JPH07219135A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material with the surface flatness in longtime preservation improved, which is hardly curled at a high temp. and a low humidity, without any trouble in developing after photographing and with a magnetic recording error eliminated by providing a silver halide emulsion layer with a hydrophilic colloid as the binder on one side of a substrate. CONSTITUTION:On silver halide emulsion layer with a hydrophilic colloid as the binder is provided on one side of a substrate. One non-photosensitive hydrophilic layer having 0.5 to 10mum thickness and one non-photosensitive layer thereon having 0.4 to 10mum thickness are formed on the other side of the substrate, and one transparent magnetic recording layer having 400 to 3000Oe coercive force is formed on the non-photosensitive layer. The thickness of the substrate is controlled to 50 to 300mum, the substrate has 50 to 200 deg.C glass transition temp., and the polyester substrate is heat-treated at 40 deg.C to glass transition temp. for 1 to 1500hr before the undercoat is formed or before the emulsion is applied after the undercoat was applied.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a halogenated product which has good flatness during storage and is resistant to curling especially at high temperature and low humidity, has no trouble during development processing after photographing, and has no magnetic recording error. A silver photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material, a photographic film, a photographic light-sensitive material) is provided, and the silver halide photographic light-sensitive material allows the photographic film to be freely drawn into and drawn from a cartridge in a camera. And a photographic system excellent in writing or reading magnetic recording data.

[0002]

2. Description of the Related Art Generally, a roll film as a photographic light-sensitive material is a color or black-and-white film which is typically used for photographing by being stored in a cartridge with a width of 35 mm or less and loaded in a camera. Conventionally, TAC has been mainly used as a support for roll film, but the feature of this support is that it has no optical anisotropy and high transparency. However, as a drawback of the TAC support, its strength is insufficient and the current international labeling standard (IS
The cartridge defined by O1007) requires a TAC thickness of 115 μm or more.

In order to overcome the disadvantage that the film strength is small, it is conceivable to use polyester mainly composed of PET as a support. However, the problems are as follows. First, there is a decrease in mechanical strength as the film becomes thinner, and the photosensitive layer made of gelatin causes shrinkage due to low humidity, resulting in a curl in the width direction (U-shape).

Secondly, there is a strong curl in the winding core portion that occurs during storage over time due to a large amount of winding. In the conventional 135 system using PET as the support, the spool diameter is 11.5 mm, but even if it accommodates up to 39 sheets, winding is usually loose inside the cartridge, so the winding core with the smallest winding diameter is practically used. The roll diameter of the film is 1
It is 3.5 mm. On the other hand, when the film is completely wound so that the winding diameter of the film is substantially 11.5 mm at the winding core portion, a remarkable curling occurs when it is stored for a long time, causing various troubles. For example, when developing with a minilab automatic developing machine, one end of the photosensitive material is fixed to the leader, but the spool itself is not fixed at the spool end, which is the other end. The film is wound up on the spool, and the supply of the processing liquid to the film at the winding portion is delayed, which causes "processing unevenness". Also, the roll-up of this film is crushed by a drying roller etc. in the minilab, and the film "folds".
Occurs. Especially when kept at high temperature during storage,
The occurrence of the curling habit is remarkable, which causes a problem.

In order to solve the problems relating to the strength and curl habit of the above-mentioned support, a polyester support represented by polyethylene terephthalate (PET), which is excellent in mechanical strength, is used, and the support is preheated to be wound. A method of improving habit is disclosed. For example, US Pat.
No. 141,735. However, the commonly used roll-shaped color negative film does not use a hydrophilic binder on the back surface, and as a new problem, when the gelatin film on the emulsion side contracts or expands due to humidity change, the flatness of the film is reduced. Has a problem of being significantly damaged. In particular, the shrinkage of the emulsion side gelatin film is remarkable at low humidity, and the film may be rolled in some cases. The poor flatness of the film is particularly remarkable in the case of a polyester support having a small support thickness.

In order to solve this problem, Japanese Patent Laid-Open No. 5-33347.
No. 1 describes that polyethylene naphthalate is used as a support and a photosensitive material having a gelatin layer on the back is provided to solve the problem. It is described that by providing this sensitive material, the handleability is good even when the thickness of the support is 55 μm to 80 μm. However, as a problem of the technique, since the gelatin is exposed as it is, it is very bad against scratches on the bag, and there is a problem that there is a defect that it is reflected in the print. Further, in the invention, it is described that when the thickness of the support is 90 μm, the curl recovery property is poor and a break occurs in an automatic developing machine, which cannot be used, and an improvement thereof is desired. It also involves a problem of blocking when stored in a roll state at a high temperature and a high humidity for a long time.

It is known that the conventional photographic film optically imprints information (for example, date and time), but more information (for example, photographing condition, person to be photographed, number of prints, trimming information, etc.). Could not be given. Recently,
Attempted to apply the magnetic recording layer to photographic film,
There is an advantage that a magnetic recording layer is provided on a photographic film and the above information is arbitrarily given. In order to provide a magnetic recording layer on a photographic film, it is essential that the photographic performance is not deteriorated and that the magnetic characteristics are sufficiently exhibited.
For example, Japanese Patent Publications No. 42-4539 and 57-6576.
And the magnetic recording layers described in JP-A-4-62543 and JP-A-5-40321. However, according to the method of this patent, there is a problem that a magnetic input / output error occurs remarkably depending on the environment during the handling.

[0008]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a light-sensitive material comprising a polyester support having high film strength and less curling over time during storage. A second object of the present invention is to provide a light-sensitive material composed of a polyester support having a small curl at low humidity. A third object of the present invention is to provide a light-sensitive material having a back layer with improved scratches. A fourth object of the present invention is to provide a photographic film having a magnetic recording layer having excellent transparency and excellent magnetic properties. Fifth of the present invention
It is an object of the present invention to provide a light-sensitive material in which blocking caused by generation of time when stored in a rolled state is improved.

[0009]

The above-mentioned objects can be achieved by the silver halide photographic light-sensitive material of the present invention described below. (1) In a silver halide photographic light-sensitive material having at least one layer of a silver halide emulsion layer having a hydrophilic colloid as a binder on one surface of the support, the coated surface of the support on the silver halide emulsion layer And at least one non-photosensitive hydrophilic layer having a thickness of 0.5 to 10 μm on the opposite back side and at least one 0.4 to 10 μm non-photosensitive hydrophobic layer as an outer layer, and At least one transparent magnetic recording layer having a coercive force of 400 to 3000 Oe is provided as an outer layer, the thickness of the support is 50 μm to 300 μm, and the glass transition point thereof is 50 ° C. to 200 ° C. before applying an undercoat layer or A silver halide copy characterized in that it is a polyester support which is heat-treated at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours after the undercoat layer is applied and before the emulsion is applied. The light-sensitive material. (2) The transparent magnetic recording layer having a coercive force of 400 to 3000 Oe, which is applied on at least one layer on the back side of the support, has a particle surface area of ^{2 to} 100 m ² / g and an average particle size of 0.01 to 0.8 μm. 10 to 300 magnetic materials
The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material contains mg / m ² .

Further, (3) the silver halide photographic light-sensitive material as described in (1) or (2) above, wherein the non-photosensitive hydrophilic layer is composed of gelatin or a gelatin derivative. is there. Still more preferably,
(4) The amount of gelatin or gelatin derivative in the non-photosensitive hydrophilic layer on the back side of the silver halide photographic light-sensitive material is
(3) The weight ratio is 0.03 to 0.7 with respect to the amount of gelatin in the silver halide emulsion layer.
The silver halide photographic light-sensitive material described in 1.

Preferably, (5) in the silver halide photographic light-sensitive material described in (1) or (2) above, the non-photosensitive hydrophilic layer is gelatin or a gelatin derivative, and the non-photosensitive material on the back side is A silver halide photographic light-sensitive material characterized in that the binder of the hydrophobic layer has a glass transition temperature of 80 ° C. or higher.

Preferably, (6) in the silver halide photographic light-sensitive material, the non-light-sensitive hydrophobic layer is selected from a polymerizable and condensable synthetic polymer and a derivative of a natural polymer containing cellulose. Any one of the above (1) to (5), which is a layer mainly composed of a kind of hydrophobic polymer and has a total film thickness of 0.5 μm to 10 μm.
A silver halide photographic light-sensitive material as described in the above item. (7) The silver halide photographic light-sensitive material as described in (6) above, wherein the cellulose derivative is cellulose diacetate, cellulose triacetate, cellulose acetate dibutyrate, or cellulose acetate dipropionate. Further preferably, (8) in the silver halide photographic light-sensitive material described in (1) to (5), the magnetic material is ferromagnetic iron oxide fine powder, Co-containing ferromagnetic iron oxide fine powder, or ferromagnetic chromium dioxide. A silver halide photographic light-sensitive material, which is one kind of ferromagnetic fine powder selected from fine powder, ferromagnetic metal fine powder, ferromagnetic alloy fine powder, barium ferrite, magnetite, and Co-containing magnetite. Further, (9) In the silver halide photographic light-sensitive material described in (1) to (8) above, at least one layer of an antistatic agent (a conductive metal oxide or / and an ionic polymer ((having an electrical resistance of 10 ¹² Ω or less, 25 ° C / 1
0% RH) and / or a fluorine-based compound) and / or a slip agent (static friction coefficient of 0.25 or less) and / or a matting agent (average particle size 0.05 to 10 μm). This is achieved by a photographic light-sensitive material.

Preferably, (10) the photographic light-sensitive material is wrapped around the silver halide photographic light-sensitive material by rotating a spool rotatably provided in the cartridge body in the feeding direction of the photographic light-sensitive material. The silver halide photographic light-sensitive material as described in any one of (1) to (9) above, wherein the tip of the material is used by sending it out from a photographic light-sensitive material outlet of the cartridge body. . Further preferably, (11) the silver halide photographic light-sensitive material is used by storing the data in a photographic camera having a magnetic recording system having a magnetic recording data writing or reading device. It is achieved by the silver halide photographic light-sensitive material described in any one of (1) to (10) above.

First, the non-photosensitive hydrophilic layer coated on the back side of the present invention will be described. The non-photosensitive hydrophilic layer on the back side of the present invention is a layer made of a hydrophilic binder,
As the hydrophilic binder used in the non-photosensitive hydrophilic layer, those having a moisture absorption rate and a moisture absorption rate close to those of the binder of the photographic layer on the surface coated with the silver halide emulsion layer are preferable from the viewpoint of curling. The binder of the non-photosensitive hydrophilic layer of the present invention is gelatin or a gelatin derivative, and the hydrophilic binder other than gelatin is colloidal albumin,
Examples thereof include proteins such as casein, agar, sodium alginate, sugar derivatives such as starch derivatives, cellulose compounds such as carboxymethyl cellulose and hydroxymethyl cellulose, and synthetic hydrophilic compounds such as polyvinyl alcohol, poly-N-vinylpyrrolidone and polyacrylamide. ..

