JPH08194284A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE: To enhance scratching resistance and adhesiveness and magnetic characteristics by forming a photosensitive silver halide emulsion layer on one side of a polyester support and a layer containing a water-soluble or water- dispersible polyester type resin and a magnetic recording layer in this order on the other side. CONSTITUTION: The photosensitive silver halide emulsion layer is formed on one side of the polyester support and the layer containing the water-soluble or water-dispersible substantially linear polyester type resin obtained by polycondensation reaction of a polybasic acid or its derivative for forming this polyester and a polyol or its derivative for forming the polyester together with a hydrophilic component as a copolymerizable monomer for forming a water-soluble or water-dispersible polymer, and the magnetic recording layer are formed in this order on the other side. It is preferred to use a cellulose ester mainly for the binder of the magnetic recording layer, especially, a cellulose diacetate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material having a magnetic recording layer and having excellent adhesion and scratch resistance.

[0002]

2. Description of the Related Art Conventionally, when a silver halide photographic light-sensitive material (hereinafter also referred to as a light-sensitive material) is photographed, information such as a photographing date / time, an aperture and an exposure time is optically inputted. In contrast, U.S. Pat.Nos. 3,782,947, 4,279,945, and 4,30
As described in each specification of No. 2,523, by providing a transparent magnetic recording layer on the back surface of the photosensitive material, for example, various information such as the type of photosensitive material, manufacturing number, manufacturer name, emulsion No., etc., Various information at the time of shooting such as shooting date, weather, aperture, exposure time, lighting condition, filter used, size of shooting frame, etc., and number of prints, size of trimming frame, message, development and print conditions, etc. It is suggested to enter in.

However, since the magnetic recording layer is provided on the back surface, if it is scratched during transportation or when it is rubbed by a magnetic head, there is a problem that it appears in a printed image or an error occurs when reproducing magnetic information. Therefore, the magnetic recording layer is required to have a property of being less likely to be scratched. Therefore, as described so far in JP-A-6-59357 and the like, a non-aqueous thermoplastic resin typified by cellulose ester is used as an organic solvent. It is formed by dissolving and dissolving magnetic powder and coating.

On the other hand, as a means for reducing the thickness of the support in order to reduce the size of the camera, a triacetate film support (hereinafter also referred to as a TAC film) conventionally used for a roll film is used instead of the triacetate film support. It has been proposed to use various polyester films having excellent mechanical strength.

When a polyester film is used as a support for a light-sensitive material, a subbing layer is usually provided, but a water-soluble or water-dispersible resin is used from the viewpoint that a working environment and explosion-proof equipment are unnecessary.

However, since the magnetic recording layer is made of a non-aqueous resin, if its adhesion to the hydrophilic undercoat layer is insufficient, it may be peeled off during the development process, or may be rubbed during transportation or by a magnetic head. However, there is a drawback that the back layer is peeled off.

[0007]

SUMMARY OF THE INVENTION The present invention has been made under the above circumstances, and an object thereof is to provide a silver halide photographic light-sensitive material having a magnetic recording layer excellent in scratch resistance, adhesiveness and magnetic characteristics. To provide.

[0008]

The above object of the present invention is to provide a photosensitive silver halide emulsion layer on one side of a polyester support and a water-soluble or water-dispersible polyester resin on the other side. A silver halide photographic light-sensitive material having a layer containing and a magnetic recording layer in this order, a magnetic recording layer containing cellulose acetate, and a polyester support containing polyethylene-2,6-naphthalate as a main component. .

The present invention will be described in detail below.

In the present invention, the water-soluble or water-dispersible polyester is a substantially linear polymer obtained by polycondensation reaction of a polybasic acid or its ester-forming derivative with a polyol or its ester-forming derivative. And is water-soluble or water-dispersible.

In order to render the polyester water-soluble or water-dispersible, a hydrophilic component as a copolymerization component, for example,
A component having a sulfonate, a diethylene glycol component, and a polyalkylene ether glycol component are used.

Examples of the polybasic acid component of the water-soluble polyester include terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 2,6-naphthalenedicarboxylic acid, 1,4-
Cyclohexanedicarboxylic acid, adipic acid, sebacic acid, trimellitic acid, pyromellitic acid, dimer acid can be used, and examples of the diol component include ethylene glycol, 1,4-butanediol, neopentyl glycol, diethylene glycol, and diethylene glycol. Propylene glycol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, xylylene glycol, dimethylolpropane, poly (ethylene oxide) glycol and polytetramethylene oxide can be used.

In the present invention, a preferable copolymer component having hydrophilicity is an aromatic dicarboxylic acid having a sulfonate group.

Examples of the aromatic dicarboxylic acid containing these sulfonate groups include 5-sodium sulfoisophthalic acid, 2-sodium sulfophthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid. An acid is mentioned. These are not limited to sodium salts, but may be salts of other cations (potassium, lithium, ammonium, phosphonium, etc.).

The aromatic dicarboxylic acid having a sulfonate group is preferably used in an amount of 2 to 20 mol% of the total polybasic acid component, more preferably 5 to 15 mol%.

It is also preferable to use a dicarboxylic acid represented by the following general formula [A] as the polybasic acid component.

General formula [A] R ₁ OOCCH ₂ (OR ₂ ) _n OCH ₂ COOR ₃ [wherein R ₁ and R ₃ are each a hydrogen atom or a carbon number of 1 to 8]
And an R ₂ represents an alkylene group having 2 to 8 carbon atoms. n represents a positive integer of 1 to 100. ] In the dicarboxylic acid represented by the above general formula [A],
(OR ₂ ) _n − is preferably a polyethyleneoxy group, a polytrimethyleneoxy group or a polytetramethyleneoxy group.

