JPH07281353A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material superior in mechanical characteristics, small in curling tendency, and superior in antitackiness and planarity. CONSTITUTION:The photosensitive material has at least one silver halide emulsion layer on one side of a polyester support and the uppermost layer of the emulsion layers is a nonphotosensitive layer having a dry film thickness of >=0.5mum, and the photosensitive material is heat treated in a wound state after coating with the uppermost layer at a temperature of dry bulb temperature 35 deg.C-50 deg.C for 60-3000hr.

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 particularly used in the form of a roll film, and in particular, it has a small curling curl after development and has excellent mechanical strength and dimensional stability. The present invention relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film unwinding at the time of photographing, the increase of photographing magnification, and the downsizing of photographing apparatus have been remarkably advanced. Therefore, a support for a photographic light-sensitive material has been required to have properties such as excellent mechanical strength and dimensional stability.

Biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) has excellent transparency, mechanical strength and dimensional stability. PET films are used in place of the triacetyl cellulose film (TAC film) that has been used in the past, for the X-ray films that are required to have strict printing sensitivity, transparency and elasticity. . However, in a photographic light-sensitive material that is used in a roll film like a general negative film, if a PET film that does not have curl recovery after development processing as seen in a TAC film is used, curl after development processing will not occur. Not only is it too strong and inferior in handleability, but problems such as scratches, defocusing, and jamming during transport occur in the process of printing an image on photographic printing paper after development, for example. .

As a method for improving the curl-up recovery property of such a PET film, there are disclosed in JP-A 1-244446 and JP-A 4-44446.
In 220329, a PET film obtained by copolymerizing a water-absorbing component is 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).

Further, as a method of making the polymer film difficult to curl, JP-A-51-16358 discloses that 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. Furthermore, JP-A-6-35
No. 118 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.

The heat treatment of such a polyester film is preferably carried out by sticking it on a flat surface in order to fix the support in the shape of a flat surface with no curl, but in reality, it takes a huge area. It is difficult to prepare a plane,
A general method is to wind the roll around a winding core having a relatively large radius of curvature and heat the roll.

At this time, the problem is adhesion in the heat treatment process. That is, the heat treatment step is usually performed after coating the undercoat layer having the function of adhering the support to the silver halide emulsion layer or other hydrophilic colloid layer and the back layer on the opposite surface, but at this time, a comparison of 50 ° C or more is performed. Due to the high temperature treatment, the undercoat layer and the back layer adhere and stick to each other, or the slip agent added to the back layer is transferred to the undercoat layer and repels when the hydrophilic colloid layer is applied, resulting in unevenness. Happens.

On the other hand, for the purpose of improving the adhesion resistance,
Japanese Unexamined Patent Publication No. 6-51426 has a means for making the glass transition point of the component constituting the outermost layer of the backing layer 110 ° C. or higher and 200 ° C. or less, and Japanese Unexamined Patent Publication No. 6-51442 has a means for using a matting agent. Although disclosed, such a method has a problem that not only the adhesion resistance is insufficient, but also the flatness of the film is impaired by the high temperature treatment in a roll form.

[0009]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide a silver halide photographic light-sensitive material having excellent mechanical properties, less curling, excellent adhesion resistance and excellent flatness. Is to provide.

[0010]

The above problems can be solved by the following method. That is, in a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on one side on a polyester film support, the uppermost layer of the silver halide emulsion layer is a non-photosensitive layer having a dry film thickness of 0.5 μm or more. Is a heat-resistant layer, and after being applied up to the uppermost layer, in a wound state, a dry-bulb temperature of 35 ° C. or higher and lower than 50 ° C.
A silver halide photographic light-sensitive material characterized by being heat-treated for ~ 3000 hours.

The present invention will be described in detail below.