Among these, gelatin and gelatin derivatives are the most preferable. As the gelatin and gelatin derivative, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin, which are commonly used in the art, can be used. Among these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used. These gelatins contain various impurities such as 0.01 to 20000 ppm of metals (Na, K, Li, Rb, Ca, Mg, Ba, Ce, F) in the production process.
e, Sn, Pb, Al, Si, Ti, Au, Ag, Z
metal such as n and Ni, and their ions), and ions (F, Cl, Br, I, sulfate ions, nitrate ions, acetate ions, ammonium ions, etc.) may be contained. Especially in lime-processed gelatin, it is common knowledge in the art to contain Ca and Mg ions, and the content is 1
It is very wide as 20,000 ppm and does not cause any particular problem in the present invention. In the case of a synthetic hydrophilic compound, other components may be copolymerized, but if the hydrophobic copolymerization component is too much, the moisture absorption amount and the moisture absorption rate of the non-photosensitive hydrophilic layer become small, which is unsuitable from the viewpoint of curling. Is. Among these, polyvinyl alcohol, poly-N-vinylpyrrolidone and polyacrylamide are preferable. These hydrophilic colloids may be used alone or in combination of two or more.

A polymer latex may be further added to the non-photosensitive hydrophilic layer of the present invention. The polymer latex used in that case has an average particle size of 20 nm to 1000 n.
The dispersion may be water, an organic solvent, or a mixture thereof, and is not particularly limited. The amount used is preferably 0.01 to 3.0, and particularly preferably 0.1 to 2.0 as a dry weight ratio with respect to 1.0 of the binder. In that case, as a preferable example of the polymer latex, styrene, an alkyl (C 1-24) ester of acrylic acid, a hydroxyalkyl ester or a glycidyl ester, or an alkyl ester, a hydroxyalkyl ester or a glycidyl ester of methacrylic acid is used as a monomer. It has a unit and an average molecular weight of 10,000 or more, particularly preferably 3
And 500,000 to 500,000 polymers, and specific examples include methyl, ethyl, propyl, butyl, hexyl, octyl,
Dodecyl, stearyl, cyclohexyl, benzyl, phenethyl, hydroxyethyl acrylate, methacrylate, polystyrene are preferred. In addition to the binder, the non-photosensitive hydrophilic layer of the present invention is for photographic use of inorganic or organic fine particles such as matting agents, surfactants, dyes, cross-linking agents, thickeners, preservatives, UV absorbers and colloidal silica. You may add an additive. Regarding these additives, for example, Research Disclosure Vol. 176, Item 17643 (197)
The description in December 8) can be referred to.

The non-photosensitive hydrophilic layer of the present invention may be one layer or two or more layers. The thickness of the hydrophilic back layer of the present invention is 0.5 μm to 10 μm, and more preferably 1 μm to 7 μm from the viewpoint of curling. When the non-photosensitive hydrophilic layer is composed of two or more layers, the sum of the thicknesses of all the non-photosensitive hydrophilic layers is the thickness of the non-photosensitive hydrophilic layer of the silver halide photographic light-sensitive material of the present invention. . Particularly preferably, in order to maintain the curl balance, it is important to define the amount of gelatin in the hydrophilic back layer in proportion to the amount of gelatin in the silver halide emulsion. The weight ratio of the amount of gelatin in the non-photosensitive hydrophilic layer on the back side to the amount of gelatin in the silver halide emulsion layer on the opposite side is preferably 0.03 to 0.7. If the weight ratio is less than 0.03, the curl balance deteriorates,
If it is 0.7 or more, the blocking property at high humidity tends to deteriorate. The weight ratio is more preferably 0.05 to 0.6, and particularly preferably 0.1 to 0.5. When the non-photosensitive hydrophilic layer on the back side is composed of two or more layers, it indicates the sum of the gelatin amounts of all the non-photosensitive hydrophilic layers. The total of gelatin on the emulsion layer side is also shown.

Next, the non-photosensitive hydrophobic layer on the back side of the present invention will be described. The constituent material of the non-photosensitive hydrophobic layer is a hydrophobic polymer layer. The non-photosensitive hydrophobic layer of the present invention is substantially non-swelling in the processing liquid. Substantially non-swelling in the processing liquid means that the thickness of the non-photosensitive hydrophobic layer after completion of the washing step during development processing is 1.05 times or less than the thickness of the non-photosensitive hydrophobic layer after completion of the drying step. Say. The binder of the non-photosensitive hydrophobic layer of the present invention is not particularly limited as long as the polymer layer is "substantially non-swelling in the processing liquid".

Specific examples of the binder for the non-photosensitive hydrophobic layer include polyethylene, polypropylene, polystyrene,
Fluorinated resins such as polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene, polyvinylidene fluoride, butadiene rubber, chloroprene rubber, natural Rubbers such as rubber, cellulose derivatives, esters of acrylic acid or methacrylic acid such as polymethylmethacrylate and polyethylacrylate, polyester resins such as polyethylene phthalate, polyamide resins such as nylon 6 and nylon 66, cellulose diacetate, cellulose triacetate, etc. Water-insoluble polymers such as cellulose resin and silicone resin, or derivatives thereof. The binder of the non-photosensitive hydrophobic layer may be a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers. Preferred non-photosensitive hydrophobic layer binders include cellulose derivatives, polyethylene, polypropylene, polystyrene, polyvinyl chloride,
Ester of acrylic acid or methacrylic acid such as polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate, polyethyl acrylate, polyester resin such as polyethylene phthalate, nylon 6, nylon 66
Can be mentioned. Particularly preferred are cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate dipropionate, cellulose tripropionate and cellulose acetate dibutyrate. Specific preferred examples of the binder of the non-photosensitive hydrophobic layer of the present invention are given below, but the binder is not limited thereto.

SB-1 methyl methacrylate: latex of acrylic acid = 97: 3 SB-2 butyl methacrylate: methacrylic acid = 9
7: 3 latex SB-3 ethyl acrylate: acrylic acid = 97: 3
Latex SB-4 methyl methacrylate: styrene: 2-ethylhexyl acrylate = 63: 9: 27 latex SB-5 styrene: butadiene: divinylbenzene:
Methacrylic acid = 20: 7 SB 2: 6: 2 latex SB-6 Vinyl acetate: ethylene: acrylic acid = 78:
20: 2 latex SB-7 Vinylidene chloride: acrylonitrile: methyl methacrylate: ethyl methacrylate: acrylic acid =
90: 1: 4: 4: 1 latex SB-8 Ethyl acrylate: glycidyl methacrylate: acrylic acid = 95: 4: 1 latex

SB-9 Silicon Acrylic Resin Siren ARJ-12L (manufactured by Nippon Pure Chemical Co., Ltd.) SB-10 Siren ARJ-1L (〃) SB-11 Water-based urethane resin HYDRAN AP60 (Dainippon Ink and Chemicals Co., Ltd. ) SB-12 〃 HYDRAN AP10 (〃) SB-13 Acrylic resin Julimer ET410 (manufactured by Nippon Pure Chemical Industries, Ltd.) SB-14 Water-based polyester resin FINETEX ES850 (manufactured by Dainippon Ink Chemicals, Inc.) SB -15 Vinyl acetate-acrylic resin POLYKEM 49S (〃) SB-16 Polyethylene resin Chemipearl S120 (Mitsui Petrochemical Co., Ltd.) SB-17 Cellulose diacetate (acetylation degree 2.5) SB-18 Cellulose triacetate (acetylation) 2.8) SB-19 Cellulose Acetate Dipropionate SB-20 Cellulose Tripropionate S B-21 Cellulose acetate dibutyrate

Among these binders of the non-photosensitive hydrophobic layer, the glass transition temperature (Tg) of 80 is more preferable.
℃ or above. This is a temperature close to the vehicle temperature in the middle of summer, and a binder having a low Tg is likely to cause a failure in which the films block each other. Specific examples of Tg of 80 ° C. or higher include cellulose derivative, acrylic resin, polystyrene, polycarbonate, phenol resin, melamine resin, and urea resin as preferable binders. Radiation curable resin can also be preferably used,
Examples thereof include compounds having an acryloyl group and a methacryloyl group. Among these, cellulose compounds are particularly preferable, and SB-17 to SB-21 described above are particularly preferable. In the non-photosensitive hydrophobic layer of the present invention, a matting agent, a surfactant, a dye, a slip agent, a cross-linking agent, a thickener,
Photographic additives such as UV absorbers and inorganic fine particles such as colloidal silica may be added. Research Disclosure, Vol. 176, 17643
The description in the section (December 1978) can be referred to.

The non-photosensitive hydrophobic layer of the present invention may be one layer or two or more layers. The thickness of the hydrophobic layer of the present invention is 0.4 to 10 μm. The more preferable thickness of the hydrophobic polymer layer depends on the binder species of the non-photosensitive hydrophobic layer, but is 0.5 to 10 μm, more preferably 0.5 to 5 μm.
Is the range. When the non-photosensitive hydrophobic layer of the present invention is composed of two or more layers, the sum of the thicknesses of all the non-photosensitive hydrophobic layers is calculated as the non-photosensitive hydrophobic layer of the silver halide photographic light-sensitive material of the present invention. The thickness. The method of applying the non-photosensitive hydrophobic layer of the present invention is not particularly limited. After coating and drying the non-photosensitive hydrophilic layer, the non-photosensitive hydrophobic layer may be coated on the non-photosensitive hydrophilic layer and then dried, or the non-photosensitive hydrophilic layer may be non-photosensitive and hydrophobic. The layers may be applied simultaneously and then dried. The non-photosensitive hydrophobic layer may be dissolved in a solvent of the binder of the non-photosensitive hydrophobic layer and applied in a solvent system, or the hydrophobic polymer may be dispersed in an appropriate medium and the dispersion may be used. Then, it may be applied by either water system or organic solvent system. In the present invention, a preferred combination in the case of coating the non-photosensitive hydrophobic layer on the non-photosensitive hydrophilic layer is a non-photosensitive hydrophilic layer is a gelatin layer, gelatin is coated,
In this method, a non-photosensitive hydrophobic layer made of a cellulose derivative is applied thereon and then dried.

The method used for coating the non-photosensitive hydrophilic layer and the non-photosensitive hydrophobic layer of the present invention is not particularly limited. Conventionally known methods in which a non-photosensitive hydrophilic layer of a silver halide photographic light-sensitive material is used for coating can be used. For example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat.
The extrusion coating method using a hopper described in No. 1,294, or the multilayer simultaneous coating method described in US Pat. Nos. 2,761,418, 3,508,947, and 2,761,791 can be used. it can. The drying method is not particularly limited, but it is preferable that the T
It is preferably dried at g or less. However, when the heat treatment is carried out to improve the curl after the coating layer of the present invention is applied, the drying condition is not particularly limited and there is no particular problem even if it is Tg or more.