Various methods can be used for synthesizing the water-soluble or water-dispersible polyester according to the present invention. For example, an initial condensate of dicarboxylic acid and glycol is formed by a transesterification method or a direct esterification method. It can be obtained by a known polyester production method in which this is melt-polymerized. Specifically, for example, a method of performing an ester exchange reaction with an ester of dicarboxylic acid, for example, a dimethyl ester of dicarboxylic acid and glycol, distilling out methanol, and then gradually reducing the pressure, and performing polycondensation under high vacuum. ,
After the esterification reaction of dicarboxylic acid and glycol and distilling off the produced water, the pressure is gradually reduced, and under high vacuum,
Examples thereof include a polycondensation method, a transesterification reaction between an ester of a dicarboxylic acid and a glycol, an esterification reaction by adding a dicarboxylic acid, and a polycondensation under high vacuum.

As the transesterification catalyst and polycondensation catalyst, known ones can be used. As the transesterification catalyst, manganese acetate, calcium acetate, zinc acetate or the like can be used, and as the polycondensation catalyst, antimony trioxide or germanium oxide can be used. , Dibutyltin oxide, titanium tetrabutoxide and the like can be used. However, various conditions such as the polymerization method and the catalyst are not limited to the above examples.

Further, the polyester in the present invention may be a copolymer or composition having a vinyl polymer as a constituent, and these copolymers or compositions are present in the presence of a water-soluble or water-dispersible polyester. By polymerizing the vinyl monomer by, for example, dissolving or dispersing the vinyl monomer in an organic solvent solution or aqueous solution of a water-soluble or water-dispersible polyester, and polymerizing the vinyl monomer. You can

In the present invention, in synthesizing the above water-soluble or water-dispersible polyester, an addition-polymerizable group,
For example, a carboxylic acid group, a glycidyl group or an amino group is introduced in advance so that a vinyl polymer is polymerized in the presence of polyester so that a branch polymer is formed on the addition-polymerizable group. You may stay.

The use of an organic solvent for the polymerization of vinyl monomers in the presence of polyester is not preferable because it complicates the process equipment and pollutes the working environment. From this viewpoint, it is preferable that the polyester is dissolved or suspended in hot water, the vinyl-based monomer is dispersed and added to the matrix of the polyester, and emulsion polymerization or suspension polymerization is performed.

A polymerization initiator is used to polymerize the vinyl monomer. Examples of the polymerization initiator that can be used include ammonium persulfate, potassium persulfate, sodium persulfate, and benzoyl peroxide. Of these, ammonium persulfate is preferable.

The polymerization of the vinyl monomer in the matrix of the water-soluble or water-dispersible polyester can be carried out without using a surfactant, but the surfactant is used for the purpose of improving the polymerization stability. It is also possible to use as an emulsifier. In this case, both general nonionic type and anionic type can be used.

When a vinyl monomer is graft-polymerized to a water-soluble or water-dispersible polyester, a graft polymer in which a vinyl polymer serving as a branch polymer is bonded to the polyester which is a trunk polymer is formed and a vinyl-based monomer is formed. Although a polymer of a polymer is also formed, these formed vinyl-based polymers may not be removed.

To obtain a copolymer or composition comprising a water-soluble or water-dispersible polyester and a vinyl-based polymer as constituents, the vinyl-based monomer is (polyester) / (vinyl-based monomer) is 99 It is preferable to use it so that it is within the range of / 1 to 5/95. More preferably (polyester) / (vinyl-based monomer) = 97/3 to 50/50, and further 95/5
~ 80/20.

Examples of vinyl-based monomers that can be used include acrylic-based monomers such as alkyl acrylate and alkyl methacrylate (wherein the alkyl group is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, phenyl group, benzyl group, phenylethyl group, etc.); 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate , Hydroxy group-containing monomers such as 2-hydroxypropyl methacrylate; acrylamide, methacrylamide, N-methylmethacrylamide, N-
Amide group-containing monomers such as methylacrylamide, N-methylolmethacrylamide, N-methylolacrylamide, N, N-dimethylolacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-phenylacrylamide; N, Amino group-containing monomers such as N-diethylaminoethyl acrylate and N, N-diethylaminoethyl methacrylate; Epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; Acrylic acid, methacrylic acid and their salts (sodium salt, potassium salt) Examples of the monomer include a carboxyl group such as a salt and an ammonium salt) or a salt thereof. Examples of non-acrylic monomers include epoxy group-containing monomers such as allyl glycidyl ether; sulfonic acids such as styrene sulfonic acid, vinyl sulfonic acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) Monomers containing groups or salts thereof; Monomers containing carboxyl groups or salts thereof, such as crotonic acid, itaconic acid, maleic acid, fumaric acid and salts thereof (sodium salt, potassium salt, ammonium salt, etc.) A monomer containing an acid anhydride such as maleic anhydride or itaconic anhydride; vinyl isocyanate; allyl isocyanate; styrene; vinyltrisalkoxysilane; alkyl maleic acid monoester; alkyl fumaric acid monoester; acrylonitrile; methacrylonitrile ; Alkyl itaconic acid monoesters; vinyl chloride Isopropylidene; vinyl acetate; vinyl chloride and the like can be mentioned. The above-mentioned monomers may be used alone or in combination of two or more.

When the polyester resin of the present invention is water-dispersible, its particle size is 5 μm or less, preferably 1 μm or less, and more preferably 0.1 μm or less. If the particle diameter is large, not only the thickness of the coating layer cannot be reduced, but also the transparency of the coating layer deteriorates.

Further, in the layer containing the water-soluble or water-dispersible polyester resin of the present invention, other binders, cross-linking agents, matting agents, antiblocking agents, antistatic agents, etc. are used as long as the effects of the present invention are not impaired. Can be added.

The matting agent is not particularly limited, and examples thereof include particles of inorganic compounds such as silicon dioxide, titanium dioxide, and aluminum oxide, and polymer compounds such as polystyrene and polymethylmethacrylate having a glass transition point Tg of 50 ° C. or higher. .

