of the lubricant under various usage conditions
Worsens. In addition, functional groups with both ends having 50 or more carbon atoms
Modified aliphatic compounds are generally unknown. This
The aliphatic hydrocarbon group may also have a linear structure,
It may contain unsaturated bonds, or may have some substituents
It may have a branched structure. This
From the viewpoint of scratch resistance, a linear structure is particularly preferable.
R^FourIt is preferable that the number of carbon atoms in the
Is. Particularly preferred is 12 or more and 25 or less.
Further, in the general formulas (1) and (2), X¹, X², X
³Is a divalent linking group. Specifically, -C (O) O-,-C (O) N
R-, -SO3-, -OSO3-, -SO2NR-, -O-, -S-, -NR-, -O
C (O) NR-, etc. are shown (R is H or has 8 or less carbon atoms.
Indicates an alkyl group). This is expressed by the general formulas (1) and (2).
Specific examples of the compound are shown below.

[0073]

[Chemical 1]

[0074]

[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.

More preferable slipping agents include polar substituents on at least one of R ¹ and R ^{2 in} the general formulas (1) and (2) or on at least one of R ³ , R ⁴ and R ^5. Is a compound with. 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, but is -O.
_{H, -COOH, -COOM, -NH 3} , -NR 4 + A-
, -CONH _{2 and the} like are preferable. Here, 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. General formula (1) of the present invention,
The amount of the slip agent represented by (2) is not particularly limited, but its content is preferably 0.001 to 0.1 g / m ² , and more preferably in order to exhibit sufficient slip and scratch resistance. It is 0.005 to 0.05 g / m ² . Specific examples will be given below, but the present invention is not limited thereto.

[0077]

[Chemical 3]

[0078]

[Chemical 4]

Since the compounds of the above-mentioned general formulas (1) and (2) are highly hydrophobic, they often have poor solubility in solvents.
Therefore, there is a method of dissolving in a non-polar organic solvent such as toluene or xylene or a method of dispersing in a coating solution, but the method of dispersing is preferable because the non-polar organic solvent is difficult to handle. At this time, as the slipping agent / dispersing agent, those described in the general formula (3) may be used in combination or alone. In the general formula (3), R ⁶ is an aliphatic hydrocarbon group having 25 or more and 70 or less 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. Also, 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, but a compound having a hydrocarbon group of 70 or more carbon atoms Is little known to the public. The number of carbon atoms is particularly preferably 30 or more, 60
It is the following. Y is a divalent linking group. Specifically, -C (O) O-, -OCO-, -C (O) NR'-, -NR'CO-, -SO2NR'-,
-NR'SO2-, -O-, -S-, -NR-, -OCOR''COO-, -OCOR''O
And the like (R ′ represents H or a hydrocarbon group having 8 or less carbon atoms, and R ″ represents a hydrocarbon group having 0 to 8 carbon atoms). Further, B is-(CH ₂ CH ₂ O) a-,
Or- (CH ₂ CH (OH) CH ₂ O) b-or-((CH ₂ ) cCH (R) CH ₂ O)
d- or- (CH ₂ CH ₂ O) e- (CH ₂ CH (OH) CH ₂ O) f-((CH ₂ ) cCH
(R) CH ₂ O) g-, which is 3 to 4
0, b, d is 3 to 30, c is 1 to 3, e is 0 to 40, f
, G is 0 to 30, e + f + g is 3 to 40, and R is H, CH ₃ , or a phenyl group. If the length of these nonionic groups is too short, sufficient solubility of the slipping 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) is a-, a is preferably 5 to 30. The use ratio of the general formula (3) to the slip agent (1) or (2) is preferably 1: 9 to 9: 1, more preferably 6: 4 to 2: 8. 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.

[0080]

[Chemical 5]

The use of a binder capable of forming a film in the layer containing the compounds represented by the general formulas (1), (2) and (3) improves the surface condition of the coated lubricant and improves the film strength of the lubricant layer. Is particularly preferable in terms of. Examples of such a polymer include known thermoplastic resins, thermosetting resins, radiation curable resins,
Reactive resins, and mixtures thereof, hydrophilic binders such as gelatin can be used. In addition, it is preferable in terms of cost to include the radiation curable resin layer of the present invention. Specifically, as the thermoplastic resin, cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate,
Hydroxyacetyl cellulose phthalate, cellulose long chain alkyl ester, nitrocellulose, cellulose acetate propionate, cellulose derivatives such as cellulose acetate butyrate resin, vinyl chloride / vinyl acetate copolymer, vinyl chloride, vinyl acetate and vinyl alcohol, maleic acid And / or a copolymer with acrylic acid, a vinyl chloride / vinylidene chloride copolymer, a vinyl chloride / acrylonitrile copolymer, a vinyl copolymer such as an ethylene / vinyl acetate copolymer, an acrylic resin, a polyvinyl acetal resin, Polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene Down resin, rubber-based 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 group, 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. ) May be introduced. The above-mentioned polymer binders are used alone or in combination of several kinds, known isocyanate-based cross-linking agents,
And / or a radiation-curable vinyl-based monomer may be added for curing treatment.