In the present invention, the heat treatment condition is a dry-bulb temperature.
It should be between 35 ° C and below 50 ° C for 60 to 3000 hours,
At this time, it is preferable that the relative humidity is 40 to 70% RH, further preferably the conditions of dry-bulb temperature 38 to 45 ° C. and relative humidity 45 to 60% RH. Within this range, adhesion resistance and flatness are Not only is it good, but the deterioration of emulsion properties such as fog can be suppressed to a minimum.

The heat treatment of the present invention may be performed subsequent to the coating of the silver halide emulsion layer or after a certain period of time, but it is preferable to start the heat treatment within a short period after coating.

Further, the period of this heat treatment can be appropriately determined according to various conditions such as the formulation of the emulsion layer and the form of the light-sensitive material wound into a roll within the scope of the present invention. 72 to 400 hours is preferable for obtaining the effect.

In the present invention, the core is used when the photosensitive material is wound into a roll.

The core to be wound is not particularly limited, but it has a strength such that it does not bend even if the film is wound and has an appropriate water vapor permeability, or the surface has fine irregularities and the atmosphere has a core. It is preferable that the structure reach up to. Examples of these include a paper roll, a resin roll, a fiber reinforced resin roll, a grooved metal roll, a mesh roll, and a ceramic coating roll. If the core diameter is too small, wrinkles and the like are likely to occur in the core, so it is preferable that the core diameter is large to some extent.
mm or more, more preferably 200 mm or more. The roll diameter of the wound film roll is preferably too small, because uniform treatment becomes difficult if it is too large.
Usually, it is preferably 1000 mm or less, more preferably 850 mm or less.

Further, in order to further secure the effect of the present invention, the film roll is made of a material having a water vapor barrier property when the film is heat-treated by containing a proper amount of water or conditioned at a relative humidity. It is preferable to wrap. The material having a water vapor barrier property is not particularly limited as long as it can withstand the heat treatment temperature. For example, it is various films such as polyethylene, polypropylene, polyester, etc., and metal-deposited films, and has a thickness of 5 to 1000 μm.

In the present invention, the method of heat-treating the photographic light-sensitive material may be any method as long as it can uniformly heat the roll-shaped photographic light-sensitive material. For example, the entire heating chamber for heat-treating the photographic light-sensitive material may be adjusted to the above heat treatment conditions, or the photographic light-sensitive material may be covered with a heating medium. As the heating medium, a heating plate, a heating coil, a combination of a heating device and a thermally conductive metal, a thermally conductive metal cover containing a fluid such as a thermally conductive medium, or the like can be used. May be

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. 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 in the polyester is 70% by weight or more, a film excellent in transparency, mechanical strength and dimensional stability can be obtained. .

The polyester constituting the polyester film of the present invention may be further copolymerized with other copolymer 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 hydrophilic group of the compound having at least one hydrophilic group is sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, polyoxyalkylene group, sulfamoyl group, carbamoyl group, acylamino group, sulfonamide. Group, disulfonamide group, ureido group, urethane group, alkylsulfonyl group, alkoxysulfonyl group, and the like, among them, sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, a polyoxyalkylene group, A disulfonamide group is preferred.

Examples of the compound having a hydrophilic group include 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, and a diol having a polyoxyalkylene group. Is mentioned. Above all, in terms of polymerization reactivity of polyester and transparency of the film,
5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and these sodiums with other metals (eg potassium, lithium, etc.) and A compound substituted with an ammonium salt, a phosphonium salt, or the like, or an ester-forming derivative thereof, polyethylene glycol, polytetramethylene glycol, a polyethylene glycol-polypropylene glycol copolymer, or a hydroxyl group at both ends thereof is oxidized to form a carboxyl group. Compounds and the like are preferable.

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 this range, 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 may contain an antioxidant. In particular, the effect becomes remarkable when the polyester contains a compound having a polyoxyalkylene group. The antioxidant to be contained is not particularly limited as to its type, and various antioxidants can be used, for example, hindered phenol compounds,
Antioxidants such as phosphite compounds and thioether compounds can be mentioned. Among them, antioxidants of hindered phenolic compounds are preferable in terms of transparency.