Next, the antistatic agent preferably used in the light-sensitive material of the present invention is not particularly limited, but, for example, a conductive polymer or a metal oxide can be used.

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 and carboxylic acid-based polymers when anionic, and tertiary amine-based and quaternary ammonium-based polymers or latexes when cationic. These conductive polymers are disclosed, for example, in Japanese Patent Publication No. 52-25251.
Anionic polymers or latexes described in JP-A-51-29923 and JP-B-60-48024, JP-B-57-18176 and 57-
-56059, 58-56856, U.S. Pat. No. 4,118,231, and other cationic polymers or latices.

Specific examples of these conductive polymers or latices will be described below, but the present invention is not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

[Chemical 4]

These conductive polymers can be used alone, but it is more preferable to apply them in combination with other binders. Furthermore, curing agents can also be used with these binders.

The content of conductive polymer is preferably 0.00
5 to 5 g / m ² , more preferably 0.01 to 3 g / m ² ,
More preferably, it is 0.02 to 1 g / m ² .

When a binder is used in combination, the weight ratio of the conductive polymer or latex to the binder is 99: 1.
To 10:90 are preferred, 80:20 to 20:80 are more preferred, and 70:30 to 30:70 are particularly preferred.

Examples of metal oxides include oxygen-rich oxides such as Nb ₂ O _{5 + x} , oxygen-deficient oxides such as RhO _2-x and Ir ₂ O _3-x , or Ni (OH) _x. Non-stoichiometric hydroxides, such as Hf
O ₂ , ThO ₂ , ZrO ₂ , CeO ₂ , ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O
₃ , SiO ₂ , MgO, BaO, MoO ₂ , V ₂ O _5, etc., or a composite oxide thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples containing heteroatoms include A for ZnO, for example.
Addition of l, In, etc., addition of Nb, Ta, etc. for TiO ₂ , SnO
_{For 2} , it is effective to add Sb, Nb, a halogen element, or the like. Addition amount of these hetero atoms is 0.01 mol% to 25 mol%
Is preferable, but the range of 0.1 mol% to 15 mol% is particularly preferable.

The particle size of the metal oxide is not particularly limited, but the primary particle size is preferably 10 μm or less, more preferably 5 μm or less, and particularly preferably 1 μm or less.

Regarding the particle size, it is preferable to adopt the average particle diameter obtained by measurement with a particle size distribution meter by a sedimentation method, a laser diffraction method or the like, but the particle diameter may be determined from an electron micrograph. However, when an electron microscope is adopted, if a higher-order structure is formed in the visual field, measurement is performed in units of higher-order structure.

The amount of the metal oxide particles added to the binder is not particularly limited, but is preferably 50 vol% or less, more preferably 40 vol% or less, further preferably 30 vol% or less.

The amount of the metal oxide used is 0.00005 to 1 g per 1 m ² of the photographic light-sensitive material.

As the binder used together with the conductive polymer and the metal oxide particles, proteins such as gelatin, colloidal albumin and casein, cellulose compounds such as carboxymethyl cellulose, hydroxyethyl cellulose, diacetyl cellulose and triacetyl cellulose; agar, sodium alginate , Sugar derivatives such as starch derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol,
Poly-N-vinylpyrrolidone, polyacrylic acid copolymer,
Polyacrylamide or derivatives or copolymers thereof, natural products such as rosin and shellac and their derivatives, and many other synthetic resins are used. Further, styrene-butadiene copolymer, polyacrylic acid, polyacrylic acid ester and its derivatives, polyvinyl acetate, vinyl acetate-
Aqueous emulsions of acrylic acid ester copolymers, polyolefins, olefin-vinyl acetate copolymers, etc. can also be used.

The volume resistivity of these metal oxide particles is preferably 10 ¹⁰ Ωcm or less, more preferably 10 ⁷ Ωcm or less, especially 10 ⁵ Ωcm or less.

With respect to the value of volume resistivity, in the case of an oxide from which a large single crystal can be obtained, it means the value of the volume resistivity of the single crystal, and when a large single crystal cannot be obtained, a powder is formed. It means the volume resistivity of the sintered body obtained by the above. When these values are unknown, a value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure in the powder state by 10 ² is adopted. The constant pressure is not particularly limited,
A pressure of 10 kg / cm ² or more is preferable, and a value obtained by dividing the volume resistivity of the material formed by applying a pressure of 100 kg / cm ² or more by 10 ² is more preferable. With respect to the pressure applied to the powder and the volume resistivity of the molded body, generally, the higher the pressure, the lower the volume resistivity. However, even when an isostatic pressure of 3 t / cm ² is applied by a hydrostatic pressure device, a value lower than the volume specific resistance value obtained with a single crystal cannot be obtained, and the value is about 100 times higher. Therefore, a value obtained by dividing the volume resistivity of the molded body obtained by applying a constant pressure in the powder state by 10 ² is adopted.

These antistatic agents may be present in at least one of the layers constituting the photosensitive material, and examples thereof include a subbing layer on the back side or a back layer.

Further, these antistatic agents may be mixed with the water-soluble or water-dispersible polyester resin of the present invention.
In this case, 50 vo
If it is 1% or less, preferably 30 vol% or less, the effect of the present invention can be obtained without impairing the adhesiveness with the adjacent magnetic recording layer.

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 powder, chromium dioxide magnetic powder, barium ferrite magnetic powder, etc. can be used. The method for producing these magnetic powders is known, and the magnetic powders used in the present invention can also be produced according to known methods.

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. There are no particular restrictions on the crystallite size or specific surface area. The magnetic powder may be surface-treated. For example, it may be surface-treated with a substance containing an element such as titanium, silicon or aluminum, or may be adsorbed with a nitrogen-containing heterocycle such as carboxylic acid, sulfonic acid, sulfuric acid ester, phosphonic acid, phosphoric acid ester or benzotriazole. It may be treated with an organic compound such as a polar compound. The pH of the magnetic powder is not particularly limited, but is preferably in the range of 5-10.

