JPH07281351A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce curling tendency and to enhance mechanical strength, scratching resistance, and antitackiness by incorporating a sliding agent having the penetration of a loaded needle of a specified value or less in the outermost layer of the backing layers of a polyester support and heat treating the outermost backing layer after applying it in specified conditions. CONSTITUTION:The photosensitive material has a photosensitive silver halide emulsion layer on one side of the polyester support and it contains the sliding agent having the penetration of a landed needle of <=5, preferably, <=3, especially, <=1 in the outermost layer of the backing layers of the support and this layer is heat treated in a temperature range from 40 deg.C to a temperature below a glass transition point Tg after applying this layer for 0.01-2000hr. At least one magnetic recording layer is formed. The polyester support is composed essentially of naphthalenedicarboxylic acid units and ethylene glycol units.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention relates to a silver halide photographic light-sensitive material having a small curling curl, excellent mechanical strength, scratch resistance and adhesion resistance, and excellent scratch resistance and high magnetic recording reliability. The present invention relates to a silver halide photographic light-sensitive material having a magnetic recording layer.

[0002]

2. Description of the Related Art In recent years, the applications of silver halide photographic light-sensitive materials (hereinafter also simply referred to as light-sensitive materials) have been diversified, and the speed of film unwinding at the time of shooting, the increase in shooting magnification, and the miniaturization of shooting devices. It has become extremely popular. Therefore, the support of the photosensitive material is required to have properties such as having excellent mechanical strength even when it is formed into a thin film and having excellent dimensional stability.

Biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) has excellent transparency, mechanical strength and dimensional stability. For this reason, the micro film that requires thinning of the film, the photosensitive material for printing that requires strict dimensional stability, and the X-ray film that requires transparency and elasticity are conventionally used. A PET film is used instead of an acetyl cellulose film (hereinafter referred to as TAC film).
However, in a light-sensitive material used as a roll film such as a general color negative film, TAC
If a PET film that does not have the curl recovery after development as seen in the film is used, the curl after development is too strong, resulting in poor handleability. For example, after development, images are printed on photographic paper. There is a problem in that scratches, defocusing, and jamming during transportation occur in the process of baking.

As a method for improving the roll-back recovery property of such a PET film, JP-A 1-244446 and JP-A-4-22 are known.
No. 0329 discloses a PET film in which a water-absorbing component is copolymerized, and further disclosed in JP-A-4-93937, JP-A-5-69524, and JP-A-5-69524.
5-235036 and JP-A-5-313302 propose a laminated film of a PET film obtained by copolymerizing these water absorbing components and a polyester film having a high glass transition temperature (hereinafter referred to as Tg).

However, P obtained by copolymerizing a water-absorbing component
The ET film needs to be copolymerized with a large amount of a water-absorbing component in order to obtain sufficient curl recovery after development.
Compared with the ET film, Tg is considerably lower and the crystallinity is also lowered. Therefore, there is a problem that only a film having very poor heat resistance and mechanical strength can be obtained. In addition, a laminated film of a PET film copolymerized with a water-absorbing component and a polyester film having a high Tg,
The aim is to solve these problems, but the polyester film with a high Tg does not have the curl recovery property.
The curl recovery property as a laminated film is insufficient, which is a practical problem.

[0006] As a method of making the polymer film hard to curl, in JP-A-51-16358, a thermoplastic resin film is heat treated at Tg-5 ° C to Tg-30 ° C for 0.1 to 1500 hours. A method has been proposed. Further, JP-A-6-35118 proposes a method in which a polyester film having a Tg of 90 ° C. to 200 ° C. is undercoated and then heat treated at 50 ° C. to Tg for 0.1 to 1500 hours.

Thermoplastic resin film Tg -5 ℃ ~ Tg
The method of heat treatment at −30 ° C. for 0.1 to 1500 hours is PET.
Film and polyethylene naphthalate film (P
It has an effect of reducing curling curl of crystalline or semi-crystalline thermoplastic resin including EN film). Although it is not a method for directly improving the curl curl of the film, it is possible to reduce curl curl after development by making the curl itself difficult to stick.

However, if it is heated to Tg or higher, the effect of making it difficult to form the curl as described above disappears. In the coating / drying process of the undercoat layer on the side having the photographic photosensitive layer (hereinafter also referred to as emulsion side) and the layer having the photographic photosensitive layer on the side opposite to the support (hereinafter also referred to as backing layer), The temperature may be higher than the Tg of the thermoplastic film, and if the above-mentioned heat treatment is performed after applying the photographic photosensitive layer, the photographic performance is adversely affected. For this reason, the above-mentioned heat treatment is generally performed after coating the undercoat layer and the backing layer on the emulsion side and before winding the photographic photosensitive layer. At this time, problems are sticking and transfer of the slipping agent in the heat treatment process.

It is known that the outermost layer of the backing layer of a silver halide photographic light-sensitive material contains a slipping agent for the purpose of improving the occurrence of scratches in cameras and laboratory equipment. However, when the heat treatment is performed at a high temperature as described above, the undercoat layer on the emulsion side and the backing layer stick to each other,
Further, the sliding agent is transferred, which causes problems such as repellency during coating of the photographic photosensitive layer and deterioration of scratch resistance.

On the other hand, there has been proposed a method of recording various information on a photosensitive material by providing a magnetic recording layer on the photosensitive material.

For example, a stripe-shaped magnetic recording layer in which ferromagnetic fine particles are dispersed is provided on the emulsion surface or the back surface next to the image area to record information such as voice and shooting conditions. Kasho 50-62627, 49-4503, U.S. Pat.Nos. 3,243,376, 3,220,843, etc., and
On the back surface of the light-sensitive material, it is possible to provide a transparent magnetic recording layer having the required transparency by selecting the amount of magnetizable particles, size, etc., U.S. Pat.Nos. 3,782,947, 4,279,945, 4,302,52.
It is described in No. 3 etc. U.S. Pat.No. 4,947,196
No. WO 90/04254 describes a photographing camera having a magnetic head together with a roll-shaped film having a magnetic recording layer containing a magnetic material on the back surface of a photographic film.

However, since the magnetic head and the magnetic recording layer are in contact with each other when a magnetic signal is input / reproduced, scratches are more likely to occur than in ordinary silver halide photographic light-sensitive materials. When scratches occur, in the worst case, an error may occur at the time of inputting / outputting a magnetic signal, or a scratch failure may occur on a finished print.