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

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 photographic light-sensitive material for color negative, it is preferably 20 to 125 μm, and particularly preferably 40 to 90 μm. Further, when used in a photographic light-sensitive material for medical use or printing, the thickness is preferably 50 to 200 μm, 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 loses its superiority to conventional supports for 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 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 Tg of the polyester film of the present invention is 60.
C. or higher is preferable, and 70 ° C. or higher and 150 ° C. or lower is more preferable. 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, a 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 to a temperature within the range of Tg + 100 ° C. from the glass transition temperature (Tg) of polyester through a plurality of roll groups and / or a heating device such as an infrared heater, and a single-stage or multi-stage longitudinal stretching is performed. Is.
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. When the sheet has a multi-layered structure, the stretching temperature is preferably set based on the highest Tg of Tg of the polyester of each constituent layer.

At this time, when polyester is laminated,
A conventionally known method may be used. For example, a co-extrusion method using a plurality of extruders and a feed block type die or a multi-manifold type die, a single layer film constituting a laminate or other resin constituting a laminate on the laminate film is melt extruded from the extruder and cooled. Examples thereof include an extrusion laminating method of cooling and solidifying on a drum, and a dry laminating method of laminating a monolayer film or a laminated film constituting a laminate with an anchor agent or an adhesive as required. Of these, the coextrusion method is preferable because it requires few manufacturing steps and has good adhesion between the layers.

Then, the polyester film uniaxially stretched in the machine direction obtained as described above was treated with Tg to Tm (melting point).
Within the temperature range of −20 ° C., transverse stretching is performed, and then heat setting is performed.
The transverse stretching ratio is usually 3 to 6 times, and the ratio of the longitudinal and transverse stretching ratios is obtained by measuring the physical properties of the obtained biaxially stretched film,
It is appropriately adjusted so as to have preferable 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 holding 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 optimal heat setting conditions, cooling conditions, and relaxation treatment conditions vary 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

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,
The magnetic powder used in the present invention can also be manufactured according to a known method.

The shape and size of the magnetic substance 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. US Pat.
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 the present invention, by setting the crystallite size of the metal oxide to 1 nm to 20 nm, it is possible to obtain a light-sensitive material having higher transparency. 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 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 and other reactive resins conventionally used as binders for magnetic recording media are used. Mixtures of can be used.

The thermoplastic resin has a Tg of −40 ° C. to 150 ° C., preferably 60 ° C. to 120 ° C., a weight average molecular weight of 10,000 to 300,000, and more preferably a weight average molecular weight. Is from 50,000 to 200,000.

The radiation-curable resin is a resin which is cured by radiation such as electron beam and ultraviolet rays, and examples thereof include maleic anhydride type, urethane acryl type, ether acryl type and epoxy acryl type.

Examples of thermosetting resins and other reactive resins include phenolic resins, epoxy resins, polyurethane-based curable resins, urea resins, alkyd resins, and silicone-based curable resins.

The above binder may have a polar group in its molecule.

A hydrophilic binder may also be used as the binder of the magnetic recording layer of the present invention. For example, Research Disclosure No. 17643, page 26, and No. 187.
The water-soluble polymers, cellulose ethers, latex polymers and water-soluble polyesters described on pages 16 and 651 can be mentioned, but gelatin is the most preferable.

The gelatin may be unmodified or modified. In addition, some of them are colloidal albumin, casein, carboxymethyl cellulose, cellulose derivatives such as hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids, for example,
It may be replaced with polyvinyl alcohol, poly N-vinylpyrrolidone, acrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates, gelatin derivatives and the like.

A hydrophilic binder containing gelatin is preferably hardened. Hardeners that can be used include aldehyde compounds, ketone compounds, reactive halogen-containing compounds, reactive olefin-containing compounds, and N-
Hydroxymethylphthalimide, N-methylol compound,
Isocyanates, aziridine compounds, acid derivatives,
Epoxy compounds, halogen carboxaldehydes and mineralized hardeners can be mentioned.