Regarding the size of magnetic particles, it is "television" that there is a correlation between the size and the transparency.
Volume 20, No. 2 "Characteristics of Ultrafine Particle 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.

US Pat. No. 2,950,971 describes that a magnetic layer of magnetic iron oxide dispersed in a binder is transparent to infrared radiation, and US Pat. No. 4,27.
No. 9,945 describes that when the particle size is reduced, the wavelength is increased even when the concentration of magnetic particles in the magnetic layer is relatively high.
It is described that the transmittance of 632.8 nm helium / neon laser light is improved.

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

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

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

Practically, the coating amount of the magnetic powder is 0.001
˜3 g / m ² , more preferably 0.01 to 1 g / m ² .

As the binder used in the magnetic recording layer,
Known thermoplastic resins, radiation-curable resins, thermosetting resins, other reactive resins, and mixtures thereof which have been conventionally used for magnetic recording media can be used.

The thermoplastic resin has a glass transition point Tg of −40 ° C.
~ 150 ° C, preferably 60 ° C to 120 ° C, the weight average molecular weight is preferably 10,000 to 300,000, and more preferably the weight average molecular weight is 50,000 to 200,
It's 000.

The binder of the magnetic recording layer in the present invention preferably contains cellulose ester as a main component. Specifically, cellulose acetate such as cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate; cellulose nitrate. Cellulose sulfate, mixed esters thereof, and the like, and preferably cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate, and particularly cellulose diacetate.

The binder may be hardened. Hardeners that can be used include aldehyde compounds, ketone compounds, compounds having a reactive halogen, compounds having a reactive olefin, N-hydroxymethylphthalimide, N-methylol compound, isocyanates, Examples thereof include aziridine compounds, acid derivatives, epoxy compounds, halogen carboxaldehydes and mineralized hardeners.

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

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

When forming an optically transparent magnetic recording layer, the binder is preferably used in an amount of 1 to 20 parts by weight based on 1 part by weight of the magnetic powder. More preferably, it is 2 to 15 parts by weight with respect to 1 part by weight of the magnetic powder. Further, the solvent is used in such an amount that the coating can be easily performed.

The thickness of the magnetic recording layer is preferably 0.1 to 10 μm, more preferably 0.2 to 5 μm, still more preferably 0.5.
~ 3 μm.

The coating liquid for forming the magnetic recording layer contains a lubricant and an antistatic agent in order to provide the magnetic recording layer with functions such as imparting lubricity, preventing electrification, preventing adhesion, and improving friction / abrasive properties. Various additives such as agents can be added. In addition, in addition to the coating liquid, for example, a plasticizer for giving flexibility to the magnetic recording layer, a dispersant for aiding dispersion of the magnetic substance in the coating liquid, and for preventing clogging of the magnetic head. Abrasives can be added.

If desired, a protective layer may be provided on the outermost layer adjacent to the magnetic recording layer to improve scratch resistance. A compound generally known as a slipping agent can be used for imparting scratch resistance, but higher fatty acid esters are preferable. When the magnetic recording layer is provided in a stripe shape, a transparent polymer layer containing no magnetic material may be provided thereon to eliminate the step due to the magnetic recording layer.
In this case, the transparent polymer layer may have various functions described above.

Next, the polyester support according to the present invention will be described.

The support of the present invention is a polyester having a dicarboxylic acid component and a diol component as main constituents.

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. Further, 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 the main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid component and ethylene glycol as the diol component are used in terms of transparency, mechanical strength, and dimensional stability. And / or a polyester having 1,4-cyclohexanedimethanol as a main constituent is preferable. Among these, a polyester composed of polyethylene terephthalate, polyethylene-2,6-naphthalate, terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and a polyester having a mixture of two or more of these polyesters as main constituents are preferable. When the content of ethylene terephthalate unit and / or ethylene-2,6-naphthalate unit is 70% by weight or more with respect to polyester, a film having excellent transparency, mechanical strength and dimensional stability can be obtained. .

The polyester constituting the polyester film according to 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. May be. Examples of these include the above-mentioned dicarboxylic acid component, diol component, and 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 photographic light-sensitive materials.

The thickness of the polyester film of the present invention is not particularly limited, but is 20 to 125 μm, particularly 40 to 90 μm.
m is preferred.

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 photographic light-sensitive material, the image printed on the photographic printing paper is blurred and unclear. The haze is measured according to ASTM-D1003-52.

The glass transition point Tg of the polyester film of the present invention is preferably 60 ° C. or higher, more preferably 70 ° C. or higher and 150 ° C.
The following are preferred. 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.

Next, the method for producing the polyester film of the present invention will be described, but the method is not particularly limited.

The method for obtaining an unstretched sheet and the method for uniaxially stretching in the machine direction can be carried out by conventionally known methods. For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled and solidified, and unstretched. Get the sheet. Then, the obtained unstretched sheet is heated in a range from Tg of polyester to Tg + 100 ° C. through a plurality of roll groups and / or a heating device such as an infrared heater, and is subjected to single-stage or multi-stage longitudinal stretching. The stretching ratio is usually in the range of 2.5 times to 6 times, and it is necessary to set it in a range in which subsequent transverse stretching is possible.