As a method for improving the occurrence of such scratches, there is known a method in which a layer contacting the magnetic head (usually the outermost layer of the backing layer) contains a slip agent.

Therefore, when the above-mentioned heat treatment is applied to the silver halide photographic light-sensitive material having the magnetic recording layer, a larger problem may occur.

[0015]

Therefore, in view of the above problems, a first object of the present invention is to provide a silver halide photographic light-sensitive material which has a small curling curl and is excellent in mechanical strength, scratch resistance and adhesion resistance. To provide the material.

A second object of the present invention is to input a magnetic signal.
An object of the present invention is to provide a silver halide photographic light-sensitive material having a magnetic recording layer with high reliability of magnetic recording, in which the occurrence of errors due to scratches during reproduction is reduced.

[0017]

The above object of the present invention has been achieved by the following constitution.

1. In a silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on one side of a polyester support, the outermost layer of the backing layer of the polyester support contains a slip agent having a penetration of 5 or less, and 1. A silver halide photographic light-sensitive material characterized by being heat-treated for 0.01 to 2000 hours at a temperature of 40 ° C. or higher and Tg or lower after coating the outermost layer of the backing layer of the support. 2. The silver halide photographic light-sensitive material as described in 1 above, which has at least one magnetic recording layer. The silver halide photographic light-sensitive material described in 1 or 2 above, wherein the polyester support is composed of a polyester containing naphthalene dicarboxylic acid and ethylene glycol as main components. The present invention will be described in detail below.

First, the slip agent in the present invention will be described.

The slip agent of the present invention may have a penetration of 5 or less, and known slip agents can be used. The penetration of the slip agent of the present invention is 5 or less, more preferably 3
It is below, and more preferably 1 or below. The penetration degree here means a value measured by the method described in JIS K-2530-1976, and the test conditions are a temperature of 25 ° C., a load of 100 g and a penetration time of 5 seconds. The penetrating degree represents the length of vertical penetration of the needle into the sample, and the unit is 0.1 mm.

Examples of the lubricant of the present invention include organopolysiloxane, higher fatty acid, higher fatty acid ester,
Metal salts of higher fatty acids, higher alcohols and their derivatives,
Hydrocarbon-based polymers, hardened paraffin, etc. can be mentioned. Of these, higher fatty acid esters and hydrocarbon polymers are preferable. Examples of slip agents that are particularly preferably used include esterified montan wax, carnauba wax, candelilla wax, low molecular weight polyethylene wax (molecular weight 2000) and low molecular weight polypropylene washes (molecular weight 4000). Is not limited to these.

The melting point of the slip agent of the present invention is not particularly limited, but is preferably 40 ° C to 200 ° C, more preferably 60 ° C to 150 ° C.
C., more preferably 80 to 120.degree.

The amount of the slip agent of the present invention used is not particularly limited, but is preferably 0.0005 to ² g / m ² , and more preferably 0.005 to ² g / m ² .
It is 001 to 1 g / m ² , more preferably 0.002 to 0.5 g / m ² .

By using the above slipping agent, it is possible to obtain a silver halide photographic light-sensitive material which is excellent in scratch resistance and does not stick to or transfer the sliding agent even when heat-treated in the state of being wound into a roll film. I can. Further, the method of incorporating the above-mentioned slip agent in the outermost layer is not particularly limited, but for example, a method of applying a liquid in which the slip agent is dissolved or dispersed in a suitable solvent, or a slip agent is contained in a binder capable of forming a film. There is a method of applying.

The solvent for dissolving or dispersing the slip agent is not particularly limited, and examples thereof include water, alcohols, ketones,
Examples thereof include hydrocarbon type and aromatic hydrocarbon type.

As the binder having a film-forming ability to contain a slip agent, known thermoplastic resins, radiation-curable resins, thermosetting resins, reactive resins and mixtures thereof,
A hydrophilic binder such as gelatin can be used.

The binder in the layer containing the slip agent preferably has a weight average molecular weight of 10,000 to 1,000,000, more preferably 20,000 to 500,000. Also, Tg is 4
The temperature is preferably 0 ° C to 150 ° C, more preferably 60 ° C to 120 ° C.

Examples of the thermoplastic resin include cellulose derivatives such as cellulose triacetate, cellulose diacetate and nitrocellulose, vinyl copolymers such as vinyl chloride / vinyl acetate copolymers, vinyl chloride and vinyl chloride / vinylidene chloride copolymers. A coalesce, an acrylic resin, a polyester polyurethane resin, a polyether polyurethane resin, a polycarbonate polyurethane resin or the like can be preferably used.

The binder may have a polar group in its molecule. Epoxy group as polar group, -CO
_{OM, -OH, -NR 2, -NR} 3 X, -SO 3 M, -OSO 3 M, -PO
₃ M ₂ , -OPO ₃ M (M is a hydrogen atom, an alkali metal atom, or ammonium, X is an acid that forms an amine salt, R is
Each represents a hydrogen atom or an alkyl group).

The hydrophilic binder usable in the present invention is, for example, Research Disclosure No. 17643, 26.
Page, and the same No. 18716, water-soluble polymer described in page 651, cellulose ether, latex polymer,
Mention may be made of water-soluble polyesters, gelatin or gelatin derivatives.

A hardener may be added to the binder,
The hardener which can be used is not particularly limited, but for example, aldehyde compounds, ketone compounds, compounds having a reactive halogen, compounds having a reactive olefin,
Examples thereof include N-hydroxymethylphthalimide, N-methylol compounds, isocyanates, aziridine compounds, acid derivatives, epoxy compounds and halogen carboxaldehydes. Inorganic hardeners can also be used.

The hardener is usually added in an amount of 0.01 to 0.01 with respect to the binder.
30% by weight is used, preferably 0.05 to 20% by weight.

The amount of the slip agent contained in the binder capable of forming a film is not particularly limited, but is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight of the binder.
%, More preferably 1 to 20% by weight.

Further, within a range that does not impair the effects of the present invention,
The outermost layer of the backing layer may contain various additives such as a matting agent.

The outermost layer of the backing layer is provided by air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat. Etc. can be used.

In order to firmly adhere the outermost layer of the backing layer to the support, the support may be provided with an undercoat layer,
In addition, surface activation treatment such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment, ozone oxidation treatment etc. You may. Furthermore, an undercoat layer may be provided after the surface activation treatment.