Next, the aromatic polyester support which is the support of the present invention will be described. The aromatic polyester of the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components. The essential aromatic dicarboxylic acid is one having at least one benzene nucleus in the dicarboxylic acid. Moreover, you may mix with an aliphatic dicarboxylic acid as needed. Such usable aromatic and aliphatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, and naphthalenedicarboxylic acid (2,6
-, 1,5-, 1,4-, 2,7-), diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride,
Succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1,1-dicarboxy-2-phenylethylene, 1,4-dicarboxymethylphenol, 1,3-
Examples thereof include dicarboxy-5 phenylphenol, sodium 3-sulfoisophthalate, and the like.

Next, as diols, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1 Examples thereof include cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, p-hydroxyethyloxybenzene, and bisphenol A. Also,
If necessary, a monofunctional or trifunctional or more polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. Further, the polyester of the present invention may be copolymerized with a hydroxycarboxylic acid having at the same time a hydroxyl group and a carboxyl group (or its ester) in the molecule.

Among these dicarboxylic acid monomers,
Preferred aromatic dicarboxylic acids are 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA),
Isophthalic acid (IPA), orthophthalic acid (OPA),
Paraphenylenedicarboxylic acid (PPDC) is preferred,
Further, 2,6-naphthalenedicarboxylic acid is preferable. The diol is preferably ethylene glycol (EG), polyethylene glycol (PEG), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA) or biphenol (BP), and more preferably ethylene glycol. Also,
As the hydroxycarboxylic acid, parahydroxybenzoic acid (PHBA) or 6-hydroxy-2-naphthalenecarboxylic acid (HNCA) may be used.

These monomers are polymerized to form polyesters. Preferred examples thereof include homopolymers such as polyethylene terephthalate, polyethylene naphthalate and polycyclohexanedimethanol terephthalate (PCT), and terephthalic acid, naphthalenedicarboxylic acid and ethylene. Copolymer of glycol (the mixing molar ratio of terephthalic acid and naphthalene dicarboxylic acid is 0.9: 0.1
0.1: 0.9 is preferable, and 0.8: 0.2-0.
2: 0.8 is more preferable. ), A copolymer of terephthalic acid, ethylene glycol, and bisphenol A (the mixing molar ratio of ethylene glycol and bisphenol A is 0.
It is preferably between 6: 0.4 and 0: 1.0, more preferably 0.
It is preferably 5: 0.5 to 0: 0.9. ) And other copolymers are preferred. Among these, polyesters containing 2,6-naphthalenedicarboxylic acid are particularly preferable. Specifically, 2,6-naphthalenedicarboxylic acid is added in an amount of 0.1 to 1.0.
It is a polyester containing. 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, an acid component may be directly esterified with a glycol component (direct weighting method), or a dialkyl ester may be used as an acid component to undergo a transesterification reaction with a glycol component, which is then heated under reduced pressure to remove excess surplus. The glycol component may be removed (transesterification method), or it can be synthesized. Alternatively, the acid component is set as an acid halide,
It may be reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. These polyester synthesis methods are described, for example, in Polymer Experimental Science No. 5
Volume "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980) No. 10
Pages 3 to 136, "Synthetic Polymer V" (Asakura Shoten, 19
71) pp. 187-286 can be referred to.

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 glass transition temperature (Tg) of the polyester of the present invention is preferably 90 ° C. or higher and 200 ° C. or lower. The glass transition temperature (Tg) in the present invention is defined as follows using a differential thermal analyzer (DSC). First, 300 mg of a 10 mg sample was heated in a nitrogen stream at a heating rate of 20 ° C./min.
After raising the temperature to ℃, it is rapidly cooled to room temperature. 20 ° C /
The arithmetic mean temperature of the temperature that begins to be biased from the baseline and the temperature that returns to the new baseline when the temperature is raised again in minutes,
Alternatively, when an endothermic peak appears in Tg, the temperature indicated by the maximum value of this endothermic peak is defined as Tg. Here, it is desirable that the sample be a powdery amorphous resin, but even if a support is used, the value hardly changes. In addition,
In the following description of the present specification, the glass transition temperature of the polyester support may be referred to for convenience of description, but the present invention is not limited thereto.

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 homopolymer-Example 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.

Polyester Copolymer-Example P-4: 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) ) Tg = 102 ° C. P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C. P-7: TPA / EG / BPA (100/50/50) Tg = 105 ° C. P-8: TPA / EG / BPA (100/25/75) Tg = 135 ° C. P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C.

P-10: 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. Polyester Polymer Blend Example 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. -20: 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.

Next, the polyester support of the present invention is treated at 40 ° C. before application of the undercoat layer or after application of the undercoat layer and before application of the emulsion.
The heat treatment is performed at a temperature not higher than the glass transition temperature for 0.1 to 1500 hours. More preferably, the heat treatment temperature is 50 ° C. or higher and lower than Tg, further preferably (Tg−20 ° C.) to lower than Tg. 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. More preferably, it is 1 hour or more and 120 hours or less. To further increase the effect of eliminating the curl, T
After heat treatment at a temperature of g or more and less than the melting point (melting temperature obtained by DSC) to erase the heat history of the support, the above-mentioned 50 ° C.
Reheat treatment may be performed at a temperature of Tg or higher and lower than Tg.

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. In the heat treatment in the roll form, unevenness is given to the surface (for example, silica or conductive inorganic fine particles such as SnO ₂ / Sb ₂ O ₅ are applied), and knurling is given to the end of the support. Is desirable. 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. These heat treatments may be carried out at any stage after the film formation on the support, after the surface treatment described below, after coating the back layer (antistatic agent, lubricant, etc.), and after coating the undercoat. However, usually, the pre-heat treatment is carried out during the film formation on the support, and the post-heat treatment is carried out at any stage after the surface treatment, after the coating of the back layer (antistatic agent, slipping agent, etc.) and after the undercoat coating.

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 support.
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. Examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, and salicylic acid-based ultraviolet absorbers.

As a preferable method for avoiding the light piping phenomenon of the polyester support of the present invention, a method of incorporating inert inorganic particles or the like into the support or adding a dye is preferable. As the dye, from the above viewpoint, Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku
It is possible to achieve the object by mixing a commercially available dye for polyester. Regarding the dyeing density, it is necessary to measure the color density in the visible light region with a color densitometer manufactured by Macbeth Co. and be at least 0.01 or more. More preferably, it is 0.03 or more. The polyester support according to the present invention is made of SiO ₂ , TiO ₂ , B as inorganic particles in order to impart slipperiness depending on the use.
Add aSO ₄ , CaCO ₃ , talc, kaolin and the like.

In order to use these polyester supports as photographic supports, it is preferable to carry out various surface treatments. For example, chemical treatment, mechanical treatment, corona discharge treatment,
Flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment,
Surface activation treatments such as active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment can be mentioned. 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 preferably carried out by the treatment methods described in JP-B-43-2603, JP-B-43-2604, and JP-B-45-3828. A mercury lamp is a high-pressure mercury lamp consisting of a quartz tube, and the wavelength of ultraviolet rays is 180-
Those between 320 nm are preferred. The UV irradiation may be performed in the stretching step of the support, at the time of heat setting, or after the heat setting.

With respect to the method of ultraviolet irradiation, a high-pressure mercury lamp having a main wavelength of 365 nm can be used as the light source if there is no problem in the performance of the support that the surface temperature of the support will rise to around 150 ° C. . When low temperature treatment is required, a low pressure mercury lamp having a dominant wavelength of 254 nm is preferable. It is also possible to use an ozone-less type high pressure mercury lamp and a low pressure mercury lamp. The amount of light processed is
A high pressure mercury lamp for a 365nm main wavelength, the irradiation light quantity 20~10000 (mJ / cm ²⁾ C., more preferably 50~2000 (mJ / cm ^2). 254n
In the case of low-pressure mercury lamp to the m and dominant wavelength, the irradiation light quantity 100~10000 (mJ / cm ²⁾ C., more preferably 300~1500 (mJ / cm ^2).

Next, the corona discharge treatment will be described by any known method, for example, Japanese Patent Publication No. 48-5043.
No. 47-51905, JP-A-47-28067.
No. 49-83767, No. 51-41770, No. 51-131576, and the like. Discharge frequency is 50Hz-5000KH
z, preferably 5 KHz to several 100 KHz, and particularly preferably 10 Hz to 30 KHz. 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 K
V · 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.

For 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, and more preferably 1/16 to 1/1.
It is 9. For natural gas, it is 1/6 to 1/10, and more preferably 1/7 to 1/9. Flame treatment amount is 1 to 50K
cal / 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 processing 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 can be carried out by any conventionally known method, for example, Japanese Patent Publication Nos. 35-7578 and 36-7.
-10336, 45-22004, 45-22
No. 005, No. 45-24040, No. 46-43480.
No. 3,057,792 and 3,057,7.
No. 95, No. 3,179,482, No. 3,288,63
No. 8, No. 3,309,299, No. 3,424,735
No. 3, 3,462,335, 3,475,307
No. 3,761,299, British Patent 997,093
JP-A No. 53-129262 and the like can be used. There are a method of introducing various gases such as oxygen, nitrogen, helium or argon into the atmosphere of glow discharge treatment, and a method of introducing water vapor. The steam partial pressure in the 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. Furthermore, it is preferable to perform the vacuum glow discharge treatment in a state where the film to be surface-treated is heated in advance. The preheating temperature is preferably 50 ° C or higher and Tg or lower, and 70 ° C or higher and Tg
The following is more preferable, and 90 ° C. or higher and Tg or lower is further preferable. Examples include raising the polymer surface temperature, heating with an infrared heater, and heating with contact with a hot roll.

The pressure during glow discharge treatment is 0.005 to 2
It is preferably 0 Torr. More preferably 0.02-
2 Torr. The voltage is preferably between 500 and 5000V. More preferably, it is 500-3000V. The discharge frequency used is from direct current to several 1000 MHz, preferably 50 Hz to 20 MH, as found in the prior art.
z, and more preferably 1 KHz to 1 MHz. Discharge treatment intensity is 0.01 KV · A · min / m ^{2 to 5} KV · A
・ Min / m ² is preferable, more preferably 0.15 KV ・
A · min / m ^{2 to 1} KV · A · min / m ² . It is preferable that the temperature of the support thus subjected to the glow discharge treatment is immediately lowered by using a cooling roll.

The photographic element is then coated onto a surface-treated polyester support of the present invention. The undercoat layer that is usually provided as an adhesive layer when attached is described. The undercoat layer may be a single layer, and may have a multilayer structure of two or more layers in some cases. 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.