The longitudinally uniaxially stretched polyester film obtained as described above was subjected to Tg-Tm (melting point) -20 ° C.
Within the temperature range of 1, the film is transversely stretched and then heat set. The transverse stretching ratio is usually 3 to 6 times, and the ratio of the longitudinal stretching ratio to the transverse stretching ratio is appropriately adjusted so that the obtained biaxially stretched film has physical properties measured and has desirable characteristics. Generally, it is preferable to balance the physical properties in the width direction and the longitudinal direction, but it may be changed depending on the purpose of use. At this time, it is preferable to laterally stretch while gradually increasing the temperature difference in the range of 1 to 50 ° C. in the stretching region divided into two or more because the distribution of the physical properties in the width direction can be reduced. After the transverse stretching, the film is preferably kept in the range of Tg-40 ° C or higher for 0.01 to 5 minutes at the final transverse stretching temperature or lower for 0.01 to 5 minutes because the distribution of physical properties in the width direction can be further reduced.

The heat setting is carried out at a temperature higher than the final transverse stretching temperature and usually within a temperature range of Tm-20 ° C. or lower for 0.5 to 300 seconds. At this time, it is preferable to heat-set while sequentially increasing the temperature difference in the range of 1 to 100 ° C. in the region divided into two or more.

The heat-fixed film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound up. At this time, 0.1-10% in the width direction and / or the longitudinal direction within the temperature range below the final heat setting temperature and above Tg.
Relaxation treatment is preferred. Further, for cooling, it is preferable to gradually cool from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second.

The more optimum heat setting conditions, cooling conditions and relaxation treatment conditions differ depending on the polyester constituting the film. Therefore, the physical properties of the obtained biaxially stretched film are measured and appropriately adjusted so as to have the desired properties. It may be determined by

With respect to the polyester film, various methods are adopted to reduce the curl. For example, JP-A-51-1
As described in No. 6358, there is a method of heat treatment at a temperature lower than the glass transition point Tg of a polyester film by 30 ° C to 5 ° C. Further, in Japanese Unexamined Patent Publication No. 1-131550, in a sequential biaxial stretching step, a temperature gradient is applied to the front and back sides of the film between longitudinal stretching and transverse stretching to give a difference in crystallinity and orientation, and a permanent curl is provided. The method is described. In addition, when the product is wound up, it is wound in the opposite direction to the curl, and the time-dependent curl that occurs when the product is stored is offset, and the polyester film formed with a temperature difference during stretching is at a temperature not lower than the glass transition temperature of 50 ° C or higher. A method of heat treatment is also known.
The support, which is less likely to have a curl due to heat treatment, is a polyester having a glass transition point of 90 ° C. or higher and 200 ° C. or lower.
This is because the effect of this heat treatment disappears when exposed to a temperature above the glass transition point, so the highest temperature exposed when used by general users (the temperature in a car in summer, sometimes exceeding 80 ° C). This is because it is necessary to have a glass transition point of 90 ° C. or higher on the basis of. In addition, there is no general-purpose polyester film which is transparent and has a glass transition temperature of more than 200 ° C. Particularly preferable as such a polyester is polyethylene naphthalate, and a copolymer or composition using this as a raw material. These supports are preferably subjected to heat setting treatment after biaxial stretching, and may be heat relaxed if necessary.

In this case, the heat treatment needs to be performed at a temperature of 50 ° C. or higher and a glass transition temperature or lower for 0.1 hour or more and 1500 hours or less. Of these, a particularly preferable heat treatment method is
For example, polyethylene naphthalate has a Tg of about 120.
Therefore, it is preferable to heat-treat at a temperature of 119 ° C. or lower for 0.2 to 72 hours, more preferably at 115 ° C. or lower for 24
It is a heat treatment for about an hour. In particular, in order to perform heat treatment in a short time, it is very efficient and preferable to raise the temperature once above Tg and gradually cool it in the vicinity of Tg. In the case of polyethylene naphthalate, for example, once maintain the temperature between 130 ℃ and 200 ℃, cool it to 125 ℃, and then cool it to 100 ℃.
By gradually cooling in minutes, the heat treatment time can be significantly shortened.
When the support subjected to such heat treatment is measured by a differential thermal analyzer, an endothermic peak appears near Tg, and the larger the endothermic peak, the less likely the winding tendency is. Further, it is preferable that the heat treatment is carried out so as to be 100 mcal / g or more, further 200 mcal / g or more.

For the polyester support of the present invention,
Support and silver halide emulsion layer, hydrophilic colloid layer,
An undercoat layer can be used as an adhesive layer between the backside layer and the undercoat layer is not particularly limited.
-19941 and 59-77439, acrylic copolymers, copolymers of diolefin monomers and vinyl monomers described in JP-A-57-128332, etc. 43-3976
And the layer containing a vinylidene chloride copolymer described in JP-A No. 64-538, JP-A No. 3-137637 and the like.

In the undercoat layer, a conductive substance, an antihalation agent, a crossover cut agent, a coloring dye, a pigment, a coating aid, an antifoggant, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, One kind or two or more kinds of various additives such as an etching treatment agent and a matting agent may be contained.

Since the polyester film support according to the present invention has a hydrophobic surface, it is usually supplemented not only with these undercoat layers but also with various surface treatments in advance to supplement its adhesiveness. What is such surface treatment?
Corona discharge treatment, fire treatment, ultraviolet treatment, high frequency treatment,
In addition to surface activation treatments such as glow discharge treatment, active plasma treatment and laser treatment, etching treatment with chemicals such as resorcinol, phenols, alkalis, amines and trichloroacetic acid may be mentioned.

Among the surface activation treatments, corona discharge treatment is the most well-known method, and any of the conventionally known methods such as JP-B-48-5043, JP-A-47-51905, and JP-A-47-47905. -28067, 49-83769, 51-41770, 51-1
It can be achieved by the method disclosed in, for example, No. 31576.

The discharge frequency is 50 Hz to 5000 kHz, preferably 5 kHz to several hundreds of kHz. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, 0.001KV · A · min / m ^{2 to} 5KV · A · min / m ² , preferably 0.01KV for improving the wettability of ordinary polyester, polyolefin and other plastic films. -A · min / m ^{2 to 1} KV · A · min / m ² is suitable. Gap clearance between electrode and dielectric roll is 0.5
Approximately 2.5 mm, preferably 1.0 to 2.0 mm is suitable.