A conductive layer may be provided in order to improve the antistatic property.

To impart conductivity, it can be formed by containing a conductive substance. These conductive substances are not particularly limited, and examples thereof include conductive polymers and inorganic metal oxides.

The conductive polymer is not particularly limited and may be any of anionic, cationic, amphoteric and nonionic, and among them, anionic and cationic are preferable. More preferred are sulfonic acid-based or carboxylic acid-based polymers when anionic, and tertiary amine-based or quaternary ammonium-based polymers or latexes when cationic.

These conductive polymers are described, for example, in Japanese Patent Publication
52-25251, JP-A-51-29923 and JP-B-60-48024, anionic polymers or latexes, JP-B-57-181
76, 57-56059, 58-56856, U.S. Pat.No. 4,118,
Examples thereof include cationic polymers or latexes described in No. 231 and the like.

The inorganic metal oxide is not particularly limited, but for example, crystalline metal oxide particles as disclosed in JP-A-56-143341, as disclosed in JP-B-35-6616. Amorphous stannic oxide sol, amorphous vanadium pentoxide described in JP-A-55-5982, JP-B-57-129
An alumina sol having an electrolyte as disclosed in No. 79 is mentioned.

The conductive material is preferably applied with a binder. The binder is not particularly limited, but for example, the binder used for the outermost layer of the backing layer described above can be used, and polyester resin or latex can also be used.

Next, the magnetic recording layer will be described.

The magnetic fine powder used in the magnetic recording layer of the present invention includes metal magnetic powder, iron oxide magnetic powder and Co.
Doped iron oxide magnetic substance powder, chromium dioxide magnetic substance powder, barium ferrite magnetic substance powder and the like can be used.

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

The shape and size of the magnetic powder are not particularly limited and can be widely used. The shape may be any shape such as a needle shape, a rice grain shape, a spherical shape, a cubic shape, or a plate shape, but a needle shape or a plate shape is preferable in terms of electromagnetic conversion characteristics. The crystallite size and specific surface area are not particularly limited. The magnetic powder may be surface-treated. For example, a material surface-treated with a substance containing an element such as titanium, silicon, or aluminum may be used, or a carboxylic acid,
It may be treated with an organic compound such as an adsorptive compound having a nitrogen-containing heterocyclic ring such as sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester and benzotriazole.

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

Examples of the iron oxide magnetic powder include γ-iron oxide. The ratio of divalent iron / trivalent iron in iron oxide can be used without particular limitation.

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

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

Therefore, it is preferable to make the particle size of the magnetic powder as small as possible within the range where the required magnetic characteristics are obtained. Further, if the coating amount of the magnetic particles is reduced to a certain extent or more, the required magnetic characteristics cannot be obtained, so it is preferable to reduce the coating amount within the range where the required magnetic characteristics are obtained. Practically, the coating amount of the magnetic powder is 0.001 to 3 g / m ² , and more preferably 0.01 to 1 g / m ² .

The binder used for the magnetic recording layer is not particularly limited, but for example, the binder which mainly constitutes the outermost layer of the backing layer can be preferably used.

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

In the case of forming an optically transparent magnetic recording layer, the binder is 1 to 20 with respect to 1 part by weight of the magnetic powder.
Parts by weight. Further, the solvent is used in such an amount that the coating can be easily performed.

Various additives such as an antistatic agent and a matting agent are added to the coating liquid for forming the magnetic recording layer in order to give the magnetic recording layer functions such as antistatic property, antiadhesive property, and improvement of friction and wear characteristics. It can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and for preventing clogging of the magnetic head. It is possible to add an abrasive.

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

The polyester constituting the polyester film of the present invention is not particularly limited, but is preferably a polyester having a dicarboxylic acid component and a diol component as main constituents and having film-forming properties.

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl ethane. Examples thereof include dicarboxylic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketone dicarboxylic acid and phenylindanedicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-
Hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol, etc. . Among the polyesters containing these as main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid as a dicarboxylic acid component, ethylene glycol and a diol component as ethylene glycol, from the viewpoints of transparency, mechanical strength, dimensional stability and the like. / Or 1,4-
Polyesters whose main constituent is cyclohexanedimethanol are preferred. Among them, polyethylene terephthalate, polyethylene-2,6-naphthalate, terephthalic acid and polyester composed of 2,6-naphthalenedicarboxylic acid and ethylene glycol, and 2 of these polyesters
Polyesters whose main constituent is a mixture of one or more kinds are preferred. When the ethylene terephthalate unit and / or the ethylene 2,6-naphthalate unit is contained in an amount of 70% by weight or more based on the polyester, a film excellent in transparency, mechanical strength, dimensional stability and the like can be obtained.

The polyester constituting the polyester film of the present invention may be copolymerized with other copolymerization components, or may be mixed with other polyesters, as long as the effects of the present invention are not impaired. Is also good. Examples of these include the above-mentioned dicarboxylic acid component, diol component, and polyester.

The polyester constituting the polyester film of the present invention may be imparted with appropriate water absorption by copolymerizing at least one compound having at least one hydrophilic group. Examples of the hydrophilic group of the compound having at least one hydrophilic group include sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, polyoxyalkylene group, sulfamoyl group, carbamoyl group, acylamino group, sulfonamide group, disulfone. Examples thereof include an amide group, a ureido group, a urethane group, an alkylsulfonyl group, and an alkoxysulfonyl group. Among them, a sulfone group, a sulfin group, a phosphone group, a carboxylic acid or a salt thereof, a polyoxyalkylene group, a disulfonamide group. Is preferred.

As the compound having a hydrophilic group, an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof, a dicarboxylic acid having a polyoxyalkylene group or an ester-forming derivative thereof, a diol having a polyoxyalkylene group, etc. Is mentioned. Above all, in terms of polymerization reactivity of polyester and transparency of the film,
5-sodium sulfoisophthalic acid, 2-sodium sulphoterephthalic acid, 4-sodium sulfoinphthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and these other metals, such as potassium, lithium, etc. Or a compound substituted with an ammonium salt, a phosphonium salt or the like, or an ester-forming derivative thereof, polyethylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymer and a carboxyl group by oxidizing the hydroxy groups at both ends thereof. And the like are preferred.