It is also preferable to obtain good adhesiveness by swelling the support in the undercoat layer and interfacially mixing with the hydrophilic undercoat polymer. Examples of compounds that swell these supports include resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, dichlorophenol, trichlorophenol, and monochlorophenol. Examples thereof include acetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. In the first undercoat layer in the multilayer method, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid,
Starting with copolymers starting from monomers selected from itaconic acid and maleic anhydride, polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and many other polymers, the undercoating second
Layers have been investigated for their properties primarily with respect to gelatin. Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates,
Examples thereof include active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine and the like), epichlorohydrin resin and the like.

The undercoat layer of the present invention comprises 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. The undercoating 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, a gravure coating method, or US Pat.
It can be applied by an extrusion coating method using a hopper described in Japanese Patent No. 681,294.

In the present invention, the preferred support is polyethylene-2,6-naphthalate at a temperature between 100 ° C. and 115 ° C.
Heat treated for a period of time and the thickness of its support is 85 μm to 105 μm
m, the surface of which is subjected to ultraviolet irradiation treatment or glow discharge treatment, the back side non-photosensitive hydrophilic layer is a gelatin layer of 1 to 7 μm, and the non-photosensitive hydrophilic layer is 0.5 to It is characterized by being a 5 μm cellulose binder. 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 magnetic recording layer of the present invention will be described in detail. The magnetic material of the present invention includes ferromagnetic iron oxide fine powder, Co-containing ferromagnetic iron oxide fine powder, ferromagnetic chromium dioxide fine powder, ferromagnetic metal fine powder, ferromagnetic alloy fine powder, barium ferrite, magnetite, Co-containing magnetite. Is preferred. Further preferred magnetic particles are ferromagnetic iron oxides such as γFe ₂ O ₃ (FeOx, 4/3 <x ≦ 3/2), Co
Co-deposited ferromagnetic iron oxide (FeO) such as γFe ₂ O ₃
x, 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, for example, Hexagonal Ba ferrite, S
r-ferrite, Pb-ferrite, Ca-ferrite, their solid solutions or ion-substituted products can be used. The manufacturing method of these ferromagnetic powders is known, and the ferromagnetic material used in the present invention can also be manufactured according to the known method.

The shape and size of the ferromagnetic material will be described.
The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape, etc., but needle shape is preferable in terms of electromagnetic conversion characteristics. The particle size and specific surface area are not particularly limited, but the specific surface area is S
A 2m ² / g~100m ² / g in _BET, 5m ² / g
To 80 m ² / g is more preferable, and further preferably 5 m
² / g to 60 m ² / g. Average particle size is 0.0
1 to 0.8 μm, and in the case of needles, the major axis is 0.01 to
0.8 μm, the short axis is 0.005 to 0.4 μm, and the ratio of the long axis to the short axis is preferably 100: 1 to 2: 1. Further, the long axis is 0.04 to 0.4 μm and the short axis is 0.1. 01-0.1 μm is more preferable, and the ratio of the major axis to the minor axis is more preferably 100: 1 to 3: 1. The particle size distribution of the magnetic material is preferably as sharp as possible. The larger the saturation magnetization (σ s) of the ferromagnetic material, the more preferable it is, but 50 emu / g or more, and more preferably 70 emu / g or more. Coercive force (Hc) is 400 Oe
Or more and 3000 Oe or less, preferably 500 Oe to 200
0 Oe or less, more preferably 600 Oe to 18
It is 00 Oe. Also, the squareness ratio (σr / σs
) Is preferably 40% or more, more preferably 45% or more, 6
0% or more is particularly preferable.

These ferromagnetic particles are prepared, for example, in 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. Examples of the coupling agent include Japanese Patent Publication No. 1-261469 and Japanese Patent Application No. 4-317118.
Known materials such as those described in can be used, eg 3
-Mercaptopropyl trimethoxysilane, 3-isocyanylpropyl methyldimethoxysilane, 3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane, 3-methoxy (poly (degree of polymerization 6) oxyethynyl) oxypropyl tri Methoxysilane,
Decyltrimethoxysilane or the like is used.

The addition amount of these silane coupling agent and titanium coupling agent to the magnetic particles is 1.0 to 2
The amount is preferably 00% by weight, preferably 1 to 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, Japanese Patent Application No. 4-3171
As described in No. 18, it is processed by a direct processing method for magnetic particles or an integral blend method, and the direct method includes a dry method, a slurry method and a spray method. In the dry method, for example, it is preferable that magnetic particles and a small amount of water, or an organic solvent containing water and a coupling agent are mixed, stirred with an open kneader to remove water, and then finely dispersed.

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 dipropionate, cellulose acetate dibutyrate, 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, Examples thereof include rubber resins such as polyester resins, polyether resins, polyamide resins, amino resins, styrene butadiene resins and butadiene acrylonitrile resins, silicone resins, and fluorine resins.

Among these binders, cellulose diacetate, cellulose triacetate, cellulose acetate dipropionate and cellulose acetate dibutyrate are 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 , where M is hydrogen, an alkali metal or ammonium, and when there are plural Ms in one group, they may be different from each other, It is preferable that R is hydrogen or an alkyl group) from the viewpoint of dispersibility and durability of the magnetic material. The content of polar groups is 10 ⁻⁷ to 10 per gram of polymer.
^-3 equivalents, and more preferably 10 ^-6 to 10 ^-4 equivalents are preferable ranges.

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; reaction products of these isocyanates and polyalcohols (for example, reaction product of tolylene diisocyanate 3 mol and trimethylolpropane 1 mol) , And polyisocyanates produced by condensation of these isocyanates.

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.

It is preferable to harden a magnetic recording material containing gelatin. As a hardener that can be used in the magnetic recording layer,
For example, various hardeners described in Japanese Patent Application No. 4-317118 are used. The amount of the hardener used is usually 0.01 to 30% by weight, preferably 0.05 to 20% by weight, based on dry gelatin. A method for dispersing the above-mentioned magnetic material in the binder is described in, for example, Japanese Patent Application No. 4-18.
In addition to 9652, various known means are possible, but a kneader, a pin type mill, an annular type mill, etc. are preferable,
A combination 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, more preferably from 0.02 to 0.5 g / m ^2. The coercive force of the film provided with the magnetic recording layer is 5
It is preferably 00 Oe or more and 3000 Oe or less, and more preferably 800 Oe or more and 1500 Oe or less. The increase in color density due to the provision of the magnetic recording layer needs to be suppressed as low as possible, but the increase in blue filter density is 0.5 or less, preferably 0.2 or less.

The magnetic recording layer of the present invention can be provided on the entire back surface of the photographic support of the present invention by coating or printing or in the form of stripes. It is also preferable to co-extrude the binder resin in which the magnetic particles are dispersed and the resin for forming the support in the form of a stripe or in the form of a stripe to form a support having a magnetic recording layer. In this case, the compositions of the two kinds of resins may be different, but it is preferable that they are the same. The magnetic recording layer coated on the support is, if necessary, immediately subjected to a treatment for orienting the magnetic material in the layer while drying, and then the formed magnetic recording layer is dried. There is a method of using a permanent magnet or a solenoid coil to orient the magnetic body. The strength of the permanent magnet is preferably 2000 Oe or more, 3
Particularly preferred is 000 Oe or more. 5 for solenoid
It may be 00 Oe or more. Further, the timing of orientation during drying is preferably at a point where the residual solvent in the magnetic recording layer is 5% to 70% as described in Japanese Patent Application No. 5-005822. If necessary, the surface is smoothed to produce the magnetic recording layer of the present invention. These are disclosed in, for example, Japanese Patent Publication No. 40-23625, Japanese Patent Publication No. 39-28368, and U.S. Pat. No. 3,473,960. Further, the method disclosed in Japanese Patent Publication No. 41-13181 is considered to be a basic and important technique in this field.

The magnetic recording layer may also have functions such as antistatic and head polishing, or another functional layer may be provided to impart these functions. For example, inorganic,
Organic fine particles (for example, silica, SiO ₂ , SnO ₂ ,
Al ₂ O ₃ , TiO ₂ , cross-linked polymethylmethacrylate, barium carbonate, silicone fine particles, etc.) are preferably added. Further, 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.
4159, JP-A-51-30725, JP-A-51-51
129216, and polymers as described in JP-A-55-95942. Examples of the cationic polymer include JP-A-49-121523 and JP-A-48-91.
No. 165 and Japanese Patent Publication No. 49-24582. In addition, ionic surfactants are also anionic and cationic. For example, JP-A-49-8582.
6, JP-A-49-33630, US 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 needle-like 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, particularly 0.00
It is desirable that the thickness is 1 to 0.3 μm. In order to more efficiently give conductivity, the primary fine particles are partially aggregated to give
It is preferable to use fine particles or filler of a conductive crystalline oxide or its composite oxide having a particle size of 01 to 0.2 μm. Further, the conductivity reached when producing an antistatic layer using these is preferably 10 ¹² Ω or less, more preferably 10 ¹² Ω or less, both in raw and after treatment.
^The electrical resistance is ¹⁰ Ω or less, particularly preferably 10 ^9.5 Ω or less. In that case, the content in the photosensitive material is generally 5
~ 500 mg / m ² is preferred and particularly preferred is 10-350 m
It is g / m ² . The amount of binder is 1 to 500 m.
g / m ² is preferable, and 5-300 mg / m ² is particularly preferable. The ratio of the amount of fine particles of the conductive crystalline oxide or its composite oxide or the acicular filler to the binder is 1/30.
0-100 / 1 is preferable, and 1/100 is more preferable.
~ 100/5.

In the present invention, a slip agent is preferably used. As the slip agent, for example, polyorganosiloxane as disclosed in Japanese Patent Publication No. 53-292 and disclosed in US Pat. No. 4,275,146 are disclosed. Higher fatty acid amides as described above, Japanese Patent Publication No. 58-33541, British Patent No. 927,446, or Japanese Patent Laid-Open No. 55-12.
6238 and 58-90633, higher fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) as disclosed in US Pat. No. 3,933,516. Higher fatty acid metal salts as disclosed in the specification and also JP-A-58-
Esters of linear higher fatty acids and linear higher alcohols, as disclosed in 50534, WO 901081.
Higher fatty acid-higher alcohol esters containing a branched alkyl group as disclosed in 15.8 are known. Specific examples of such compounds are shown below, but the present invention is not limited thereto. First, the polysiloxane compound will be described.