In many cases, the glow discharge treatment, which is the most effective surface treatment, is carried out by any conventionally known method, for example, Japanese Patent Publications No. 35-7578, No. 36-10336, No. 45-22004,
45-22005, 45-24040, 46-43480, U.S. patents
3,057,792, 3,057,795, 3,179,482, 3,28
No. 8,638, No. 3,309,299, No. 3,424,735, No. 3,462,335
, 3,475,307, 3,761,299, British Patent 997,093
JP-A-53-129262 and the like can be used. The glow discharge treatment condition is generally a pressure of 0.005 to 20 Torr, preferably 0.02 to 2 Torr. If the pressure is too low, the surface treatment effect is reduced, and if the pressure is too high, an excessive current flows, sparks easily occur, which is dangerous and may damage the object to be treated. The electric discharge is generated by applying a high voltage between metal plates or metal rods arranged in a vacuum tank with one or more pairs of spaces. This voltage can take various values depending on the composition and pressure of the atmospheric gas, but usually within the above pressure range, 500 to 5000 V
A stable steady glow discharge occurs between the two. A particularly suitable voltage range for improving adhesion is 2000 to 4000V. Further, as seen in the prior art, a suitable discharge frequency is from DC to several 1000 MHz, preferably 50 Hz to 20 MHz. Regarding the discharge treatment strength, 0.01KV · A · min / m ^{2 to} 5KV · A · min /
m ² , preferably 0.15 KV · A · min / m ^{2 to 1} KV · A · min / m ² ,
Is appropriate.

The silver halide emulsion of the light-sensitive material of the present invention is
For example, Research Disclosure (RD) No.17643,
22-23 (December 1978) “I. Emulsion prep
ara-tion and types) ”and the same (RD) No.18716, 648
P. Glafkides, Chemic et Phisique Photographiqu.
e, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GFDuffin, Photographic Emulsi
on Chemistry, Focal Press 1966), "Photoemulsion production and coating" by Zelikmann et al., published by Focal Press (VLZe
likman et al, Making and Coating Photographic Emul
sion, Focal Press, 1964) and the like.

Emulsions are disclosed in US Pat. Nos. 3,574,628 and 3,6.
The monodisperse emulsions described in 65,394 and GB 1,413,748 are also preferred.

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)).

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, the photographic additives that can be used are also described in the above RD. Further, various couplers can be used, and specific examples thereof are also described in RD17643 and RD308119.

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

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

In the case of constructing a color photographic light-sensitive material, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned RD308119 VII-K can be adopted.

Development processing of the silver halide photographic light-sensitive material of the present invention is carried out, for example, by TH James, Theory.
4th Edition of The Photographic Process
y of The Photografic Process Forth Edition) Pages 291 to 334 and the Journal of the American Chemical Societies
ciety) 73, 3,100 (1951),
Developers known per se can be used. Also,
For color photographic light-sensitive materials, see RD17643, pages 28-29, RD1871.
Development can be carried out by a usual method described on page 615 and RD308119 XIX.

[0100]

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 >> Dimethyl 2,6-naphthalenedicarboxylate
To 100 parts by weight of ethylene glycol and 60 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. To the obtained product, 0.05 part by weight of antimony trioxide and 0.03 part by weight of trimethyl phosphate were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out under the conditions of 290 ° C. and 0.05 mmHg to obtain polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

After vacuum-drying this at 150 ° C. for 8 hours, 3
Melt extrusion was carried out in layers from a T die at 00 ° C., and it was brought into close contact with 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 at a second stretching zone at 155 ° C. in 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.
Then, while being relaxed in the lateral direction by 5%, it was gradually cooled to room temperature over 30 seconds to obtain a polyethylene naphthalate film having a thickness of 85 μm.

Wrap this around a stainless steel core, and
A support was prepared by heat treatment at 0 ° C. for 48 hours.

Both sides of this support were subjected to a corona discharge treatment of 12 W / m ² / min, one side was coated with an undercoating coating solution B-1 so that a dry film thickness was 0.4 μm, and 12 W was applied thereon. / M ² / mi
Corona discharge treatment of n was applied, and the undercoat coating solution B-2 was applied so as to have a dry film thickness of 0.06 μm.

On the other surface subjected to the corona discharge treatment of 12 W / m ² / min, the undercoating coating solution B-3 or B-4 was dried to a film thickness.
It is applied to 0.2 μm, and 12 W / m ² / min of corona discharge treatment is applied on it, and water-dispersible coating solutions R-1 to R-
No. 8 was applied so that the dry film thickness would be 0.2 μm, and as a comparison, one in which nothing was applied on B-3 or B-4 was also prepared.

After coating each layer, each layer was dried at 90 ° C. for 10 seconds, after coating four layers, heat-treated at 110 ° C. for 2 minutes and then cooled at 50 ° C. for 30 seconds.

<Undercoating liquid B-1> Copolymer latex liquid (solid content: 30% by weight, t-butyl acrylate 20% by weight, styrene 25% by weight, and 2-hydroxyethyl acrylate 25% by weight). 30%) 125g Compound (UL-1) 0.4g Hexamethylene-1,6-bis (ethyleneurea) 0.05g Finish with water 1000ml <Undercoating liquid B-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 Water-finished 1000 ml <Undercoating liquid B-3> 40 wt% butyl acrylate, 20 wt% styrene and Glycidyl acrylate 40% by weight copolymerized latex liquid (solid content 30%) 40 g Compound (UL-1) 0.4 g Tin oxide sol manufactured by Taki Chemical Co., Ltd. (solid content 10%) 360 g Finished with water 1000 ml <Undercoating liquid B- > Butyl acrylate 40 wt% of styrene 20% by weight and glycidyl acrylate 40 wt% of copolymerized latex solution (solid content 30%) 270 g Compound (UL-1) 1000 ml finish in 0.6g water

[0109]

Embedded image

<Coating liquid R-1> 40 mol% of dimethyl terephthalate and dimethyl isophthalate as dicarboxylic acid components
30 mol%, sodium salt of dimethyl 5-sulfoisophthalate 10 mol% and 1,4-cyclohexanedicarboxylic acid 20 mol%, ethylene glycol 70 mol% as a glycol component
And 30 mol% of 1,4-cyclohexanedicarboxylic acid were copolymerized by a conventional method. The copolymer A thus obtained was stirred in hot water of 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion A. 130 g of this water dispersion A and 0.4 g of compound (UL-1) were mixed and mixed with water.
Diluted to 1000 ml.