These compounds having a hydrophilic group may be used alone or in combination of two or more. In particular, it is preferable that both the aromatic dicarboxylic acid component having a sulfonate group and the compound component having a polyoxyalkylene group are copolymerized with the polyester because the water absorption of the film is further improved.

The copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group is preferably 0.5 to 10 mol% based on the difunctional dicarboxylic acid constituting the polyester.

The number average molecular weight of the compound component having a polyoxyalkylene group is preferably 300 to 20000, more preferably 600
Those in the range of up to 10,000, particularly 1000 to 5000 are preferred. The copolymerization ratio is preferably 0.5 to 15% by weight based on the polyester of the reaction product.

When the copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group, the number average molecular weight of the compound component having a polyoxyalkylene group, and the copolymerization ratio are within these ranges, the transparency and mechanical strength of the film are impaired. It is possible to improve the water absorption. For the purpose of improving the heat resistance of the film, a bisphenol compound,
A compound having a naphthalene ring or a cyclohexane ring can be copolymerized. The copolymerization ratio of these is preferably 3 to 20 mol% based on the difunctional dicarboxylic acid constituting the polyester.

The polyester used in the present invention preferably contains a dye for the purpose of preventing the light piping phenomenon. The dye to be blended for such a purpose is not particularly limited in its type, but in the production of the film, it is necessary that it has excellent heat resistance, and anthraquinone-based or perinone-based dyes may be used. Can be mentioned. Further, as the color tone, gray dyeing is preferable as seen in general light-sensitive materials.

The polyester film of the present invention may have a multilayer structure composed of different polyesters. For example,
When the above-mentioned polyester layer is the A layer and the above-mentioned other polyester layer is the B layer or the C layer, a two-layer structure consisting of the A layer and the B layer may be used.
A three-layer structure such as B layer / A layer, A layer / B layer / C layer, B layer / A layer / B layer or B layer / A layer / C layer may be used. Further, a structure having four or more layers is of course possible, but it is not preferable in practice because the manufacturing equipment becomes complicated. The thickness of layer A is
The thickness is preferably 30% or more, and more preferably 40 to 70% of the total thickness of the polyester film. In this case, the thickness of the A layer is the thickness of the layer when the A layer has only one layer, and is the sum of the thicknesses when the A layer has two or more layers. The thickness of the B layer or C layer is preferably 5 to 60 μm, more preferably 10 to 50 μm. When the thickness of each layer is within the above range, transparency, mechanical strength, and dimensional stability are excellent, and further, water absorbability is provided, and thus a polyester film having excellent curl recovery property can be obtained.

The polyester constituting the layer B or the layer C is formed by laminating polyethylene terephthalate, which is excellent in transparency, mechanical strength and dimensional stability, or another homopolyester, or another copolymerized polyester layer, The transparency, mechanical strength, dimensional stability, etc. of the entire film can be improved.

The method of synthesizing the polyester as the raw material of the polyester film of the present invention is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first a dialkyl ester is used as a dicarboxylic acid component, and an ester exchange reaction is performed between this and the diol component, and this is heated under reduced pressure. A transesterification method in which the excess diol component is removed to perform polymerization can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. In addition, in each process during synthesis, coloring agent, antioxidant,
A crystal nucleating agent, a slip agent, a stabilizer, an antiblocking agent, an ultraviolet absorber, a viscosity adjusting agent, a defoaming agent, a clarifying agent, an antistatic agent, a pH adjusting agent, a dye, a pigment and the like may be added.

The thickness of the polyester film of the present invention is not particularly limited. It may be set so as to have a required strength according to the purpose of use. Particularly when the polyester film is used for a silver halide photographic light-sensitive material for color negative, the thickness is preferably 20 to 125 μm, particularly preferably 40 to 90 μm. When it is used in a silver halide photographic light-sensitive material for medical use or printing, it is preferably 50 to 200 μm, and particularly preferably 60 to 150 μm. If it is thinner than this range, the required strength may not be obtained in some cases, and if it is thicker, it is no longer superior to conventional supports for silver halide photographic light-sensitive materials.

Further, the polyester film of the present invention is
The haze is preferably 3% or less. More preferably, it is 1% or less. When the haze is more than 3%, when the film is used as a support for a silver halide photographic light-sensitive material, an image printed on photographic printing paper is blurred and unclear. The haze is measured according to ASTM-D1003-52.

The Tg of the polyester film of the present invention is
The temperature is preferably 60 ° C or higher, more preferably 70 ° C or higher and 150 ° C or lower. Tg is determined by measuring with a differential scanning calorimeter. When the Tg is in this range, the film is not deformed in the drying process of the development processor, and a photosensitive material having a small curl after curling can be obtained.

The polyester film of the present invention can be reduced in curl due to heat treatment at a temperature of 40 ° C. or higher and Tg or lower for 0.1 to 2000 hours.

This heat treatment is preferably carried out after coating the undercoat layer and backing layer on the emulsion side and before coating the photographic photosensitive layer.

The condition of this heat treatment is not particularly limited, but it is preferable to perform the heat treatment in a state of being wound on a roll in order to improve production efficiency.

Typical examples of the silver halide photographic light-sensitive material of the present invention include a black-and-white light-sensitive material, a color negative light-sensitive material, and a color reversal light-sensitive material.

The silver halide emulsion used in the present invention is, for example, Research Disclosure (RD) No. 17643, 22.
Pp. 23 (December 1978) "I. Emulsion preparat
ionand types) ”and the same (RD) No.18716, 648
P., Graphide, Physics and Chemistry of Photography, published by Paul Montel (P. Glafkides, Chemic et Phisique Photographi
Quque, Paul Motel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photogra
Phic Emulsion Chemistry Focal Press 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., V.L. Zelikman et al., Making and Coating Phot
It can be prepared using the method described in ographic Emulsion, Focal Press, 1964) and the like.

Emulsions are disclosed in US Pat. Nos. 3,574,628 and 3,665,394.
Monodisperse emulsions described in U.S. Pat.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such processes are RD No.17643, No.18716 and N.
o.308119 (hereinafter RD17643, RD18716 and RD3081 respectively
(Abbreviated as 19)). The description is shown below.

[Item] [RD308119] [RD17643] [RD18716] Chemical sensitizer, page 996, section III-A, page 23, page 648, spectral sensitizer, page 996, IV-A, B, C, D, I, J, section 23 -24 pages 648-9 Supersensitizer page 996 IV-AE, J section 23-24 pages 648-9 pages Antifoggants page 998 VI pages 24-25 pages 649 stabilizers 998 pages VI pages 24-25 pages 649 Page When the silver halide photographic light-sensitive material of the present invention is a color photographic light-sensitive material, photographic additives that can be used are described in the above RD. The following shows the relevant locations.