The hydrophilic binders are described in Research Disclosure No. 17643, page 26, and No. 18716, page 651. Water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. It is illustrated. 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, -NR4} +, - CONH 2,
_{-SH, -OSO 3 M, -SO 3} M , and the like. Acetyl cellulose and the like can be mentioned as a particularly preferable example.

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 the} 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 -OS
O ₃ − and —SO ₃ −. M ¹ is H or a cation such as an alkali metal, an alkaline earth metal or a quaternary ammonium salt. Specific examples of the compound represented by the general formula (4) are shown below.

[0084]

[Chemical 6]

[0085] The addition amount of the additives represented by the general formula (4) of the present invention is preferably an amount up to solid content of 0.001 g / m ² or more slip agents, slip from 0.005 g / m ² An amount up to 1/2 of the solid content of the agent is more preferable. 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. Such emulsification / dispersion methods are described in textbooks such as "Karimai, Pebble, Hidaka" and "Handbook for Emulsification / Dispersion Technology Application" (Science Forum Edition).

As the slip agent used in the present invention, various methods of dispersing it 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 slip agent is solid-dispersed in an organic solvent by a ball mill, a sand grinder, or the like, a slip agent 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 them, the preferred method is a method in which the slip 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 preferable method is a method in which the lubricant is heated and dissolved at 60 ° C. to 150 ° C. and is dispersed as a cooling medium in a solvent having a solubility of 1% or less at room temperature. 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.

The diluting solvent used for coating may be any one 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.

Next, the film 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 Nos. 1-312537 and 1-31 are known.
2538.

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 the cartridge diameter of the current 25 m / m may be 22 m / m or less, preferably 20 m / m or less, 14
When it is m / m 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 or more 25
g or less, preferably 5 g or more and 15 g or less. The ratio of the internal volume of the cartridge to the cartridge and the plastic used in the cartridge is 4 to 0.7, preferably 3 to 1.

In the case of a patrone containing the preferred 135 color light-sensitive material in the present invention, the total weight of the plastic used in the patrone and the patrone case is usually 1
It is g or more and 25 g or less, preferably 5 g or more and 15 g or less. The patrone of the present invention is not particularly limited in its form.

Further, the cartridge used in the present invention for feeding the film by rotating the spool will be described. First of all, you can load it into the camera without pulling out the tip of the photo film from the Patrone body in advance.
There is a photographic film cartridge that can simplify the feeding mechanism on the camera side. 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. 1-3068).
In the film cartridge disclosed in (No. 45), flanges are rotatably provided at both ends of the spool shaft around which the film is wound.
There is a tongue that is raised inward. 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 projection 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, in the vicinity of the port portion, the wide-opening projection constantly pushes the flanges apart, 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 shading 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.

In the film cartridge disclosed in Japanese Patent Laid-Open No. 4-115251 (US Pat. No. 5,226,613), the flanges rotatably provided at both ends of the spool shaft and the inside of the outer circumference of these flanges are provided. And a tongue that is formed so as to project and that prevents winding looseness on the outermost periphery of the film that is wound around the spool shaft, and that is provided inside the cartridge and the flange is rotatably regulated at an angle inclined with respect to the spool shaft. And a second regulating rib that regulates the limit of the angle at which the flange inclines with respect to the spool shaft, and the width of the film tip is narrower than the distance between the tips of the tongues. The step between the side edge of the tip and the side edge of the part that can be photographed is formed as a gentle curve, and this step comes into contact with the tongue when the film is fed and the flange is attached. It is obtained as to widen. 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 for regulating the film in a state where the film is in contact with the tongue piece and widening the flange distance at a position toward the port opening, and provided inside the cartridge.
A restricting rib is provided for restricting the flange to be rotatable at an angle inclined with respect to the spool shaft. Further, in the present invention, the cartridges shown in FIGS. 1 to 5 are also preferably used, and the adaptation thereof was excellent.

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. The raw film and the developed photographic film may be stored in the same new cartridge,
Different patrones may be used. 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. Further, the developed photographic film may be stored in a new cartridge after applying a lubricant or an antistatic agent by a final processing bath or a coating method (for example, spraying, transferring, coating method, etc.) during the developing processing. .