(S-1) (CH ₃ ) ₃ SiO- (Si (CH ₃ ) ₂ O) a-Si (CH ₃ ) ₃ a = 5 to 1000 (S-2) (C ₆ H ₅ ) ₃ SiO _{- (Si (CH 3) 2} O) a-Si (CH 3) 3 a = 5 ~1000 (S-3) (CH 3) 3 SiO- (Si (C 5 H 11) (CH 3) -O) _{a-Si (CH 3) 3} a = 10 (S-4) (CH 3) 3 SiO- (Si (C 12 H 25) (CH 3) -O) 10- (Si (CH 3) 2 O) 18 _{-Si (CH 3) 3 (S} -5) (CH 3) 3 SiO- (Si (CH 3) 2 O) x - (Si (CH 3) ((CH 2) 3 -O (CH 2 CH 2 O _{) 10 H) -O) y -} (Si (CH 3) 2 O) z-Si (CH 3) 3 x + y + z = 30 (S-6) (CH 3) 3 SiO- (Si (CH 3 ) ₂ O) x-(Si (CH ₃ ) {(CH ₂ ) ₃ -O (CH ₂ CH (CH ₃ ) -O) ₁₀ (CH ₂ CH ₂ O) ₁₀ C ₃ H ₇ } O) y-( Si (CH ₃ ) ₂ O) z-Si (CH ₃ ) ₃ x + y + z = 35

The higher fatty acids and their derivatives, the higher alcohols and their derivatives include higher fatty acids, higher fatty acid metal salts, higher fatty acid esters, higher fatty acid amides, higher fatty acid polyhydric alcohol esters, and higher aliphatic compounds. Alcohol, higher alkyl alcohol monoalkyl phosphite, dialkyl phosphite, trialkyl phosphite, monoalkyl phosphate, dialkyl phosphate, trialkyl phosphate, higher aliphatic alkyl sulfonic acid, amide compound or salt thereof, etc. Can be used. Specific examples of such compounds are shown below, but the present invention is not limited thereto.

(1-1) n-C ₁₅ H ₃₁ COOC ₃₀ H ₆₁ -n (1-2) n-C ₁₇ H ₃₅ COOC ₃₀ H ₆₁ -n (1-3) nC ₆ H ₁₃ CH (OH) C ₇ H ₁₅ COOC ₄₀ H ₈₁ -n (1-4) nC ₆ H ₁₃ CH (OH) C ₇ H ₁₅ COOC ₅₀ H ₁₀₁ -n (1-5) n-C ₂₇ H ₄₃ COOC ₂₈ H ₅₇ -n (1-6) nC ₁₆ H ₃₃ CH (SO ₃ Na) COOC ₄₀ H ₈₁ -n (2-1) n-C ₂₁ H ₄₃ COO- (CH ₂ ) ₇ CH (CH ₃ )-
_{C 9 H 19 (2-2) n} -C 21 H 43 COOC 24 H 49 -iso (3-1) n-C 18 H 37 OCO (CH 2) 18 COOC 18 H 37 -
n (3-2) n-C ₄₀ H ₈₁ OCO (CH ₂ ) ₂ COOC ₅₀ H ₁₀₁
-n

(4-1) iso-C ₁₅ H ₃₁ COO (CH ₂ ) ₆
OCOC ₂₁ H ₄₃ -n (5-1) n-C ₃₀ H ₆₁ O (CH ₂ CH ₂ O) ₁₀ H (5-2) n-C ₄₀ H ₈₁ O (CH ₂ CH ₂ O) ₁₅ H (5 -3) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₅ H (5-4) n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₃₀ H (5-5) n-C ₅₀ H _{101 - (CH (CH 3)} CH 2 O)
₃ (CH ₂ CH ₂ O) ₁₆ H (5-6) n-C ₅₀ H _101- (CH ₂ CH (OH) CH ₂ O)
_{3 - (CH (OH) CH} 2 O) 3 - (CH 2 CH 2 O)
₁₅ H (6-1) n-C ₄₀ H ₈₁ OCOCH ₂ CH ₂ COO (CH ₂
CH ₂ O) ₁₆ H (6-2) n-C ₅₀ H ₁₀₁ OCOCH = CHCOO (CH ₂
CH ₂ O) ₁₆ H (6-3) n-C ₅₀ H ₁₀₁ OCOCH ₂ CH ₂ COO- (C
_{H 2 CH (OH) CH 2} O) 3 - (CH 2 CH 2 O) 15
H

By using such a slip agent, the scratch resistance is excellent, and the repelling on the undercoat surface does not occur,
A silver halide photographic light-sensitive material whose slipperiness is not deteriorated can be obtained by developing the photographic light-sensitive material. The amount of the slip agent used in the present invention is not particularly limited, but its content is 0.000.
5 to 2 g / m2 is preferable, more preferably 0.001
˜1 g / m ² , particularly preferably 0.002 to 0.5 g /
m ² . The layer to which the slip agent of the present invention is added is not particularly limited to this, but it is preferably contained in the outermost layer on the back surface. The surface layer containing the above-mentioned slipping agent can be formed by applying a coating solution prepared by dissolving this in an appropriate organic solvent onto a support or a support having a back layer on which other layers are applied, and drying. The slip agent can also be added to the coating solution in the form of a dispersion. Examples of the solvent used include water, alcohols (methanol, ethanol, isopropanol, butanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), esters (acetic acid, formic acid, oxalic acid, maleic acid, succinic acid, etc.). Methyl, ethyl, propyl, butyl ester, etc.), hydrocarbon type (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-methylpyrrolidone), ethers (diethyl ether, dioxane, tetrahydrofuranyl, etc.), ether alcohols such as propylene glycol monomethyl ether, glycerin, diethylene glycol, dimethyl sulfoxide, etc. are preferable. At this time, various surfactants can be used as the dispersant, and examples thereof include sodium cetyl sulfate and sodium p-pentadecylphenyl sulfonate.

In coating the above-mentioned slip agent, it is possible to use it together with a binder capable of forming a film. As such a polymer, a known thermoplastic resin, thermosetting resin, radiation curable resin, reactive resin, a mixture thereof, or a hydrophilic binder such as gelatin can be used. Examples of the thermoplastic resin include cellulose triacetate, cellulose diacetate, cellulose acetate maleate, cellulose acetate phthalate, hydroxyacetyl cellulose phthalate, cellulose long chain alkyl ester, nitrocellulose, cellulose acetate propionate, and cellulose acetate butyrate resin. Cellulose derivative, vinyl chloride
Vinyl acetate copolymer, vinyl chloride, vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid copolymer, vinyl chloride / vinylidene chloride copolymer, vinyl chloride / acrylonitrile copolymer, ethylene / vinyl acetate copolymer Vinyl-based copolymers such as polymers, acrylic resins,
Polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, silicone resin, Fluorine-based resins may be mentioned.

The slip agent that can be used in the present invention can be achieved by applying heat or air for drying after coating, but it is preferable to pass it through heated air or a roll, for example, at 50 ° C. or higher, more preferably 80 ° C. C. or higher is preferable, and 100.degree. C. or higher is particularly preferable, and the entire drying zone may be heated, or the transport roll may be heated. The coefficient of static friction is preferably 0.25 or less for the sliding performance, and the sample is kept at a temperature of 25.
After conditioning the humidity for 2 hours at ℃ and 60% RH, HEIDON
-10 A value measured with a static friction coefficient measuring machine using a 5 mmφ stainless steel ball. The smaller the value, the better the slipperiness. By reducing the coefficient of static friction, it is possible to reduce the friction between the emulsion surface and the back surface of the film or the inner surface of the film and the film, and between the film and the exit of the film cartridge when the film is sent out by the spool rotation from the film cartridge, which will be described later. Reduction can be achieved and scratches on the film can be prevented. The coefficient of static friction of the film before and after the development treatment is preferably 0.25 or less, more preferably 0.20 or less, still more preferably 0.16 or less, and particularly preferably 0.12 or less. At this time, it is preferable that both the emulsion surface and the back surface are small, but the smaller the back surface is, the better. In order to reduce the coefficient of static friction after development of the present invention to 0.25 or less, a lubricant may be contained in the emulsion layer and the back layer of the film, and it is particularly preferable to contain a lubricant in the outermost layers on both sides. The method for containing the slipping agent can be achieved by containing the composition in a coating solution and applying the composition, or the composition may be adhered to the film after the film is formed. There is also a means using a bar coating method, a spin coating method, or the like. To improve the slipperiness for this,
In the transport system at the time of manufacturing and handling, the sliding friction coefficient is lowered, and it is very preferable that not only the dynamic friction coefficient but also the static friction coefficient by the clip method is greatly reduced. That is, it is possible to obtain a dynamic friction coefficient or a static friction coefficient of 0.25 or less with respect to various conveying materials,
Furthermore, it is possible to obtain a coefficient of 0.16, and more preferably 0.12 or less.

Next, the film cartridge used in the present invention will be described. The cartridge used in the present invention is not particularly limited, but may be made of metal or a cartridge mainly made of synthetic plastic. Specific examples of the plastics material used in the present invention are shown below, but the present invention is not limited thereto, and specific examples include polystyrene, polyethylene, polypropylene, polymonochlorotrifluoroethylene, vinylidene chloride resin, vinyl chloride resin, and chloride. Vinyl-vinyl acetate copolymer resin, acrylonitrile-
There are butadiene-styrene copolymer resin, methyl methacrylic 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. To mold the plastics preferably used in the present invention, a plasticizer is mixed with the plastics as needed. As the plasticizer, for example, trioctyl phosphate, tributyl phosphate, dibutyl phthalate,
Typical examples are diethyl sebacate, methyl amyl ketone, nitrobenzene, γ-valerolactone, di-n-octyl succinate, bromonaphthalene and butyl palmitate. Further, the cartridge of the present invention may contain various antistatic agents. The antistatic agent is not particularly limited, but carbon black, metal oxide particles, nonion, anion, cation and betaine-based surfactants or polymers can be preferably used. As these antistatic patrones, JP-A-1-125537
No. 1-312538. Especially 2
The electrical resistance at 5 ° C. and 25% RH is preferably 10 ¹² Ω or less. 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 patrone may be the same as it is or the current cartridge diameter of 25 m / m is 22 m / m
Below, it is effective to reduce the size of the camera, preferably 20 m / m or less and 14 m / m or more.

The volume of the cartridge case is 30 cm ^3.
It is preferably 25 cm ³ or less, more preferably 20 c or less.
It is preferably m ³ or less. The weight of the plastic used for the cartridge and the cartridge case is 1 g or more and 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. Preferred 135 in the present invention
In the case of a cartridge containing a color sensitive material, the total weight of the plastic used in the cartridge and the cartridge case is usually 1 g or more and 25 g or less, preferably 5 g or more 15
g or less. The patrone of the present invention is not particularly limited in its form.

Further, a cartridge which is preferably used in the present invention and which sends a film by rotating a spool will be described. First, there is a photographic film cartridge that can be loaded into the camera without pulling out the tip of the photographic film from the main body of the cartridge in advance, and that the feeding mechanism on the camera side can be simplified. In this photo film cartridge, the tip of the film is stored in the cartridge body,
It is a structure in which the tip of the film is sent to the outside from the port of the cartridge by rotating the spool shaft in the film sending direction. In such a photographic film cartridge, U.S. Pat. No. 4,834,306 (JP-A-1-30)
In the film cartridge disclosed in Japanese Patent No. 6845), flanges are rotatably provided at both ends of the spool shaft around which the film is wound, and these flanges are bulged inward. A tongue is provided.
The method of blocking the light from 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 leading end of the film does not necessarily have to be arranged so as to be aligned with the leading end of the film drawing port, and may be housed inside the cartridge body, but it is preferably housed inside the film drawing port. A film cartridge disclosed in JP-A-4-115251 (US Pat. No. 5,226,613) is also preferably used. Further, the film cartridge disclosed in JP-A-5-210202 has a door type opening, and such a mechanism is also preferable.