[Item] [RD308119] [RD17643] [RD18716] Color turbidity inhibitor page 1002 VII-I section 25 page 650 Dye image stabilizer page 1001 VII-J section 25 whitening agent 998 page V 24 page UV light Absorber page 1003 VIII-C, XIII-C page 25 to 26 Light absorber page 1003 VIII page 25 to 26 Light scattering agent page 1003 VIII Filter dye page 1003 VIII page 25 to 26 binder 1003 page IX 26 page 651 static Inhibitor 1006 page XIII 27 page 650 Hardener 1004 page X 26 page 651 Plasticizer 1006 page XII 27 page 650 Lubricant 1006 page XII 27 page 650 Activator / coating aid 1005 page XI 26-27 Page 650 matting agent page 1007 page XVI developer (containing in light-sensitive material) page 1011 XX-B Further, when the silver halide photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used. Specific examples thereof are described in RD17643 and RD308119 below. The relevant description is shown below.

[Item] [RD308119] [RD17643] Yellow coupler page 1001 VII-D section 25 page VII-C to G magenta coupler page 1001 VII-D section 25 page VII-C to G cyan coupler 1001 VII- Item D Page 25 Items VII-C to G Colored Coupler Page 1002 Item VII-G Item 25 Page VII-G Item DIR Coupler Page 1001 Item VII-F Item 25 Page VII-F BAR Coupler Page 1002 Item VII-F Other useful residue Group-releasing coupler page 1001 VII-F Alkali-soluble coupler page 1001 VII-E Further, these additives can be added to the photographic photosensitive layer by the dispersion method described in RD308119 page 1007, item XIV.

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

In the case of forming a color photographic light-sensitive material, the above
RD308119 Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in Section VII-K can be adopted.

In order to firmly adhere these photographic constituent layers (eg, photosensitive silver halide emulsion layer, intermediate layer, filter layer, magnetic recording layer, conductive layer) to the support, an undercoat layer is provided on the support. It is not necessary to provide the support, and the support is subjected to chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatment such as laser treatment, concentrated acid treatment, or ozone oxidation treatment may be performed. Further, an undercoat layer may be provided after the surface activation treatment, and a photographic emulsion layer may be coated thereon.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T. H. James, Theory of the Photografic Process Forth Editi
on) pages 291 to 334 and the Journal of the American Chemical Society (Journal of the Ameri
can Chemical Society) Vol. 73, page 3,100 (1951), known per se can be used. Also. The color photographic light-sensitive material is the above-mentioned RD17643.
Development can be carried out by a usual method described on pages 28 to 29, RD18716 page 615 and RD308119 XIX.

[0087]

The present invention will be described in detail below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Support> Polyester A to polyester D were prepared as follows.

(Polyester A) 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were added as calcium ester hydrate 0.1 as a transesterification catalyst.
Part by weight was added, and transesterification was performed according to a conventional method. Antimony trioxide (0.05 parts by weight) and phosphoric acid trimethyl ester (0.03 parts by weight) were added to the obtained product.
Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 290 ° C. and 0.5 mmHg to obtain polyethylene 2,6-naphthalate having an intrinsic viscosity of 0.60.

(Polyester B) 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were added as calcium ester hydrate 0.1 as an ester exchange catalyst.
Part by weight was added, and transesterification was performed according to a conventional method. 5-sodium sulfodi (β
-Hydroxyethyl) isophthalic acid in ethylene glycol (concentration 35% by weight) 5 parts by weight, antimony trioxide 0.
05 parts by weight, 0.03 parts by weight of phosphoric acid trimethyl ester, 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) and 0.04 parts by weight of sodium acetate were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 290 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.55.

(Polyester C) Dimethyl terephthalate
To 100 parts by weight of ethylene glycol and 65 parts by weight of ethylene glycol, 0.05 part by weight of magnesium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. Antimony trioxide (0.05 parts by weight) and phosphoric acid trimethyl ester (0.03 parts by weight) were added to the obtained product. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.65.

(Polyester D) Polyester A and polyester C were blended in a tumbler type mixer in a weight ratio of 80/20.

A film was obtained as follows using each of the polyesters obtained as described above.

(Film 1) Using polyester A,
After vacuum-drying at 150 ° C. for 8 hours, it was melt-extruded in layers from a T-die at 300 ° C., adhered onto a cooling drum at 50 ° C. while electrostatically applied, and cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The uniaxially stretched film thus obtained was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and then in a second stretching zone at 155 ° C. and a total transverse stretching ratio of 3.3 times. Was stretched. Then, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at first heat-setting zone 200 ° C. for 5 seconds, and second heat-setting zone 240 ° C. for 15 seconds. Next, a biaxially stretched film having a thickness of 80 μm was obtained, which was gradually cooled to room temperature over 30 seconds while being relaxed in the transverse direction by 5%.

(Film 2) Using polyester D,
After vacuum-drying at 150 ° C. for 8 hours, it was melt-extruded in layers from a T-die at 300 ° C., adhered on a cooling drum at 40 ° C. while electrostatically applied, and cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 130 ° C. using a roll type longitudinal stretching machine.

The uniaxially stretched film thus obtained was stretched in a first stretching zone at 140 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and then at a second stretching zone at 150 ° C. and a total transverse stretching ratio of 3.3 times. Was stretched. Then, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at first heat-setting zone 200 ° C. for 5 seconds, and second heat-setting zone 240 ° C. for 15 seconds. Next, a biaxially stretched film having a thickness of 80 μm was obtained, which was gradually cooled to room temperature over 30 seconds while being relaxed in the transverse direction by 5%.

(Film 3) Polyester A and polyester B were vacuum dried at 150 ° C. for 8 hours, respectively, and then
Using two extruders, melt extruding at 300 ° C, joining in layers in a T-die, adhering to a 40 ° C cooling drum while applying static electricity, and cooling and solidifying to obtain a two-layer unstretched sheet. It was At this time, make sure that the thickness ratio of each layer is 1: 1.
The amount of each extrusion was adjusted. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched at 50% of the total transverse stretching ratio in the first stretching zone 145 ° C. using a tenter type transverse stretching machine, and further in the second stretching zone 155 ° C. and the total transverse stretching ratio 3.3 times. Was stretched. Then, it was heat-treated at 110 ° C. for 2 seconds, further heat-set at first heat-setting zone 200 ° C. for 5 seconds, and second heat-setting zone at 240 ° C. for 15 seconds. Next, a biaxially stretched film having a thickness of 80 μm was obtained, which was gradually cooled to room temperature over 30 seconds while being relaxed in the transverse direction by 5%.