<Coating Liquid R-2> 50 mol% of dimethyl terephthalate and 50 mol% of dimethyl isophthalate as dicarboxylic acid components, and 50 mol% of ethylene glycol and 50 mol% of diethylene glycol as glycol components were copolymerized by a conventional method.

The copolymer B thus obtained was stirred in hot water at 95 ° C. for 3 hours to obtain a 15% by weight aqueous dispersion B. 130 g of this aqueous dispersion B and 0.4 g of compound (UL-1) were mixed and 1000 ml of water was added.
Diluted.

<Coating Liquid R-3> In the aqueous dispersion A, 10 mol% of acrylamide, 20 mol% of glycidyl methacrylate,
A mixed solution of 60 mol% of styrene and 10 mol% of ethyl acrylate was used so that the solid content was 20% by weight of the polyester copolymer A, and emulsion polymerization was carried out using ammonium peroxide as a polymerization initiator. % Of acrylic modified polyester copolymer C was prepared. This water dispersion C13
0 g and 0.4 g of compound (UL-1) were mixed and diluted with water to 1000 ml.

<Coating Liquid R-4> In the aqueous dispersion B, 10 mol% of acrylamide, 15 mol% of glycidyl methacrylate,
A mixture of 75 mol% of styrene was used so that the solid content was 20% by weight of the polyester copolymer B, and emulsion polymerization was carried out using ammonium peroxide as a polymerization initiator. An aqueous dispersion D of coalescence D was prepared. This aqueous dispersion D130g and compound (UL-1) 0.4g
And Spherica slurry 300 made by Catalysts & Chemicals (average particle size 0.2
7 μm, solid content 20% by weight) 1.0 g, and 1000 ml with water
Diluted.

<Coating liquid R-5> 130 g of a copolymer latex (solid content 30% by weight) of 10 mol% acrylamide, 20 mol% glycidyl methacrylate, 60 mol% styrene and 10 mol% ethyl acrylate and a compound (UL -1) 0.4 g was mixed and diluted to 1000 ml with water.

<Coating Liquid R-6> 60 g of powder of antimony-doped tin oxide SN-100P manufactured by Ishihara Sangyo Co., Ltd. and 267 g of water dispersion B (solid content 15% by weight) were mixed, diluted to 400 g with water and stirred. The mixture was dispersed by a machine and a sand mill to obtain a 25% by weight aqueous dispersion E. 400 g of this water dispersion E and 0.6 g of compound (UL-1) were mixed and diluted with water to 1000 ml.

<Coating liquid R-7> 60 g of powder of antimony-doped tin oxide SN-100P manufactured by Ishihara Sangyo Co., Ltd., 200 g of water dispersion B (solid content 15% by weight), and a mixture of ethyl acrylate, methyl methacrylate and methacrylic acid. 100 g of polymer latex (ethyl acrylate / methyl methacrylate / methacrylic acid = 45/45 / 10-molar ratio, solid content 10% by weight) is mixed, diluted with water to 400 g and dispersed by a stirrer and a sand mill, 25% by weight Of water dispersion F. This water dispersion F400
g and the compound (UL-1) 0.6 g were mixed and diluted to 1000 ml with water.

<Coating Liquid R-8> 60 g of antimony-doped tin oxide SN-100P powder manufactured by Ishihara Sangyo Co., Ltd., 40 g of polyester “Vylon 200” manufactured by Toyobo Co., Ltd., methyl ethyl ketone 9
00 g and cyclohexanone 100 g were mixed with a dissolver and dispersed by a sand mill.

Next, one of the following magnetic recording layer coating solutions M-1 to M-5 was dried on the surface coated with the water-dispersible coating solution to a dry film thickness of 0.
It was applied so as to have a thickness of 8 μm, and the sliding layer O-1 was applied thereon so that the dry film thickness was 0.02 μm. After coating, each layer was dried at 80 ° C. for 10 seconds and then heat-treated at 90 ° C. for 2 minutes.

<Coating liquid M-1> Diacetyl cellulose 82
g, Co deposition γ-Fe ₂ O ₃ (long axis 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2,
Hc = 600 oersted) 6.6 g, α-alumina (average particle size 0.5 μm) 4 g, acetone 990 g and cyclohexanone 1
10 g were mixed, mixed with a dissolver for 1 hour, and then dispersed with a sand mill for 2 hours to obtain a dispersion liquid.

<Coating liquid M-2> A coating liquid in which nitrocellulose is used in place of the diacetyl cellulose of the coating liquid M-1.

<Coating Solution M-3> 82 g of a copolymer of butyl acetate and vinyl chloride (butyl acetate / vinyl chloride = 50/50),
Co-deposited γ-Fe ₂ O ₃ 6.6g and α-alumina (average particle size 0.5μ
m) 4 g, methyl ethyl ketone 500 g, toluene 400 g, and cyclohexanone 100 g are mixed, and 1 with a dissolver.
After mixing for an hour, the mixture was dispersed in a sand mill for 2 hours to obtain a dispersion liquid.