The photographic film used in the present invention may be a so-called raw film before development, or may be a developed photographic film. 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. .

The light-sensitive material comprising the aromatic polyester support of the present invention, which has a magnetic recording layer, can be used in a conventional camera without any problem, but from the viewpoint of applying the magnetic recording layer, a magnetic head is built in the camera. Preferably, the system is The cameras are not particularly limited, but cameras with magnetic heads proposed by various companies in recent years are particularly preferable. For example, Japanese Patent Application Nos. 2-097314, 2-120676, 3-066951 and 3-1.
No. 12418, No. 3-045571, No. 4-0177
No. 48 etc. can be mentioned. Further, it is also preferably used in a camera having various other functions, and it is more preferable that these various functions are combined and given to the same camera. For example, Japanese Patent Application No. 3-305022
No. 3,222,292, 3,221,046, and 3,197,118 are also preferable.

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, roentgen, graphic arts sensitive material and the like. Here, a color silver halide photographic light-sensitive material will be described. The color light-sensitive material of the present invention may be provided with at least one silver halide emulsion layer of a blue color sensitive layer, a green color sensitive layer and a red color sensitive layer on a support. There is no particular limitation on the number of layers and the order of layers of the emulsion layer and 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, even if the above installation order is reversed depending on the purpose,
Further, the order of installation may be such that different photosensitive layers are sandwiched in the same color-sensitive layer.

A non-photosensitive layer such as an intermediate layer containing a color mixing inhibitor for each layer may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The plurality of silver halide emulsion layers constituting each unit photosensitive layer are those having regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal shapes such as spheres and plates. Those having crystal defects such as twin planes, 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.

As the silver halide emulsion, those which have been physically ripened, chemically ripened and spectrally sensitized are usually 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. The additives used in such a process are Research Disclosure N.
No. 17643 and No. 18716, the relevant parts are summarized in the table below. Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure (RD) N mentioned above.
No. 17643, VII-CG. Yellow couplers, 5-pyrazolone-based and pyrazoloazole-based magenta couplers, cyan couplers such as phenol-based and naphthol-based couplers, colored couplers for correcting unnecessary absorption of coloring dyes, and photographically useful with coupling. And a DIR coupler that releases a development inhibitor, and a coupler that releases a nucleating agent or a development accelerator in an image during development. Other couplers that can be used in the light-sensitive material of the present invention include US Pat.
Competitive couplers described in U.S. 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, JP-A-62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, after removal as described in EP 173,302A. Couplers that release dyes that recolor, R.I. D. No. 11449 and 2
4241, a bleaching accelerator releasing coupler described in JP-A-61-201247 and the like, a ligand-releasing coupler described in US Pat. No. 4,553,477 and the like, JP-A-63-7.
Examples thereof include couplers releasing the leuco dye described in No. 5747.

The coupler used in the present invention can be introduced into the photographic 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 include phthalic acid esters, phosphoric acid or phosphonic acid esters, benzoic acid esters, amides, alcohols or phenols, aliphatic carboxylic acid esters, aniline derivatives, hydrocarbons and the like. Examples of the auxiliary solvent include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

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, Photographic Science and Engineering (Ph.) By A. Green et al.
otogr. Sci. Eng. ), Volume 19, Issue 2, 12
Can be measured by using a type of Swellometer described (swelling meter) pp 4~129, T _^1/2 is 3 in the color developing solution
0 ° C., 90% of the maximum swollen film thickness reached when treated for 3 minutes 15 seconds and the saturated film thickness, which time defined to reach the thickness of the T ^_1/2.

[0082] 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 anion, nonion, cation, and betaine fluorine-containing surfactant can be used in combination. Preferred examples of these are described below.

F-1 C ₈ F ₁₇ SO ₃ K F-2 C ₇ F ₁₅ COONa F-3 C ₈ F ₁₇ SO ₂ N (C ₃ H ₇ ) -CH ₂ COO
_{K F-4 C 8 F 17} SO 2 N (C 3 H 7) - (CH 2 CH
_{(OH) CH 2 O) 3} - (CH 2) 4 SO 3 Na F-5 C 8 F 17 SO 2 N (C 3 H 7) (CH 2 CH 2
_{O) 4 (CH 2) 4} -SO 3 Na F-6 C 8 F 17 SO 2 N (C 3 H 7) CH 2 CH 2 -
O-P (= O) ( ONa) 2 F-7 C 8 F 17 CH 2 CH 2 OOC-CH 2 -CH
_{(SO 3 Na) -OCOC 8 H} 17 F-8 C 8 F 17 SO 2 NHCH 2 CH 2 CH 2 (OCH
_{2 CH 2) 3 -N (+} ) (CH 3) 2 -CH 2 COO (-) F-9 C 8 F 17 SO 2 NHCH 2 CH 2 N-N (+)
_{(CH 3) 3 · I (} -) F-10 C 8 F 17 SO 2 NHCH 2 CH 2 CH 2 (OCH 2 CH 2) 3 N (+) (CH 3) 3 ·
_{CH 3 -C 6 H 4 -SO 3} (-) F-11 C 8 F 17 SO 2 N (C 10 H 21) - (CH 2 CH
₂ O) ₁₆ H

In the present invention, a nonionic surfactant may be used. Specific examples of the nonionic surfactant preferably used in the present invention are shown below. _{N-1 C 11 H 23 COO} (CH 2 CH 2 O) 8 H N-2 C 17 H 33 COO (CH 2 CH 2) 5 (CH 2 -CH (OH) -CH 2) 3
_{(CH 2 CH 2 O) 5} H N-3 C 16 H 33 O (CH 2 CH 2 O) 12 H N-5 C 9 H 19 -C 6 H 4 -O (CH 2 CH 2 O) 10
H The layer to which the fluorine-containing surfactant and the nonionic surfactant used in the present invention are added is not particularly limited as long as it is at least one layer of the photographic light-sensitive material, and examples thereof include a surface protective layer, an emulsion layer, an intermediate layer and an undercoat layer. A layer, a back layer, etc. can be mentioned. The amount of the fluorine-containing surfactant and nonionic surfactant used in the present invention may be 0.0001 g to 1 g per 1 square meter of the photographic light-sensitive material, more preferably 0.0005 to 0.5 g, Especially preferred is 0.000
It is 5 g to 0.2 g. Further, two or more kinds of these surfactants of the present invention may be mixed.

[0085]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. (Example 1) 1-1) Supports Each support used in this example was prepared by the following method. a) PEN: 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinu as an ultraviolet absorber
vinP. 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 subsequently 13
The film was transversely stretched 3.3 times at 0 ° C., and heat-set at 250 ° C. for 6 seconds to obtain a PEN film. Then, wind a part of it around a stainless steel core with a diameter of 20 cm,
Heat treatment was carried out for 48 hours and heat history was applied. b) PET: A commercially available polyethylene terephthalate polymer was biaxially stretched and heat-set according to a conventional method to obtain a PET film. Further, a part thereof was wound around a stainless steel core having a diameter of 20 cm, and heat-treated at 70 ° C. for 48 hours to obtain a heat history.

C) PEN / PET = 4/1 (weight ratio);
PEN and PET pellets were vacuum dried in advance at 150 ° C. for 4 hours, kneaded and extruded at 280 ° C. using a biaxial kneading extruder, and then pelletized. This polyester was formed into a film under the same conditions as the above PEN. Then, wind a part of it around a stainless steel core with a diameter of 20 cm,
Heat treatment was performed at 5 ° C. for 48 hours to give a thermal history. d) TAC: methylene chloride / methanol = 82/8 by a normal solution casting method of triacetyl cellulose
wt ratio, TAC concentration 13%, plasticizer TPP / BDP = 2
/ 1 (where TPP; triphenyl phosphate, B
DP; Biphenyldiphenylphosphate) 15w
It was created by the t% band method.

1-2) Coating of undercoat layer Each of the above supports is subjected to corona discharge treatment, ultraviolet irradiation treatment, glow discharge treatment and flame treatment on both sides thereof, and then,
The undercoat liquid having the following composition was applied on both sides to be provided. Corona discharge treatment is made by Pillar solid state corona treatment machine 6KV
A 30 cm wide support is treated at 20 m / min using the A model. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings.
The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm.
Also, the ultraviolet irradiation treatment is 254n while heating at 175 ° C.
Discharge treatment was performed at 1500 mJ / m ² at m. Further, the glow discharge treatment is 0.15 Torr, 3000 W with a cylindrical electrode,
It was carried out at 27 KHZ for 10 seconds. Furthermore, flame treatment is performed using propane gas at a distance of 2 mm between the support and the inner flame of 100 mm.
It was applied at 0 ° C. for 2 seconds. At this time, the transport roller was cooled to 0 ° C. before use.

(Undercoating liquid) Gelatin 3 g Distilled water 25 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.01 g Diacetyl cellulose 0.05 g P-chlorophenol 0.05 g Resorcin 0.05 g Cresol 0.05 g (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g trimethylolpropane triazine 0.02 g trimethylolpropane tristoluenediisocyanate 0.02 g Polyglycol polyamine glycidyl addition / hydrochloride 0.02 g Methanol 15cc acetone 85cc acetic acid 0.01g concentrated hydrochloric acid 0.01g

1-3) Coating on the back side An antistatic layer having the following composition, a non-photosensitive hydrophilic layer, a non-photosensitive hydrophobic layer and a slip layer are formed on one side (back layer side) of the above-mentioned support after undercoating. An agent layer was applied. 1-4) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) 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 tin oxide-antimony oxide composite fine particle powder having an average particle size of 0.005 μm as bluish primary particles. It was The volume resistivity of this fine particle powder was 5 Ω-cm. A mixed solution of 40 parts by weight of the above fine particle powder and 60 parts by weight of water was adjusted to pH 7.0, roughly dispersed by a stirrer, and then a horizontal sand mill (trade name: Dynomill; WILL).
YA. It was prepared by dispersing with BACHOFENAG) until the residence time reached 30 minutes. At this time, the average particle size of the secondary agglomerate in which the primary particles were agglomerated was about 0.04 μm.

1-5) Preparation of Antistatic Layer The following formulation was applied to a dry film thickness of 0.2 μm,
It was dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion prepared in 1-4) 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 nonyl phenyl ether 0.01 parts by weight The following non-photosensitive materials are further added. The hydrophilic hydrophilic layer was applied and dried. The coating amount of tin oxide-antimony oxide composite is 0.1.
It was set to 0 mg / m ² . The drying temperature is 75 ° C.