[0098]

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. (Example 1) 1) Support The support used in this example was prepared by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 2 parts by weight of 326 (manufactured by Geigy) was dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C., and then at 130 ° C. for 3.3 times. The film was transversely stretched 3 times and further heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 85 μm. Furthermore, wrap a part of it around a stainless steel core with a diameter of 20 cm, and
A thermal history of 10 ° C. for 48 hours was given. 2) Coating of undercoat layer The above support is subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides thereof,
An undercoat liquid having the following composition was applied to each surface to form an undercoat layer on the high temperature surface side during stretching. For the corona discharge treatment, use a solid state corona treatment machine 6KVA model manufactured by Pillar Co.
A 0 cm wide support is treated at 20 m / min. At this time, the object to be treated is 0.375 KV.
A · minute / m ² was processed. The discharge frequency during processing is
The gap clearance between the electrode and the dielectric roll was 9.6 KHz and 1.6 mm. UV discharge treatment is 75 ° C
Discharging was performed while heating at. Further, the glow discharge treatment was performed by irradiating with a cylindrical electrode of 3000 W for 30 seconds. Gelatin 3 g Distilled water 25 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g P-chlorophenol 0.5 g Resorcinol 0.5 g Cresol 0.5 g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g trimethylolpropane triazine 0.2 g trimethylolpropane tristoluenediisocyanate 0.2 g methanol 15 cc acetone 85 cc formaldehyde 0.01 g acetic acid 0.01 g concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer having the following composition were provided as a back layer on one surface of the support. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid) 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 aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution reached 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. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water, and sprayed in a baking furnace heated to 650 ° C. to obtain a bluish average particle diameter of 0.0
A fine powder of 05 μm tin oxide-antimony oxide composite was obtained. The specific resistance of this fine particle powder was 5 Ω · cm. A mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name Dynomill; WILLYA.BACHOF).
It was prepared by dispersing with ENAG) until the residence time reached 30 minutes. The average particle size of the secondary aggregate at this time is about 0.04μ.
It was m.

3-1-2) Coating of conductive layer The following formulation was applied to give a dry film thickness of 0.2 μm,
It was dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0.01 parts by weight 3-2) Magnetic recording Coating of Layers 1100 g of the magnetic material shown in Table 1 was added with 220 g of water and 150 g of the silane coupling agent of the compound example [1] -19 in the text, and kneaded well for 3 hours with an open kneader. This roughly dispersed viscous liquid was dried at 70 ° C. for one day and night to remove water, and then heated at 110 ° C. for 1 hour for treatment to prepare surface-treated magnetic particles. Furthermore, with the following prescription,
It was kneaded again in the open kneader. The surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g Further, 200 with a sand mill (1/4 G) with the following formulation.
Finely dispersed at rpm for 4 hours. The above kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g Further diacetyl cellulose and C ₂ H ₅ as a curing agent
_{C (CH 2 OCONH-C 6} H 3 (CH 3) NCO) 3
Was added to the binder in an amount of 20 wt%. The obtained liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity was about 80 cp. The coating was carried out by a bar coater and the film thickness was 1.2μ. The amount of magnetic material was adjusted so that the saturation magnetization shown in Table 2 was obtained. Further, silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as an abrasive were added so as to be 10 mg / m ² and coated. Drying was carried out at 115 ° C. for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C.). 3-3) Preparation of Sliding Layer The following prescription liquid was applied so that the solid coating amount of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ (compound) 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (compound) 9 mg / m ² The compound and the compound were added after forming a dispersion (average particle diameter 0.02 μ) in acetone.

4) Coating of light-sensitive material layer Next, each layer having the following composition was multilayer coated on the side opposite to the back layer obtained above to prepare a color reversal photographic film. (Photosensitive layer composition) JP-A-2-854, Example 1, Sample 10
The reverse color emulsion layer described in 1 was coated. With respect to the layer structure of the emulsion layers, the first layer is an antihalation layer, the second layer is an intermediate layer, the third to fifth layers are red-sensitive emulsion layers, and the seventh to ninth layers are green-sensitive emulsion layers. The 11th to 13th layers are blue-sensitive emulsion layers, the 14th to 15th layers are protective layers, and the 6th and 10th layers are intermediate layers.
The development processing was performed by Fuji Photo Film Co., Ltd., color reversal processing CR-56 processing. As a developing machine, E-6360 manufactured by Noritsu Koki Co., Ltd. was used.