(Film 4) Using polyester C,
90μ thickness after biaxial stretching and heat setting
A PET film of m was obtained.

<Preparation of Photosensitive Material> The prepared support was subjected to an undercoating process as described below to form a backing layer and an emulsion layer.

Both sides of the support were subjected to a corona discharge treatment of 8 W / (m ² · min), and one side of the support was coated with the undercoat coating solution A.
-1 is applied to a dry film thickness of 0.8 μm to form an undercoat layer A-
1 is formed on the undercoat layer A-1 and 8 W / (m ² · mi
n) is subjected to corona discharge, and the following subbing coating solution A-2 is applied onto the subbing layer A-1 to give a dry film thickness of 0.1 μm.
Formed 2.

On the other surface of the support, the following coating liquid B-1 was applied.
To a dry film thickness of 0.5 μm to form a conductive layer B-
1 was formed.

<Undercoating Liquid A-1> Copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content). 30%) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating liquid A-2> Gelatin 10g Compound (UL-1) 0.2g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size 3 μm) 0.1 g Finish with water 1000 ml <Coating liquid B-1> LX-1 aqueous dispersion (solid content 30% by weight) 270g Compound (UL-1) 0.6g Dispersion A 560g Finish with water 1000ml <LX-1> 5-Sulfoisophthalic acid 5mol% Isophthalic acid 15mol% Terephthalic acid 30mol% Ethylene glycol 25mol% Diethyleneglycol Le 25 mole% of copolymerized latex (average particle size 60 nm) pH the mixture of powder 400g water 600g of <tin oxide dispersion liquid> Ishihara Sangyo Co., Ltd. antimony-doped tin oxide SN-100P
After adjusting to 7.0, disperse with a stirrer and sand mill,
Dispersion A was prepared.

Further, 8 W / on the conductive layer B-1.
(M ² · min) corona discharge was applied to the following coating layer OC-1
Alternatively, OC-2 was applied so as to have a dry film thickness of 1 μm.

<OC-1> Nitrocellulose 70 parts by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight <OC-2> Nitrocellulose 63 parts by weight Sliding agent (see wax type below) 7 parts by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight The coating layer OC-1 was applied to the surface of OC-1 and subjected to a corona discharge of 8 W / (m ² · min) to obtain the following sliding layer W.
X-1 was applied at 10 ml / m ² .

<WX-1> Lubricating agent (see wax type described below) 2 g Toluene 700 ml Methyl ethyl ketone 300 ml

[0108]

[Chemical 1]

[0109] With respect to the obtained sample, the adhesion resistance and the scratch resistance were measured by the following methods.

The scratch resistance was evaluated for the sample which was heat-treated at 80 ° C. for 24 hours and the sample which was not heat-treated. This heat treatment was performed by winding the backing layer inward on a winding core having a diameter of 30 cm.

The results are shown in Tables 1 and 2.

<Adhesion resistance> A sample cut into 35 mm × 1 m is
The humidity is controlled for 24 hours under the conditions of 23 ° C. and 55% RH, and a 3-inch core is wound with a load of 1 kg. The sample is sealed in a can and heat-treated at 80 ° C. for 24 hours. The heat-treated sample is left to cool to 23 ° C. in a can while being sealed, then taken out of the can and the sample wound on the core is unwound at 23 ° C. and 55% RH. 40 cm to 60 cm from the outside of the sample
In the range, the ratio of the adhered area to the measurement range is measured, and the following four levels are evaluated.

⊚: 0% ∘: 0 to 20% Δ: 20 to 40% x: 40% or more Incidentally, if it is Δ or more, there is no problem in practical use.

<Scratch resistance> A sample was tested at 23 ° C. and 55% RH.
Humidified for 24 hours, and made into HEIDON-18 type manufactured by Shinto Chemical Co., Ltd.
As a scratching needle, attach a diamond needle with a tip of 0.0025 mm, and continuously change the load from 0 g to 50 g,
The sample was scratched. Scratch speed is 10mm / sec,
The scratch distance is 100 mm. The scratched sample is observed with transmitted light, and the load at which the scratch becomes visible is measured. The unit is g. The larger the value, the better the abrasion resistance.

[0115]

[Table 1]

[0116]

[Table 2]

From the above results, it can be seen that the use of the slip agent of the present invention makes the present invention excellent in both adhesion resistance and abrasion resistance as compared with the comparison.

Example 2 <Preparation of support> Film 1 having three thicknesses of 90, 80 and 70 μm was prepared in the same manner as in Example 1 except that the extrusion amount was appropriately controlled to change the film thickness. To obtain film 4.

A commercially available cellulose triacetate film (film thickness 100, 80 μm) was prepared and used as film 5.

<Preparation of Photosensitive Material> In the same manner as in Example 1, each support was provided with an undercoat layer A-1, A-2 and a conductive layer B-1, and a coating layer OC-1 or OC-2. Was set up. Further, a sliding layer WX-1 was provided on OC-1.

Next, each sample was heat-treated. The heat treatment conditions are shown in Table 4. This heat treatment has a diameter
The backing layer was inwardly wound on a 30 cm core.

Further, on the undercoat layer A-2, 25 W / (m ² · mi
The corona discharge of n) was applied and the following photographic constituent layers were sequentially formed to prepare a multilayer color photographic light-sensitive material.

The coating amount in the photographic constituent layers shown below is the amount expressed in g / m ² unit in terms of metallic silver for silver halide and colloidal silver, and for couplers and additives. Is the amount expressed in g / m ² and
The sensitizing dye is shown by the number of moles per mole of silver halide in the same layer.