1-6) Non-photosensitive hydrophilic layer Gelatin The coating amount is shown in Tables 1 and 2. Polymethylmethacrylate fine particles (average particle size 1 μm) 50 mg / m ² sodium dodecylbenzene sulfonate 5 mg / m ² polystyrene sulfonic acid Sodium 20 mg / m ² N, N′-ethylenebis- (vinylsulfoneacetamide) 30 mg / m ² Polyethyl acrylate latex (average particle size 0.1 μ) 0.2 g / m ² Polyoxyethylene nonylphenyl ether 5 mg / m ² C ₈ F ₁₇ SO ₃ K 3 mg / m ² The following non-photosensitive hydrophobic layer was further coated on this and dried (75
(° C, 10 minutes).

1-7) Non-photosensitive hydrophobic layer Hydrophobic polymer (types are as shown in Tables 1 and 2) Coating amount is shown in Tables 1 and 2 Polymethylmethacrylate / divinylstyrene = 7/3 molar ratio) Fine particles (average particle size 3μ) 10 mg / m ² C ₈ F ₁₇ SO ₃ K 5 mg / m ² C ₆ H ₁₃ CH (OH) C ₇ H ₁₅ COOC ₅₀ H ₁₀₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O ) ₁₆ H = (5/5 weight ratio) (slipper; added as a methanol dispersion with an average particle size of 0.02 μm) 5 mg / m ² magnetic substance (Co-deposited γ-Fe ₂ O ₃ , coercive force 900 Oe , Surface area 40 m ² / g, long axis 0.15 μm, short axis 0.03 μm) 60 mg / m ² Toluene diisocyanate 0.2 parts by weight

Here, the magnetic substance is Co-deposited γ-Fe ₂ O ₃ (11
(200 g) and trimethyloxy poly (degree of polymerization 16) oxyethyleneoxysilane (150 g) were added, and the mixture was well kneaded in an open kneader for 3 hours. 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. Further, the following formulation was used, and the mixture was kneaded again in an open kneader. Further sand mill (1
/ 4G) and finely dispersed at 200 rpm for 4 hours. 1-8) Lubricant Layer The following formulation 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 colloidal silica (particle size 0.02 μm) 5 mg / m ² silica (particle size 0.3 μm) 10 mg / m ² C ₆ H ₁₃ CH (OH) C ₇ H ₁₅ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (5/5 weight ratio) (slipping agent; added as a methanol / acetone dispersion having an average particle size of 0.02 μm) 15 mg / m ^{2 The} coating solvent is acetone, methyl ethyl ketone, Methanol was used.

2) Coating of a sensitive material layer A sensitive material was used as the sample 103 in Example 1 of JP-A-5-323540.
The material (sample) was prepared by applying the light-sensitive material described in 1. to the opposite side of the back layer. 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. 3) Evaluation The following evaluation was performed on the obtained sample. The photographic film was processed into the film form of the cartridge of FIG. 9 described in JP-A-5-210202 and incorporated in the cartridge. The film width was 24 mm, the spool diameter was 7 mm and the inner diameter was 20 mm.

3-1) Lead-out, curl measurement, uneven development, rear-end folding
After allowing to cool in a room at 5 ° C., the spool was rotated in the direction opposite to the winding direction of the film, and whether or not the leading end of the film came out was evaluated. Ten cartridges were tested to evaluate the number of troubles in which the tip did not come out. The greater the number of times, the worse. Next, the sample from which the film tip is taken out is an automatic processor (Minilab FP-550B: made by Fuji Photo Film)
It was developed. The developing solution is Fuji Photo Film C
N16FA was used. The curl value was immediately measured at 25 ° C. and 60% RH according to the ANSI curl measurement method. Further, the image unevenness during development and the trailing edge fold of the film were visually observed. Incidentally, for the sample in which the leading end of the film could not be taken out at all, the cartridge was disassembled and developed, and the subsequent evaluation was carried out. 3-2) Flatness on a printer Print a negative film that has been developed under the conditions of 25 ° C and 10% RH, and the degree of blurring in the central part and the peripheral part is large (x),
The visual evaluation was carried out in three grades of medium (Δ) and small (◯). The smaller, the better.

3-3) Magnetic Properties Using a VSMP10-15P manufactured by Toei Kogyo Co., Ltd., a film having a width of 24 mm after development was head gap 5 μm and the number of turns was 20 from the coated surface side of the magnetic recording layer.
After recording an FM signal at a feed speed of 100 mm / s with a head capable of inputting / outputting 00, the signal was read at the same head and the same speed, and it was determined whether or not the signal was correctly output.
Table 1 shows the ratio of the number of bits in which an error occurred to the number of input bits. If this error rate is 10 ^-4 or less, there is no practical problem, but if the error rate is 10 ^-3 or more, N
G.

4) Results The above results are shown in Tables 1 and 2. In the case of Comparative Samples 1 to 4 in which the polyester support of the present invention is not used, the support is TAC, and when the thickness of the support is reduced, the presence or absence of heat treatment and the non-photosensitive hydrophilic gelatin of the present invention Even if it was given, the curl value was large, the work of exposing the tip portion was difficult, and the magnetic characteristics were also poor, so that all could not be satisfied. Further, even in the polyester support of the present invention, Comparative Samples 5 and 13 which are not subjected to the heat treatment similarly cause not only the rear end bending but also the work of exposing the front end is difficult and the development unevenness occurs. It was a thing. Further, in Comparative Sample 23, which was outside the heat treatment temperature of the present invention, it was difficult to work out the leading end, uneven development, rear end folds, and the flatness of the printer was poor and the magnetic properties were remarkably poor. On the other hand, Samples 7 to 12, 15 to 16 of the present invention, which consist of the polyester support having the heat treatment and thickness of the present invention,
In Nos. 18 to 22, the workability of exposing the leading end was good, and neither uneven development nor rear end folding occurred.

It should be noted that, although within the scope of the present invention, Samples 10 and 21 having a thin support have a tendency to have a slightly large curl. On the other hand, Comparative Samples 6 and 14, to which the non-photosensitive hydrophilic gelatin of the present invention was not applied, had a large curl and had poor flatness in a printer, and the magnetic properties were remarkably inferior. Further, Comparative Sample 17, in which the thickness of the non-photosensitive hydrophobic layer was outside the thickness of the present invention, resulted in poor magnetic properties. Although not shown in Tables 1 and 2, even if the type of the support is PET or PEN, the thickness of the support is 50
When the thickness is less than μm, the flexural elasticity that can withstand the shrinkage stress of the photosensitive layer cannot be obtained, and a gutter-like curl is generated, and a rear end fold and a scratch are generated in the development processing step.

As a polymer having a glass transition temperature Tg of more than 200 ° C., poly (oxyisophthalooxy-2,6-dimethyl-1,4-phenyleneisopropylidene-3,5-dimethyl-1,2 having a Tg of 225 ° C. is used. 4-phenylene) could not be applied to a light-sensitive material because a transparent support was not obtained. Further, when the conductive particles in the back layer are not used, static marks are all generated, and in the present invention, the addition of the conductive layer is essential to enhance the commercial property of the photosensitive material. there were. further,
The sample to which the corona discharge treatment, the UV discharge treatment, the glow discharge treatment and the flame treatment were not applied in the coating of the undercoat layer did not have any adhesiveness, and both the back layer and the emulsion layer easily fell off. . In addition, the sample from which the dispersion of the slipping agent was removed in the non-photosensitive hydrophobic layer on the back layer side had a drawback that scratches occurred remarkably during handling, it clearly appeared on the print, and the commercial value was impaired. there were.

[0101]

[Table 1]

[0102]

[Table 2]

(Example 2) 2-11) Support In Example 1, first, PEN, PET and PEN / P were prepared.
ET = 4/1 (weight ratio) was wrapped around a stainless steel core having a diameter of 20 cm, and a heat history of heat treatment at 110 ° C. for 48 hours was given, but in Example 2, the following 2-1 was previously performed.
2) to 2-14), a back layer is applied, and then these supports are wound around the stainless steel core having a diameter of 20 cm, and a heat history of heat treatment at 110 ° C. for 48 hours is applied. It was 2-12) Coating of undercoat layer An undercoat layer was prepared in the same manner as in Example 1. 2-13) Coating on Back Side An antistatic layer having the following composition, a non-photosensitive hydrophilic layer and a non-photosensitive hydrophobic layer were provided on one surface of the above-mentioned support after undercoating. 2-14) Preparation of conductive fine particle dispersion (tin oxide-antimony oxide composite dispersion) Stannous chloride hydrate 230
Parts by weight and antimony trichloride 23 parts by weight ethanol 30
It was dissolved in 100 parts by weight 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 volume resistivity 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.BACH).
OFENAG) was dispersed until the residence time reached 30 minutes to prepare a dispersion liquid of a tin oxide-antimony oxide composite having a secondary aggregation of about 0.4 μm.

2-15) Preparation of conductive layer: The following formulation was applied to give a dry film thickness of 0.2 μm, and the mixture was dried at 115 ° C. for 6 hours.
It was dried for 0 seconds. 2-13) Conductive fine particle dispersion liquid 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 nonyl phenyl ether 0.01 parts by weight The following non-photosensitive materials are further added. The hydrophilic hydrophilic layer was applied and dried. The drying temperature is 75 ° C.

2-16) Non-photosensitive hydrophilic layer Gelatin The coating amount is shown in Table 3. Polymethylmethacrylate fine particles (average particle size 1 μm) 50 mg / m ² sodium dodecylbenzenesulfonate 5 mg / m ² sodium polystyrenesulfonate 20 mg / m ² N, N′-ethylenebis- (vinyl sulfone acetamide) 30 mg / m ² polyethyl acrylate latex (average particle size 0.1 μ) 0.5 g / m ² polyoxyethylene nonylphenyl ether 5 mg / m ² C ₈ F ₁₇ SO ₃ K 3 mg / m ² The following non-photosensitive hydrophobic layer was further coated on this and dried (75
(° C, 10 minutes).