Hardeners are typically 0. 0 for dry gelatin.
It is used in an amount of 01 to 30% by weight, preferably 0.05 to 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 per 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 method for providing the magnetic recording layer on the support includes air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, A spray coat can be used. In order to perform multi-stripe coating, these coating heads may be arranged in multiple rows. Specific stripe coating methods include, for example, JP-A-48-25503, JP-A-48-25504, JP-A-48-98803, and JP-A-50-13803.
No. 7, No. 52-15533, No. 51-3208, No. 51-6
No. 239, No. 51-65606, No. 51-140703, No. 29-4221, US Pat. No. 3,062,181
The description in the specification of 3,227,165 can be referred to.

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 impart functions to the magnetic recording layer such as imparting lubricity, preventing electrification, preventing adhesion, and improving friction and abrasion characteristics. 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 necessary, a layer for supplementing adhesion with other layers may be provided in the layer adjacent to the magnetic recording layer, or a protective layer adjacent to the magnetic recording layer may be provided to improve scratch resistance.

For imparting scratch resistance, a compound generally known as a slipping agent can be used, 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.

After providing the magnetic recording layer, calendering is performed on this layer to improve smoothness, and S of magnetic output is provided.
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 uppermost layer of the silver halide emulsion layer of the present invention has a dry film thickness of 0.5 μm or more, preferably 0.5 μm or more 1.
It is 5 μm or less. Within this range, not only the adhesion and flatness are good even when the heat treatment is performed under the conditions of the present invention, but the emulsion properties are not impaired, which is preferable.

The film thickness can be measured by enlarging and photographing the cross section of the dried sample with a scanning electron microscope, and the film thickness of each constituent layer in the multilayer structure can be individually determined by the measuring method.

The silver halide emulsion used in the present invention is, for example, Research Disclosure (RD) No. 17643, 22.
Page 23 (December 1978) “I. Emulsion prepar
a-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.

The emulsion is described 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, RD No.18716 and
No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). 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 Page 24 page 648-9 Supersensitizer page 996 IV-AE, J section 23-24 page 648-9 page Fogging agent page 998 VI page 24-25 page 649 stabilizer 998 page VI page 24-25 page 649 Page When the 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.

[Items] [RD308119] [RD17643] [RD18716] Color turbidity inhibitor page 1002 VII-I section 25 page 650 Dye image stabilizer 1001 page 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 page 1006 XII 27 page 650 Lubricant 1006 page XII 27 page 650 Activator and coating aid 1005 page XI 26-27 Page 650 matting agent page 1007 page XVI developer (included in light-sensitive material) page 1011 XX-B When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used. Examples are described below in RD17643 and RD308119. The relevant description is shown below.

[Item] [RD308119] [RD17643] Yellow coupler page 1001 VII-D item 25 page VII-C to G magenta coupler 1001 page VII-D page 25 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, RD308119 of the future
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, the forward layer, the reverse layer, and the reverse layer described in RD308119 VII-K above.
Various layer configurations such as a unit configuration 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 may be provided, or the support may be treated with a chemical,
Mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment,
Surface activation treatment such as high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, concentrated acid treatment, 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.W. H. James, Theory of the Photographic Process 4th Edition (Th
e Theory of The Photografic Process Forth Editio
n) 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. In addition, the color photographic light-sensitive material is RD17643 described above.
Development can be carried out by a usual method described on pages 28 to 29, RD18716 page 615 and RD308119 XIX.

[0081]

EXAMPLES Specific examples of the present invention will be described below.
The embodiments of the present invention are not limited to these.

Example 1 Preparation of Support (Polyester A) To 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol, 0.1 part by weight of calcium acetate hydrate as an ester exchange catalyst was added, followed by a conventional method. The transesterification reaction was carried out according to.