The following evaluations were performed on the obtained samples. A) Magnetic properties Coercive force, saturation magnetization, and squareness ratio of the coated material were measured using VSMP10-15P manufactured by Toei Industry Co., Ltd. After slitting the film to a width of 35 mm, an FM head having a head gap of 5 μm and a turn count of 2000 can be input / output from the coated surface side of the magnetic recording layer at a feed rate of 100 mm / s for FM.
After recording the signal, the signal was read at the same head and the same speed, and it was determined whether the signal was output correctly. Table 2 shows the ratio of the number of error bits to the number of input bits.
It was shown to. When the error rate is 10 ⁻⁴ or less, there is no practical problem, but when the error rate is 10 ⁻³ or more, the result is NG. B) Optical performance A sample was prepared by removing only the magnetic material from the sample prepared above, and the status A of X-rite manufactured by X-rite was prepared.
The blue filter transmission density was measured by. Table 2 shows the increase in permeation density when the magnetic substance was added from this value. (C) Photographic performance Stain After each image in Table 2 was printed with various images and developed, the effect of stain concentration on the image quality was determined by a sensory test for the sample to which no magnetic substance was added.
O was given when the stain was acceptable, and X was given when the stain was not noticeable. After printing and developing various images on each sample in the same manner as in the granular form, the effect of the magnetic substance grains on the granular form was determined by a sensory test for the sample to which the magnetic substance was not added. O was given to those which were acceptable, and X was given to those which were not acceptable due to the noticeable graininess. From Table 2, it is understood that the film having the magnetic recording layer of the present invention has both excellent magnetic performance and photographic performance.

[0104]

[Table 1]

[0105]

[Table 2]

Example 2 For the sample (1A) used in Example 1, the antistatic layer was changed to that shown in Table 3 and the above error rate was measured 10 times for each sample. The error rate is 10 ^{-3 in the} 10 error rate measurements.
The number of times that the above became NG is shown in Table 3, and it can be seen that the magnetic performance deteriorates unless the electric resistance is set to 10 ¹² Ω · cm or less as in the present invention.

[0107]

[Table 3]

(Example 3) The error rate was measured 10 times for each sample by changing the sample (1A) used in Example 1 to one without a sliding layer.
Table 4 shows the number of times that the error rate became 10 ⁻³ or more and became NG in the 10 times of error rate measurement. As a result, it was found that the magnetic performance deteriorates if the sliding layer is not provided as in the present invention. .

[0109]

[Table 4]

(Embodiment 4) The same procedure as in the first to third embodiments was carried out except that the light-sensitive material was changed to the light-sensitive material described in Example 1 of JP-A-2-93641. To create a sample. That is, the first layer is an antihalation layer, the second layer is an intermediate layer, the third to thirteenth layers are photosensitive layers, and the fourteenth to fifteenth layers are protective layers. Development of the obtained photographic film was carried out by the following method. The developing machine used was a cine type automatic developing machine FNCP-900 manufactured by Fuji Photo Film Co., Ltd. Development of these samples was carried out as follows. 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 05 seconds The composition of the treatment liquid used in each step is as follows. It was

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 sulphate 4.5 g Water was added to 1.0 liter pH 10.0 Bleaching solution Ethylenediaminetetraacetic acid ferric iron Ammonium salt 100.0 g Ethylenediaminetetraacetic acid disodium salt 10.0 g Ammonium bromide 150.0 g Ammonium nitrate 10.0 g Water added 1.0 liter pH 6.0 Fixer ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4 0.0 g ammonium thiosulfate aqueous solution ( 0%) 175.0 g Sodium bisulfite 4.6 g Water was added to 1.0 liter pH 6.6 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10 ) 0.3g Water was added and 1.0 liter As a result, the same result as Examples 1-3 was obtained.

Example 5 Sample (1A) of Example 1
A sample which does not give a thermal history of 110 ° C. for 48 hours was prepared on the support used in step 1, slit into a width of 35 mm, and then mounted in a 135 standard cartridge. In addition, the same sample was used as the support for polyethylene naphthalate (PEN).
Was prepared by using polyethylene terephthalate (PET) instead of. Each of the above cartridges was left in an atmosphere of 40 ° C. for 24 hours and then left in an atmosphere of 25 ° C. overnight. These samples (other than Sample 1A) had a strong curl due to curl. After that, the error rate was measured 10 times as in Example 3, and the error rate was 10 times.
Table 5 shows the number of times NG became ^-3 or more and became NG. It can be seen that if the support is not previously given a heat history as in the present invention, the curl becomes strong and the magnetic performance is deteriorated in the subsequent heat treatment.