First layer: antihalation layer Black colloidal silver 0.16 Ultraviolet absorber (UV-1) 0.20 High boiling point solvent (OIL-1) 0.16 Gelatin 1.60 Second layer: Intermediate layer Compound (SC-1) 0.14 High boiling point solvent (OIL-2) 0.17 Gelatin 0.80 Third layer: low-sensitivity red-sensitive layer Silver iodobromide emulsion A 0.15 Silver iodobromide emulsion B 0.35 Sensitizing dye (SD-1) 2.0 × 10 ^-4 Sensitizing dye (SD- 2) 1.4 × 10 ^-4 Sensitizing dye (SD-3) 1.4 × 10 ^-5 Sensitizing dye (SD-4) 0.7 × 10 ^-4 Cyan coupler (C-1) 0.53 Colored cyan coupler (CC-1) 0.04 DIR compound (Di-1) 0.025 High boiling point solvent (OIL-3) 0.48 Gelatin 1.09 4th layer: Medium-sensitive red-sensitive layer Silver iodobromide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-1) 1.7 × 10 ^-4 sensitizing dye (SD-2) 0.86 × 10 ^-4 sensitizing dye (SD-3) 1.15 × 10 ^-5 sensitizing dye (SD-4) 0.86 × 10 ^-4 cyan coupler (C-1) ) 0.33 Colored Coupler (CC-1) 0.013 DIR compound (Di-1) 0.02 high boiling point solvent (OIL-1) 0.16 gelatin 0.79 Fifth layer: high-sensitivity red-sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-1) 1.0 × 10 ^-4 Sensitizing dye (SD-2) 1.0 × 10 ^-4 Sensitizing dye (SD-3) 1.2 × 10 ^-5 Cyan coupler (C-2) 0.14 Colored cyan coupler (CC-1) 0.016 High boiling point Solvent (OIL-1) 0.16 Gelatin 0.79 Sixth layer: Intermediate compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 Seventh layer: Low sensitivity green sensitive layer Silver iodobromide emulsion A 0.12 Iodine Silver bromide Emulsion B 0.38 Sensitizing dye (SD-4) 4.6 × 10 ^-5 Sensitizing dye (SD-5) 4.1 × 10 ^-4 Magenta coupler (M-1) 0.14 Magenta coupler (M-2) 0.14 Colored magenta Coupler (CM-1) 0.06 High boiling point solvent (OIL-4) 0.34 Gelatin 0.70 Eighth layer: Intermediate layer Gelatin 0.41 Ninth layer: Medium-sensitive green sensitive layer Iodine Halide emulsion B 0.30 Silver iodobromide emulsion C 0.34 Sensitizing dye (SD-6) 1.2 × 10 -4 Sensitizing dye (SD-7) 1.2 × 10 -4 Sensitizing dye (SD-8) 1.2 × 10 - ⁴ Magenta coupler (M-1) 0.04 Magenta coupler (M-2) 0.04 Colored magenta coupler (CM-1) 0.017 DIR compound (Di-2) 0.025 DIR compound (Di-3) 0.002 High boiling point solvent (OIL-4) 0.12 Gelatin 0.50 10th layer: High-sensitivity green-sensitive layer Silver iodobromide emulsion D 0.95 Sensitizing dye (SD-6) 7.1 × 10 ^-5 Sensitizing dye (SD-7) 7.1 × 10 ^-5 Sensitizing dye (SD -8) 7.1 × 10 ^-5 Magenta coupler (M-1) 0.09 Colored magenta coupler (CM-1) 0.011 High boiling point solvent (OIL-4) 0.11 Gelatin 0.79 Layer 11: Yellow filter layer Yellow colloidal silver 0.08 Compound (SC) -1) 0.15 High boiling point solvent (OIL-2) 0.19 Gelatin 1.10 12th layer: Low sensitivity blue sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide emulsion B 0.24 Silver iodobromide emulsion C 0.12 Sensitizing dye (SD-9) 6.3 × 10 ^-5 Sensitizing dye (SD-10) 1.0 × 10 ^-5 Yellow coupler (Y-1) 0.50 Yellow coupler (Y-2) 0.50 DIR compound (Di-4) 0.04 DIR compound (Di-5) 0.02 High boiling point solvent (OIL-2) 0.42 Gelatin 1.40 13th layer: High sensitivity blue sensitive layer Silver iodobromide emulsion C 0.15 Iodine Silver bromide emulsion E 0.80 Sensitizing dye (SD-9) 8.0 × 10 ^-5 Sensitizing dye (SD-11) 3.1 × 10 ^-5 Yellow coupler (Y-1) 0.12 High boiling point solvent (OIL-2) 0.05 Gelatin 0.79 Layer 14: First protective layer Silver iodobromide emulsion (average grain size 0.08 μm, silver iodide content 1.0 mol%) 0.40 UV absorber (UV-1) 0.065 High boiling point solvent (OIL-1) 0.07 High Boiling point solvent (OIL-3) 0.07 Gelatin 0.65 Fifteenth layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethylmeth Tacrylate (average particle size 3 μm) 0.04 Lubricant (WAX-1) 0.04 Gelatin 0.55 In addition to the above composition, coating aid Su-1 and dispersion aid Su
-2, viscosity modifier, hardener H-1, H-2, stabilizer ST
-1, antifoggant AF-1, two types of AF-2 having an average molecular weight of 10,000 and an average molecular weight of 1,100,000, and preservative DI-1 were added.

[0125]

[Chemical 2]

[0126]

[Chemical 3]

[0127]

[Chemical 4]

[0128]

[Chemical 5]

[0129]

[Chemical 6]

[0130]

[Chemical 7]

[0131]

[Chemical 8]

[0132]

[Chemical 9]

[0133]

[Chemical 10]

[0134]

[Chemical 11]

A film was prepared by cutting each of the prepared samples to a width of 35 mm.

The emulsions used for the above samples are as follows. The average particle size is shown as a particle size converted into a cube.
Further, each emulsion was optimally subjected to gold / sulfur sensitization.

[0137]

[Table 3]

The sample was applied by a multi-slide hopper type coater at the first time, and the first to eighth layers were simultaneously applied, and at the second time, the ninth to 15th layers were simultaneously applied thereon.
Sample 101 had a silver coating amount of 6.25 g / m ² , a dry film thickness of 18 μm, and a specific photographic speed of ISO 420.

The obtained light-sensitive material was subjected to perforation processing as described in JIS K7519-1982.
Using this photosensitive material, the suitability for cine type automatic processor processing was examined as follows.

<Cine-type automatic processor suitability> A normal developing process was carried out using NCV60 manufactured by Noritsu Koki Co., Ltd. 200 samples each having a length of 1 m were passed through to examine whether breakage occurred. The evaluation criteria are the following three levels.