The product obtained contains antimony trioxide 0.05.
Parts by weight and 0.03 parts by weight of phosphoric acid trimethyl ester were added. Then gradually raise the temperature and reduce the pressure, and carry out polymerization under the conditions of 290 ° C and 0.05 mmHg to obtain polyethylene-2,6- with an intrinsic viscosity of 0.60.
I got naphthalate.

(Support 1) Using Polyester A, 15
After vacuum drying at 0 ° C. for 8 hours, the mixture was melt-extruded in layers from a T-die at 300 ° C., adhered onto a cooling drum at 50 ° C. while electrostatically applied, and solidified by cooling 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 obtained uniaxially stretched film 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 further 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 transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

Both sides of the support 1 were subjected to a corona discharge treatment of 8 W / (m ² · min), and one surface was coated with the subbing coating solution B-1 to a dry film thickness of 0.8 μm. A layer B-1 was formed, and a corona discharge treatment of 8 W / (m ² · min) was further applied onto the layer B-1 to apply the undercoat coating solution B-2 to a dry film thickness of 0.1 μm.

<Subbing Coating Liquid B-1> Copolymer latex liquid (solid content: 30% by weight, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate) 30%) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g 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 Finished with water 1000 ml Also, on the other surface of the support, the following antistatic layer coating solution B-3
Was applied to give a dry film thickness of 0.8 μm.

<Antistatic Coating Liquid B-3> Copolymerized latex liquid of butyl acrylate 40% by weight, butylene 20% by weight and glycidyl acrylate 40% by weight (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene -1,6-Bis (ethylene urea) 0.8g Ishihara Sangyo Co., Ltd. Antimony-doped tin oxide powder SN-100P 200g Finish with water 1000ml Adjust the pH of the mixture to 7.0, and use a stirrer and a sand mill to disperse the dispersion. Prepared.

On top of this, the following magnetic recording layer coating liquid B-4 was added.
Was applied to give a dry film thickness of 1.0 μm.

<Magnetic Recording Layer Coating Liquid B-4> Carnauba wax (10 parts by weight) was heated and dissolved in toluene (150 parts by weight), cooled and mixed with cyclohexanone (75 parts by weight) and methyl ethyl ketone (150 parts by weight). Made by Nitrocellulose BTH-1 / 2 100 parts by weight (solid content 70% by weight) and Co deposited γ-Fe ₂ O ₃ (major axis 0.8 μm, Fe ²⁺ / Fe ³⁺ = 0.2, Hc = 600 oersted) 5 Part by weight was added, and the mixture was mixed for 1 hour with a dissolver, and then dispersed with a sand mill to obtain a dispersion liquid.

Coating of Emulsion Layer Further, a corona discharge of 25 W / (m ² · min) was applied on the subbing layer B-2 to sequentially form the following photographic constituent layers to obtain a multilayer color photographic light-sensitive material. It was created.

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. The amount in g / m ² is shown, and for the sensitizing dye, it is shown as the number of moles per mole of silver halide in the same layer. For the 15th layer, the dry film shown in Table 2 is shown. The total weight was adjusted to be thick.

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 cyan 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 layer Compound (SC-1) 0.09 High boiling point solvent (OIL-2) 0.11 Gelatin 0.80 7th layer: low-sensitivity green-sensitive layer Silver iodobromide emulsion A 0.12 Silver iodobromide 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 sensitivity green-sensitive layer silver iodobromide emulsion B 0.30 silver iodobromide emulsion C 0.34 sensitizing dye (SD-6) 1.2 × 10 -4 sensitization Containing (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 11th layer: 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 solvent ( OIL-2) 0.42 Gelatin 1.40 13th layer: High-sensitivity blue-sensitive layer.

Silver iodobromide emulsion C 0.15 Silver iodobromide 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 14th layer: 1st 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 15th layer: Second protective layer Alkali-soluble matting agent (average particle size 2 μm) 0.15 Polymethyl methacrylate (average particle size 3 μm) 0.04 Sliding agent (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.

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.