[0113]

[Table 5]

Example 6 When each sample of Example 1 was subjected to the developing treatment by preparing a sample not subjected to the surface treatment, the surface of the light-sensitive material layer was peeled off. Further, the above-mentioned peeling did not occur by performing at least one of the surface treatment of ultraviolet irradiation, corona discharge, glow discharge, and flame.

Example 7 Samples 1A to 1 of Example 1
Each photosensitive material sample of C was incorporated into the cartridge shown in FIG.
When an experiment similar to the above was performed, the same good result as in Example 1 was obtained.

Example 8 Samples 1A to 1 of Example 1
When each photosensitive material sample of C was incorporated in the cartridge shown in FIGS. 1 to 5 and the same experiment as in Example 1 was conducted, the same good result as in Example 1 was obtained.

[0117]

According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having a magnetic recording layer which has good magnetic recording characteristics and has little adverse effect on photographic properties.

[Brief description of drawings]

FIG. 1 shows an exploded view of a cartridge used in the present invention.

FIG. 2 shows an assembly drawing of a film cassette of a cartridge used in the present invention.

FIG. 3 shows an assembly drawing of a film cassette of a cartridge used in the present invention.

FIG. 4 shows a side view of a cartridge used in the present invention.

FIG. 5 shows a view of a spool of a cartridge used in the present invention.

[Explanation of symbols]

 1 film cassette 3 cassette shell 5, 7 shell 9 light-shielding door 11 film spool 13 filmstrip 15 spool core 17 spool lock 19 label 21 spool tooth 23 meshing space 25, 27 spool disk 29 film end 31 door cam 33 spool lock fastener 35 , 37, 39, 41 Window 43 Flange

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/85 1/91 3/00 530 555 A G11B 5/633

Claims (9)

[Claims] 1. A transparent support having at least one silver halide emulsion layer, and a transparent magnetic recording layer on the entire surface of the screen on the opposite side of the transparent support from the silver halide emulsion layer. In the silver halide photographic light-sensitive material, the magnetic recording layer has a saturation magnetization of 1.5 to 7.0 emu / m ² , a squareness ratio of 55% or more, and a coercive force of 750 to 1200 Oe. A silver halide photographic light-sensitive material characterized in that the increase in transmission density due to installation is 0.15 or less in terms of blue filter density. 2. The ferromagnetic powder contained in the magnetic recording layer has a saturation magnetization of 70 emu / g or more and a coercive force of 650 Oe to 950.
Needle-like C with Oe, Fe ²⁺ / Fe ³⁺ ratio 0-10%, major axis length 0.05-0.3μ, major axis / minor axis ratio 4-15
2. O-deposited gamma ferric oxide.
The silver halide photographic light-sensitive material described in. 3. The silver halide photographic light-sensitive material has an electrical resistance of 10 at 25 ° C. and 10% RH.
^The silver halide photograph according to claim 1 or 2, which has at least one antistatic layer using a conductive metal oxide or / and an ionic polymer as an antistatic agent so as to have a resistance of ¹² Ω · cm or less. Photosensitive material. 4. The silver halide photographic light-sensitive material according to claim 1, further comprising a lubricant layer on the magnetic recording layer. 5. The transparent support has a thickness of 50 to 105.
μ, a polyethylene aromatic dicarboxylate polyester having a glass transition temperature of 50 to 200 ° C., at a temperature of 40 ° C. or more and a glass transition temperature or less before applying the undercoat layer or after applying the undercoat layer and before applying the emulsion layer. The silver halide photographic light-sensitive material according to claim 1, which is heat-treated for 1 to 1500 hours. 6. The polyethylene aromatic dicarboxylate-based polyester support is a polyester containing benzenedicarboxylic acid, naphthalenedicarboxylic acid and ethylene glycol as main raw materials, and has a glass transition temperature of 90 to 200.
6. The silver halide photographic light-sensitive material according to any one of claims 1 to 5, which has a temperature of ° C. 7. The silver halide photographic light-sensitive material according to claim 1, wherein the polyethylene aromatic dicarboxylate polyester support is a polyethylene naphthalate derivative. 8. The halogen according to claim 1, wherein the surface treatment of the support is performed by at least one of ultraviolet irradiation treatment, corona discharge treatment, glow discharge treatment, and flame treatment. Silver halide photographic light-sensitive material. 9. A spool rotatably mounted on the cartridge body is rotated in the film feeding direction,
The silver halide photographic light-sensitive material according to claim 1, wherein the tip of the silver halide photographic light-sensitive material wound around the spool is sent to the outside from the film outlet of the cartridge body. Characteristic silver halide photographic light-sensitive material.