Rank Number of broken pieces ◎ No breaking occurred ○ 1 to 4 × 5 or more ○ Not less than practically acceptable level if it was not less than ○.

In addition, the curl curl recovery and surface failure were measured by the following methods.

<Recovery property of curl> Sample size 12 cm x
A 35 mm film is wound on a core having a diameter of 10 mm so that the emulsion surface is inwardly wound, and treated at 55 ° C. and 20% RH for 3 days,
Attach a curly habit. After that, it is released from the core, immersed in pure water at 38 ° C. for 15 minutes, and then dried with a hot air dryer at 55 ° C. for 3 minutes while applying a load of 50 g. Remove the load, hang the sample,
The distance between both ends of the sample was obtained, and how much the original distance 12 cm was recovered was evaluated. The evaluation was performed according to the following criteria.

⊚: 70% or more ◯: 60% or more and less than 70% Δ: 50% or more and less than 60% ×: less than 50% If it is a Δ level or more, there is no problem in practical use.

<Coating Failure> The number of coating failures of the photographic photosensitive layer per 1 m ^{2 of} film was visually evaluated and ranked according to the following criteria. The practicality of this ranking is
It is decided based on the acceptability of the quality as a photographic light-sensitive material, and it is necessary that the rank is O or higher.

Rank Number of surface faults ◎ 0 ○ 1 to 3 × 4 or more The results are shown in Table 4.

[0147]

[Table 4]

From the above results, it can be seen that the sample of the present invention is superior in cine type automatic processor processing suitability, curl recovery and coating failure as compared with the comparison.

Example 3 <Preparation of Support> Films 1 to 4 were prepared in the same manner as in Example 1. All film thicknesses are 90 μm.

<Preparation of Photosensitive Material> In the same manner as in Example 1, the undercoat layers A-1, A-2 and the conductive layer B-1 were coated on each support. Further, a corona discharge of 8 W / (m ² · min) was applied on the conductive layer B-1, and the following magnetic recording layer MG-1 or MG-2 was applied so as to have a dry film thickness of 1 μm. 8 W / (m ² · on the MG-1
min) corona discharge was performed, and the sliding layer WX-1 was provided in the same manner as in Example 1.

<MG-1> Nitrocellulose 70 parts by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co Coated γ-Fe ₂ O ₃ (long axis 0.2 μm, short axis 0.02 μm, Hc = 650 oersted) 5 parts by weight <MG-2> Nitrocellulose 63 parts by weight Sliding agent (see Example 1) 7 parts by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co-deposited γ-Fe ₂ O ₃ (long axis 0.2 μm , Minor axis 0.02 μm, Hc = 650 oersted) 5 parts by weight Next, each sample was heat-treated. The heat treatment conditions are shown in Table 5. This heat treatment was performed by winding the backing layer inward on a winding core having a diameter of 30 cm.

Further, a photographic constituent layer was formed on the undercoat layer A-2 in the same manner as in Example 2.

Thus, a multilayer color photographic light-sensitive material having a magnetic recording layer was prepared.

Each of the prepared samples was cut as shown in FIG. 1 and packed in a cartridge to prepare a film having a width of 35 mm and 24 shots. This was loaded into a camera with a magnetic head described in US Pat. No. 5,021,820. Tracks C0 to C in FIG.
3, F00 and F29 represent tracks for recording magnetic information by the signal input method as described in the above specification, and 101 represents perforation.

This film was subjected to the development processing shown below.

<Development Processing> 1. Color development ・ ・ ・ 3 minutes 15 seconds 38.0 ± 0.1 ℃ 2. Bleaching ... 6 minutes 30 seconds 38.0 ± 3.0 ° C 3. Washing with water ・ ・ ・ ・ 3 minutes 15 seconds 24-41 ℃ 4. Settling ··· 6 minutes 30 seconds 38.0 ± 3.0 ° C 5. Washing with water ... 3 minutes 15 seconds 24-41 ° C 6. Stability ・ ・ ・ ・ 3 minutes 15 seconds 38.0 ± 3.0 ℃ 7. Drying ... 50 ° C or less The composition of the processing liquid used in each step is shown below.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid sodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1 liter (pH = 10.1) <bleaching liquid> Ethylenediaminetetraacetic acid iron (III ) Ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 g Water is added to make 1 liter and pH is adjusted with ammonia water.
Adjust to 6.0.

<Fixer> Ammonium thiosulfate 175.0 g anhydrous sodium sulfite 8.5 g sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

The sample after this development processing was put into a magnetic recording / reproducing apparatus, and a reproduction output error was examined. The reproduction output error means that the average reproduction output per track is 70% or less of the reproduction output when the magnetic head normally contacts the film.

The scratch resistance was measured by the following method.

<Scratch resistance> A load of 100 g is applied to the magnetic head in the above magnetic recording / reproducing apparatus, and the reading operation is performed 50 times. The number of scratches entered by the magnetic head was visually observed and evaluated according to the following evaluation criteria.

⊚: 0 lines ∘: 1-2 lines x: 3 or more lines ∘ or more is a level with no practical problem.

The results are shown in Table 5.

[0165]

[Table 5]

From the above results, it can be seen that the sample of the present invention is excellent in reproduction output error and scratch resistance as compared with the comparison.

[0167]

The silver halide photographic light-sensitive material according to the present invention has a small curl curl and is excellent in mechanical strength, scratch resistance and adhesion resistance. It has a magnetic recording layer in which the occurrence of errors is reduced and the reliability of magnetic recording is high.

[Brief description of drawings]

FIG. 1 is a plan view of a light-sensitive material of the present invention.

[Explanation of symbols]

 101 Perforation C0 to C3 tracks (record magnetic information) F00 to F29 tracks (record magnetic information)

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having a photosensitive silver halide emulsion layer on one side of a polyester support, wherein the outermost layer of the backing layer of the polyester support has a penetration of 5 or less. A silver halide photographic light-sensitive material, which comprises the outermost layer of the backing layer of a support and is heat-treated at a temperature of 40 ° C. or higher and Tg or lower for 0.01 to 2000 hours. 2. The silver halide photographic light-sensitive material according to claim 1, which has at least one magnetic recording layer. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the polyester support is composed of a polyester containing naphthalenedicarboxylic acid and ethylene glycol as main components.