[0098]

[Table 1]

The samples were simultaneously coated with a multi-slide hopper type coater at the first time, from the first layer to the eighth layer, and at the second time, thereon from the ninth layer to the fifteenth layer.
The specific photographic speed was ISO420. The structure of each compound used for the preparation of the sample is shown below.

[0100]

[Chemical 1]

[0101]

[Chemical 2]

[0102]

[Chemical 3]

[0103]

[Chemical 4]

[0104]

[Chemical 5]

[0105]

[Chemical 6]

[0106]

[Chemical 7]

[0107]

[Chemical 8]

[0108]

[Chemical 9]

[0109]

[Chemical 10]

[0110]

[Chemical 11]

<Heat Treatment of Film Support> According to the above method, the undercoat layer and the antistatic layer are coated and then wound up (this is referred to as step K-1), the undercoat layer, the antistatic layer and the magnetic layer. Heat treatment is carried out under the conditions shown in Table 2 either at the time of winding after coating to the recording layer (step K-2) or at the time of coating the silver halide emulsion layer (step K-3). did. All the heat treatments are performed with a stainless steel core having a diameter of 30 cm, and the back layer is wound outside, and the back winding is performed when the back layer is wound inside. In addition, the total length of the roll is 1,000m.

<Evaluation of Sample> With respect to the photographic film sample thus produced, the portion up to 5 m from the outside of the roll was visually observed, and its adhesion resistance and flatness were ranked according to the following criteria.

<Adhesion resistance> Rank ⊚: No sticking at all ◯: Sticking only at both ends on the outermost side of the winding Δ: Sticking in places on the entire observation surface X: Almost sticking to the entire observation surface The ideal adhesion resistance is ⊚, but if it is ∘, it means that the product can be used as a product by discarding only the outer peripheral portion of the winding, and this level or higher is necessary.

<Flatness> Rank ⊚: Good with no waviness ◯: Ripples are visible when seen closely ×: Large waviness Incidentally, the practicality in this ranking is determined based on the acceptability of quality as a photographic light-sensitive material. It is required to be ranked ○ or above.

<< Aptitude of Splicer >> The silver halide photographic light-sensitive material produced was slit into a width of 35 mm and a length of 120 cm. After conditioning the humidity at 23 ° C and 55% RH for one day, wrap the photosensitive layer inside and wrap it around a spool with an outside diameter of 9 mm to make the inside diameter of the body 1
After putting it in a 8.5 mm patrone, put it in a closed container 80
It was heated at 0 ° C for 2 hours and attached with a curl.

The sample subjected to the above treatment was left at 55 ° C. for 4 hours. The samples were connected by a film splicer processor (PS-35-2: Noritsu Koki Co., Ltd.) under the conditions of 23 ° C. and 55% RH.

(Evaluation of Suitability of Splicer) Ten samples of each sample were passed through a splicer and evaluated in the following four stages. In practical use, clogging and breaking of the film in the film splicer processor should never occur, and a grade of O or higher is required.

⊚: No clogging or breakage was observed ○: No clogging or breakage was observed, the tip of the film was slightly difficult to enter Δ: Clogging or breakage was 2 or less ×: Clogging or breakage was 3 On the other hand, <Evaluation of Fog> On the other hand, each sample was exposed to light for sensitometry, and the following development processing was performed to examine the increase in fog (ΔFog) in the magenta image area.

The development processing conditions are 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 (Konica Corporation) 7.5 ml Water is added to make 1 liter.

The evaluation results are shown in Table 1.

[0125]

[Table 2]

From the above results, it is apparent that the light-sensitive material having the constitution of the present invention has excellent adhesion resistance and flatness, good splicer suitability and small curl.

Example 2 In addition to the support 1 prepared in Example 1, the following supports were prepared.