<Coating liquid M-4> A urethane resin UR-8200 82 g manufactured by Toyobo Co., Ltd. was used instead of the butyl acetate / vinyl chloride copolymer of the coating liquid M-3.

<Coating liquid M-5> 135 g of water-based polyurethane XW76-P15 (solid content 30% by weight) manufactured by Takeda Pharmaceutical Co., Ltd., 5 g of Co-deposited γ-Fe ₂ O ₃ and α-alumina (average particle size 0.5 μm) ) 4g
Was kneaded and dispersed to obtain a dispersion liquid.

<Coating liquid O-1> Carnauba wax 7 g Toluene 700 g Methyl ethyl ketone 300 g << Preparation of photosensitive material >> The same photographic emulsion layer as the commercially available color negative film Konica Color LV400 manufactured by Konica Corporation is used as the undercoating liquid B. -2 was applied after corona discharge was applied to the coated surface.

Treatment of each of the obtained samples was performed as follows.

<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 color negative film thus obtained was evaluated as follows with a film in a dry state before development (hereinafter referred to as a raw film), with a film in a dry state after development (hereinafter referred to as a dry film) and scratch resistance as follows. It was evaluated by the method.

Evaluation Method with Film (with Raw Film and with Dry Film) A razor blade was used on the surface of the back surface layer of the sample that had been dried before or after development.
A scratch that reaches the support is made at an angle of 45 °, an adhesive tape (cellophane adhesive tape) is pressure-bonded onto the scratch, and then the tape is rapidly peeled at an angle of about 45 °. At this time, the area of the back surface layer which is peeled off together with the tape is compared with the area where the tape is stuck, and the following five grades are evaluated.

Evaluation 5 4 3 2 1 Peeling condition None at all 0-20% 21-50% 51-100% 101% or more If the evaluation is 4 or more, it can be considered that the film formation is sufficiently strong in practical use.

(Scratch resistance) The sample after the development treatment was conducted at 23 ° C. and 55%.
After leaving it for 12 hours at RH, apply a sapphire needle with a tip diameter of 25 μm vertically to the back surface and apply a continuous load of 0 to 50 g for 10 hours.
Scratch at a speed of mm / sec. The scratch-resistant sample was placed on Schaukasten, and the load-bearing strength at which scratches began to be seen by permeation was defined as scratch resistance. The larger the value, the better the scratch resistance.

The above results are shown in Table 1.

[0136]

[Table 1]

Example 2 Thickness in place of polyethylene naphthalate film support
A sample similar to the sample No. 3 of Example 1 except that a 90 μm polyethylene terephthalate (PET) film support is used is prepared and is designated as sample No. 24. Also, 90 μm thick terephthalic acid / naphthalene dicarboxylic acid / adipic acid / 5-sulfoisophthalic acid / ethylene glycol (20/70 / 6.5 /
Sample No. 25 is prepared in the same manner as in Sample No. 3 of Example 1 except that a condensate film of 3.5 / 100) is used as a support.

On the other hand, a coating solution composition for an antistatic layer having the following composition was applied on the back side of a cellulose triacetate having a thickness of 115 μm so as to have a dry film thickness of 0.2 μm, and Example 1 was applied thereon.
Coating solutions M-1 (dry film thickness 0.8 μm) and O-1 (dry film thickness 0.02 μm) were applied.

(Coating liquid for antistatic layer) 60 g of antimony-doped tin oxide SN-100P powder made by Ishihara Sangyo Co., Ltd., water dispersion B
(Solid content 15% by weight) 267 g, pure water 250 g, methanol 100
50 g of N, N-dimethylformamide was dispersed with a stirrer and a sand mill.

Further, an undercoat layer having the following composition was provided on the emulsion layer coated side of the support.

(Undercoat Layer Coating Liquid) Gelatin 1 g Distilled water 1 g Acetic acid 1 g Methanol 50 g Acetone 50 g N, N-Dimethylformamide 4 g Each layer is dried at 90 ° C. for 10 seconds after coating, and then 110
Heat treatment was performed at 2 ° C. for 2 minutes. Next, the same emulsion layer as in Example 1 was coated on the above subbing layer. This is designated as Sample No. 26.

With respect to each of the obtained samples, the same as in Example 1 was evaluated for live film formation, dry film formation and scratch resistance. Also, JIS K7
After performing the perforation processing described in 519-1982, the perforation strength was measured as follows.

Tensilon RTA-100 manufactured by Orientec Co., Ltd.
Then, the end portion 3 of the perforation strength measuring jig shown in FIG. 2 is grasped by a tensilon chuck. A perforation part of a film having a length of 250 mm is fitted into the sprocket part 1, the film is passed through, and a 100 g weight is hung on the film end part 2. The other film end 4 was grasped by a chuck and pulled at a speed of 40 mm / min, and the maximum load when the perforation part broke was defined as the perforation strength.

The above results are shown in Table 2.

[0145]

[Table 2]

[0146]

As demonstrated in the examples, when the polyester film has a magnetic recording layer as a support, the adhesion and scratch resistance of the magnetic recording layer can be improved by adopting the undercoating composition layer of the present invention. Can be improved.

[Brief description of drawings]

FIG. 1 is a perspective view showing a schematic configuration of a tester used for measuring perforation strength of a light-sensitive material of the present invention.

[Explanation of symbols]

 1 Sprocket part 2 Film edge 3 Testing machine edge 4 Film edge

Claims (3)

[Claims] 1. A polyester support having a photosensitive silver halide emulsion layer on one side, and a layer containing a water-soluble or water-dispersible polyester resin and a magnetic recording layer on the other side in this order. A silver halide photographic light-sensitive material characterized by: 2. The silver halide photographic light-sensitive material according to claim 1, wherein the magnetic recording layer contains cellulose acetate. 3. The polyester support is polyethylene-2,6
-The silver halide photographic light-sensitive material according to claim 1 or 2, which comprises naphthalate as a main component.