2-17) Non-photosensitive hydrophobic layer Hydrophobic polymer (types are as shown in Table 3) Coating amount is shown in Table 3 Magnetic substance described in 1-7) Magnetic substance (Co-adhered γ-Fe) ₂ O ₃ , coercive force 900 Oe, surface area 40 m ² / g, major axis 0.15 μm, minor axis 0.03 μm) 60 mg / m ² Hydrophobic polymer (types are shown in Table 3)) Coating amount is listed in Table 3 Polymethyl Methacrylate / divinylstyrene = 7/3 molar ratio) Fine particles (average particle size 3μ) 10 mg / m ² Poly (methyl methacrylate / divinylbenzene = 8/2 weight ratio) fine particles (average particle size 0.5 μ) 10 mg / m ² C ₈ F ₁₇ SO ₃ K 5 mg / m ² C ₆ H ₁₃ CH (OH) C ₇ H ₁₅ COOC ₅₀ H ₁₀₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H = (5/5 weight ratio) ( Lubricant; added as a methanol dispersion with an average particle size of 0.02 μm) 5 mg / m ² C ₆ H ₁₃ CH (OH) C ₇ H ₁₅ COOC ₄₀ H ₈₁ / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H (4/6; weight ratio) 25 mg / m ² (slipper, average particle size 0.1 02 μm added as an acetone dispersion) C ₈ F ₁₇ O (CH ₂ CH ₂ O) ₁₆ H 5 mg / m ² Toluene diisocyanate 0.2 weight of the coating amount of the hydrophobic polymer Pentaerythritol and toluene diisocyanate Reaction product of isocyanate (molar ratio 1: 3) 0.3 weight of the coating weight of the hydrophobic polymer (acetone, methyl ethyl ketone, cyclohexanone, methylene chloride, propylene glycol monomethyl ether was used as the solvent for the coating fluid)

2-18) Coating of Photosensitive Layer Then, on the surface opposite to the support, JP-A-5-323540 was used.
The emulsion layer side of the light-sensitive material 103 of Example 1 was multilayer-coated with the emulsion layer and the surface protective layer in the order from the support to prepare a multilayer color light-sensitive material. The thickness of the emulsion layer is 25 μm
(At this time, the total amount of gelatin was about 14 g / m ² ). 2-19) Scratch evaluation In the atmosphere of the back side of the sample at 25 ° C and relative humidity of 60%, a steel ball of 5 mmφ was spun at a speed of 60 cm / min.
A continuous load was applied from 0 gram, and the load when scratches were observed with transmitted light was measured. It is shown that the heavier the load, the greater the resistance to scratches on the back surface and the better.

2-20) Blocking Evaluation A sample was cut into a piece of 24 mm × 24 mm, and the back surface and the emulsion surface were overlapped by the following two conditions (wet and dry), and a weight of 350 g was applied. Then, the back surface and the emulsion surface were peeled off, and the blocked area was evaluated.
The larger the area, the worse the blocking property. Wet condition: Samples were conditioned for 2 hours in an atmosphere of 25 ° C and 80% relative humidity, and the samples were overlaid, sealed in a polyethylene bag, weighted with 500 g, and placed in an oven at 45 ° C for 24 hours. did. Dry conditions: Samples are conditioned for 2 hours in an atmosphere of 25 ° C and 60% relative humidity, and then the samples are stacked and sealed in a polyethylene bag. did. The evaluation of blocking was performed according to the following display of the blocking area. ⊚: 0%, ∘: 5% or less, Δ: 5 to 25% or less, ×;
25-50% or less, XX; 50% or more

2-31) Results As shown in Table 3, T which is not the polyester support of the present invention
Comparative samples 24 and 25 using AC were difficult in workability of extracting the tip portion, were not significantly scratched, and had large curl and poor magnetic properties. Further, it can be seen that the comparative sample 26, which is the support of the present invention, but which is not heat-treated, has a difficulty in workability of extracting the tip portion, has a bad curl, and has a bad magnetic property. Further, it can be seen that the comparative sample 27 having no non-photosensitive hydrophilic layer of the present invention also has large curl and bad magnetic properties. On the other hand, Comparative Sample 28 without the non-photosensitive hydrophobic layer of the present invention had a small curl but was significantly inferior in scratching. On the other hand, the samples 29 to 36 of the present invention satisfy the performance in all respects, and it is clear that the present invention is remarkably excellent. Further, by using a cellulose ester as the non-photosensitive hydrophobic layer of the present invention, the scratch and blocking properties were remarkably improved, and the effect of the present invention was further exhibited. The non-photosensitive hydrophobic layer has a glass transition temperature of 8
The sample 36 using the polymer at 0 ° C. or lower showed a tendency that the blocking property was slightly inferior.

[0111]

[Table 3]

The conductivity of the sample of the present invention is 25
At 10 ° C. and 10% RH, the resistance was 10 ¹⁰ or less, and the antistatic property was excellent. On the other hand, in 29, which is the sample of the present invention, tin oxide /
When antimony oxide was not added, the electric resistance was 10 ¹⁵ or more, and static marks were remarkably generated during handling, which was not preferable for an image. Therefore, in the present invention, a remarkably excellent photosensitive material can be provided by adding an antistatic agent. Further, in the sample 29 of the present invention, when the surface treatment of the support (glow, corona, flame, UV irradiation) was not performed, sufficient adhesion could not be obtained on both the emulsion surface and the back surface, Moreover, the photosensitive material layer and the back layer were peeled off, which was not preferable as a photosensitive material. The sample of the present invention has a sliding property of the back of 0.5 cm.
With 100 g of stainless steel balls,
The coefficient of dynamic friction at 0 cm / min was 0.09 or less. On the other hand, in the case of the sample 29 in which the sliding agent on the back surface was not added, the coefficient of dynamic friction was 0.45, the slipperiness was very poor, and the scratches tended to deteriorate to about 33 g. It has been found that addition of a slip agent is preferable. In addition, the sample 29 of the present invention was prepared according to Japanese Patent Application No. 2-1206.
Taken with a camera with a magnetic head described in No. 76, its magnetic input / output property is also good and there is no uneven development or post-bending during development processing.
It was also confirmed that there was no problem with scratches and blocking during storage, and that it was also excellent as an image.

[0113]

INDUSTRIAL APPLICABILITY According to the present invention, in a silver halide photographic light-sensitive material having at least one layer of a silver halide emulsion layer having a hydrophilic colloid as a binder on one surface of the support, the silver halide emulsion layer of the support is used. Of at least one layer on the back side opposite to the coated surface of 0.5 to 10 μm
Of at least one non-photosensitive hydrophilic layer and its outer layer.
Having a non-photosensitive hydrophobic layer of 4 to 10 μm and having a surface area of at least ² to 100 m ² / g and an average particle size
A magnetic material having a thickness of 0.01 to 0.8 μm is used in the range of 10 to 300.
It has a transparent magnetic recording layer containing mg / m ² and a coercive force of 400 to 3000 Oe, and the thickness of the support is 50 μm.
m-300 μm, its glass transition point is 50 ° C to 200 ° C
0.1 to 1 at a temperature of 40 ° C. or higher and a glass transition temperature or lower before applying the undercoat layer or after applying the undercoat layer and before applying the emulsion.
Since it is a silver halide photographic material characterized by being an aromatic polyester support that has been heat-treated for 500 hours, by rotating a spool rotatably provided in the cartridge body in the film feeding direction, When the tip of the silver halide photosensitive material wound on the spool is sent to the outside from the film outlet of the cartridge body, the tip can be easily pulled out, it is hard to curl, there is little curl after development processing, and there is no trailing edge fold. Few. Further, it was also extremely excellent in terms of scratches and blocking, and a good image was obtained with the film produced from the support. Further, the silver halide photosensitive material of the present invention is applied to a photographic camera having a magnetic recording system having a magnetic recording data writing or reading device to provide a photographic system excellent in writing or reading magnetic recording data. I was able to.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location G03C 1/76 502 1/81 1/85 3/00 530 555 A

Claims (11)

[Claims] 1. A silver halide photographic light-sensitive material having at least one layer of a silver halide emulsion layer having a hydrophilic colloid as a binder on one surface of a support, said support being coated with said silver halide emulsion layer. On the opposite side to the back side, at least one layer of non-photosensitive hydrophilic layer having a thickness of 0.5 to 10 μm and at least one layer of 0.4 to 10 μm on the outer layer.
m, a non-photosensitive hydrophobic layer, and at least one transparent magnetic recording layer having a coercive force of 400 to 3000 Oe as its outer layer, and the thickness of the support is 50 μm to 300 μm.
μm, its glass transition point is 50 ° C. to 200 ° C., and 40 ° C. before applying the undercoat layer or after applying the undercoat layer and before applying the emulsion.
A silver halide photographic light-sensitive material, which is a polyester support heat-treated at a temperature not higher than the glass transition temperature for 0.1 to 1500 hours. 2. A transparent magnetic recording layer having a coercive force of 400 to 3000 Oe, which is coated on at least one layer on the back side of the support, has a surface area of particles of ^{2 to} 100 m ² / g and an average particle size of 0.01 to 0. The magnetic material having a thickness of 0.8 μm is 10
The silver halide photographic light-sensitive material according to claim 1, which contains 300 mg / m ² . 3. The silver halide photographic light-sensitive material according to claim 1 or 2, wherein the non-photosensitive hydrophilic layer is composed of gelatin or a gelatin derivative. 4. The amount of gelatin or gelatin derivative in the non-photosensitive hydrophilic layer on the back side is 0.03 to 0.7 in weight ratio with respect to the amount of gelatin in the silver halide emulsion layer. 4. The silver halide photographic light-sensitive material according to claim 3. 5. The silver halide according to claim 1, wherein the binder of the non-photosensitive hydrophobic layer on the back side has a glass transition temperature of 80 ° C. or higher. Photographic material. 6. The non-photosensitive hydrophobic layer is a layer mainly composed of one kind of hydrophobic polymer selected from polymerizable and condensable synthetic polymers and derivatives of natural polymers including cellulose, The silver halide photographic light-sensitive material according to any one of claims 1 to 5, wherein the total film thickness is 0.5 µm to 10 µm. 7. The silver halide photographic light-sensitive material according to claim 6, wherein the cellulose derivative is cellulose diacetate, cellulose triacetate, cellulose acetate dibutyrate, or cellulose acetate dipropionate. 8. A strong magnetic material selected from ferromagnetic iron oxide, Co-containing ferromagnetic iron oxide, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, barium ferrite, magnetite, and Co-containing magnetite. The silver halide photographic light-sensitive material according to claim 1 or 2, which is a magnetic fine powder. 9. The method according to claim 1, wherein at least one layer contains an antistatic agent composed of a conductive metal oxide or / and an ionic polymer, and / or a slip agent and / or a matting agent. 9. The silver halide photographic light-sensitive material according to any one of item 8. 10. A silver halide photographic light-sensitive material is rotated in a photographic light-sensitive material feed direction by rotating a spool rotatably provided in a cartridge body so that the tip of the photographic light-sensitive material wound around the spool is rotated by the cartridge. 10. The apparatus according to claim 1, wherein the photographic light-sensitive material of the main body is used by being sent to the outside through an outlet.
The silver halide photographic light-sensitive material according to any one of 1. 11. The silver halide photographic light-sensitive material is housed in a photographic camera having a magnetic recording system having a magnetic recording data writing or reading device to record the data. The silver halide photographic light-sensitive material according to any one of claims 1 to 10, characterized in that.