(Polyester B) 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were added to calcium acetate hydrate 0.1 as an ester exchange catalyst.
Part by weight was added, and transesterification was performed according to a conventional method. 5 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration 35% by weight), 0.05 parts by weight of antimony trioxide, 0.03 parts by weight of phosphoric acid trimethyl ester, Irga 0.2 parts by weight of Knox 1010 (manufactured by Ciba Geigy) and 0.04 parts by weight of sodium acetate were added. Next, gradually raise the temperature and reduce the pressure, and polymerize at 290 ° C and 0.5 mmHg to obtain an intrinsic viscosity.
A polyester of 0.55 was obtained.

(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, gradually raise the temperature and reduce the pressure, and polymerize at 280 ° C and 0.5 mmHg to obtain an intrinsic viscosity.
0.65 polyester was obtained.

(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.

(Support 2) Using polyester D, 15
After vacuum drying at 0 ° C. for 8 hours, the mixture 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. 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 transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

(Support 3) Polyester A and polyester B were vacuum dried at 150 ° C. for 8 hours, respectively, and then 2
Using a single extruder, melt extrude at 300 ° C, join in layers in a T-die, adhere to a 40 ° C cooling drum while applying static electricity, and cool to solidify to form a laminated unstretched sheet with a two-layer structure. Obtained. At this time, the extrusion rate of each extruder was adjusted so that the thickness ratio of each layer was 1: 1. 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 in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further 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 110 ° 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 transverse direction by 5%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

(Support 4) Using Polyester C, 15
After vacuum-drying at 0 ° C. for 8 hours, it was melt-extruded in layers from a T-die at 285 ° C., adhered onto a cooling drum at 30 ° C. while electrostatically applied, and cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched in the machine direction at 95 ° C using a roll-type machine.
It was stretched 3.3 times.

The obtained uniaxially stretched film was stretched by a tenter type transverse stretching machine at 100 ° C. in the first stretching zone at 50% of the total transverse stretching ratio, and further in the second stretching zone at 115 ° C., the total transverse stretching ratio was 3.3 times. Was stretched. Then, it was heat-treated at 70 ° C. for 2 seconds, further heat-set at the first heat-setting zone of 150 ° C. for 5 seconds, and second heat-setting zone of 230 ° C. for 15 seconds.
Then, while being relaxed in the transverse direction by 5%, it was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 95 μm.

(Support 5) As the support 5, a cellulose triacetate film 120 μm was prepared.

Regarding each support thus obtained,
The characteristic values are shown in Table 2. The intrinsic viscosity, glass transition temperature, and melting point of each of the obtained polyesters were measured. The intrinsic viscosity of polyester A was 0.58, the glass transition temperature was 120 ° C, the melting point was 270 ° C, the intrinsic viscosity of polyester B was 0.52, and the glass Transition temperature is 123 ° C, melting point is 265 ° C, intrinsic viscosity of polyester C is 0.63, glass transition temperature is 76 ° C, melting point is 260 ° C, intrinsic viscosity of polyester D is 0.60, glass transition temperature is 105 ° C, melting point is 267 ° C. Met.

Further, since the support 3 showed curl convex on the polyester A side, the subsequent processing was carried out so that the convex side was the photographic photosensitive layer side.

[0141]

[Table 3]

The above-mentioned various characteristic values are obtained by the following.

(1) Glass transition temperature Tg and melting point Tm 10 mg of film or pellet is melted at 300 ° C. in a nitrogen stream of 300 cc / min and immediately cooled in liquid nitrogen.
A differential scanning calorimeter (manufactured by Rigaku Denki Co.,
DSC8230 type) in a 100cc / min nitrogen stream,
The temperature is raised at a heating rate of 10 ° C./min to detect Tg and Tm.
Tg was the average value of the temperature at which the baseline began to become eccentric and the temperature at which the baseline newly returned, and Tm was the peak temperature of the endothermic peak. The measurement start temperature is the measured Tg.
The temperature should be lower than 50 ℃.

(2) Film haze The film haze was measured according to ASTM-D1003-52.

(3) Intrinsic viscosity The film or pellet was dissolved in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (weight ratio 60/40), and the concentration was 0.2 g / dl, 0.6 g / dl, 1.0 A g / dl solution is prepared, and the specific viscosity (ηsp) at each concentration (C) is determined by an Ubbelohde viscometer at 20 ° C. Then
ηsp / C is plotted against C, and the obtained straight line is extrapolated to zero concentration to obtain the intrinsic viscosity [η]. The unit is dl /
indicated by g.

[0146] (4) Elastic modulus and breaking strength The film is cut into a size of 10 mm in width and 200 mm in length, and 23
After conditioning the humidity for 12 hours under the conditions of ℃ and 55% RH, using Tensilon (RTA-100) manufactured by Orientec Co., Ltd., the distance between the chucks was set to 100 mm, and the tensile test was performed at a pulling speed of 100 mm / min. The rate and the breaking strength were determined.

(5) Curling degree in width direction A sample having a width of 35 mm and a length of 2 mm was cut out and humidity-controlled for 1 day at 23 ° C. and 20% RH. The curl degree in the width direction is expressed by the reciprocal thereof. The unit is m ^-1 .

The above-mentioned supports were coated with the subbing layer coating solutions B-1 and B-2 in the same manner as in Example 1, and the antistatic layer coating solution B-3 was coated on the opposite surface thereof, and the following coatings were applied thereon. Liquid OC-1
Was applied at 10 ml / m ² .

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml Further, a photographic constituent layer was coated on B-2 in the same manner as in Example 1. The twelfth layer was set so as to have a dry film thickness of 0.6 μm, and was reversely wound in step K-3 shown in Example 1 at 43 ° C. and 55 ° C.
Heat treatment was performed at% RH for 200 hours.

The samples thus produced were evaluated for adhesion resistance, flatness and suitability for splicer in the same manner as in Example 1, and further evaluated for curl resolving property as follows.

(Winding curl eliminating property) 23 ° C., 55% after development processing
Under the RH atmosphere, grab the outside of the film and hang it.
The humidity was controlled over the days. The length of the part 12 cm from the tip corresponding to the core when naturally hanging was measured, the ratio to the original length was obtained, and the results were ranked according to the following criteria.

Rank ⊚: 70% or more ◯: 60% or more and less than 70% Δ: 50% or more and less than 60% ×: less than 50% Incidentally, if it is Δ level or more, there is no practical problem.

[0153]

[Table 4]

From the above results, the light-sensitive material having the constitution of the present invention has excellent effects. In particular, it was revealed that when the supports 1, 2 and 3 were used, the curl eliminating property was also excellent.

[0155]

The uppermost layer of the silver halide emulsion layer has a dry film thickness.
In a silver halide photographic light-sensitive material having a non-photosensitive layer of 0.5 μm or more, a dry-bulb temperature of 35 ° C. or higher and less than 50 ° C. is 60 to 3000.
It was possible to provide a photographic light-sensitive material using a polyester support which was excellent in curl eliminating property and flatness without deterioration in photographic performance by heat treatment for a long time.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on one side of a polyester film support, wherein the uppermost layer of the silver halide emulsion layer has a dry film thickness of 0.5 μm or more. Is a non-photosensitive layer of
The silver halide photographic light-sensitive material is characterized in that, after coating to the uppermost layer, it is heat-treated in a wound state at a dry-bulb temperature of 35 ° C or higher and lower than 50 ° C for 60 to 3000 hours. 2. The heat treatment is performed at a relative humidity of 40% RH or more and 70% RH.
The silver halide photographic light-sensitive material according to claim 1, which is carried out below. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the heat treatment is carried out in a state where the silver halide emulsion layer is wound outside. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the polyester film contains polyethylene-2,6-naphthalate as a main constituent. 5. A polyester film support having at least one magnetic recording layer on the surface opposite to the surface having the photosensitive silver halide emulsion layer on the polyester film support.
The silver halide photographic light-sensitive material according to claim 2, 3 or 4.