JPH07306497A - Photographic supporting body - Google Patents

Abstract

PURPOSE:To provide a photographic supporting body excellent in mechanical strength and dimensional stability, reduced in winding habit curl, free from transporting defect in pre-splice process even if the diameter of a core is made small, excellent in classifying workability after developing and composed of a biaxialby oriented polyester film. CONSTITUTION:This photographic supporting body is composed of the biaxially oriented polyester film and is obtained by processing the biaxial oriented polyester film humidified to 0.1-1.5% moisture content at the temp, lower than Tg by 15-30 deg.C for >=0.1hr and after that, applying at least one layer of an under layer on the surface of the biaxial oriented polyester film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic support comprising a biaxially stretched polyester film having excellent mechanical strength and dimensional stability and having a reduced curl curl.

[0002]

2. Description of the Related Art In recent years, the use of photographic light-sensitive materials (hereinafter, also simply referred to as light-sensitive materials) has been diversified, and it has become possible to speed up film unwinding during shooting, increase shooting magnification, and downsize shooting devices. Remarkably advanced. Therefore, a support for a photographic light-sensitive material is required to have properties such as excellent mechanical strength and dimensional stability. Further, in the roll film-shaped photographic light-sensitive material, it is required to reduce the diameter of the winding core.

A triacetyl cellulose film (hereinafter also referred to as a TAC film) has been conventionally used for a roll film-shaped photographic light-sensitive material such as a general color negative film. However, the TAC film has a small mechanical strength and has a large dimensional change due to moisture absorption, so that the film cannot be thinned. Further, the curling curl is increased by reducing the diameter of the winding core. For this reason, there is a new problem of conveyance failure in the press-price process before the development process. In other words, in a large-scale processing lab, it is normal to process several photographic films that have already been taken, one by one, by joining them together to make them long, and then processing them all at once. If the curling curl of the photographed photographic film is too large, it becomes difficult to bond the photographic film.

A biaxially stretched polyethylene terephthalate film (hereinafter also referred to as a PET film) has excellent transparency, mechanical strength and dimensional stability. It is used in printing light-sensitive materials that are required to have strict properties, and in films for X-rays that require transparency and elasticity.

However, the PET film does not have the curl curl recovery after the developing treatment as seen in the TAC film, and when it is used for a roll film type photographic light-sensitive material, the curl curl after the developing treatment is too large. In addition to being inferior in handling at the time of sorting work, there is a problem that scratches occur, defocus, jamming at the time of conveyance, etc. occur in a step of printing an image on photographic printing paper after development processing, for example.

The PET film is more difficult to wind than the TAC film, but when the diameter of the core is reduced,
It wasn't enough.

Generally, polyester films are excellent in mechanical strength and dimensional stability. Therefore, by reducing the curl curl of the polyester film typified by the PET film, the curl curl after the development processing can be reduced, and it is considered that the above various problems can be solved.

From this point of view, as a method for reducing curling curl of a polyester film, Japanese Patent Laid-Open No. 51-16358 has been proposed.
No. 5, thermoplastic resin film Tg-5 ° C to Tg-30
A method of heat-treating at ℃ for 0.1 to 1500 hours has been proposed. Further, in JP-A-6-35118, Tg is 90 ° C to 200 ° C.
After undercoating the polyester film of
A method of heat treatment for up to 1500 hours has been proposed.

Thermoplastic resin film Tg-5 ℃ ~ Tg
The method of heat treatment at −30 ° C. for 0.1 to 1500 hours is PET.
Film and polyethylene naphthalate film (P
EN film) and other crystalline or semi-crystalline thermoplastic resins have the effect of reducing curling curl and seemed effective. However, such a long-time heat treatment at a relatively high temperature has a problem that the quality of the film is significantly impaired.

That is, in general, a light-sensitive material has a plastic film as a base material, and various functional layers such as an adhesive layer and an antistatic layer, and a photographic light-sensitive layer are laminated on the surface thereof. As a manufacturing procedure, usually, a wide and long plastic film is coated with the above-mentioned functional layer, and the film is wound as an intermediate product on a core having a relatively large diameter. After that, it is cut into the final product form and packaged.

It is advantageous that this intermediate product is as wide and long as possible in terms of shortening the switching time and improving the productivity, and the weight of the intermediate product tends to increase more and more. As a result, a considerable load is applied to the winding core.

By the way, it is well known that when a thermoplastic resin film is heated near its Tg, its elastic modulus is rapidly lowered. Therefore, under the condition that a large load is applied, the Tg
If the film is heat-treated in the vicinity for a long time, the film cannot bear the load, and wrinkles, folds, and pushes occur.
Even if the surface failure is such a minute that it cannot be seen with the naked eye, if an undercoat layer is applied in the subsequent undercoat layer application step, it will become apparent as a coating failure or deterioration of the flatness of the film. The reality is that it cannot be used as a photographic support.

The method of undercoating a polyester film having a Tg of 90 ° C. to 200 ° C. and then heat treating it at 50 ° C. to Tg for 0.1 to 1500 hours is, in principle, completely different from the method described in JP-A-51-16358. It is the same method, and therefore, heat treatment in the vicinity of the Tg of the film is necessary to sufficiently reduce the curl. For example, a polyester film with a Tg of 90 ° C cannot achieve its full effect without heat treatment at 60 ° C or higher, and a polyester film with a Tg of 120 ° C has a
The fact is that the effect cannot be sufficiently obtained unless heat treatment is performed at 0 ° C or higher. Therefore, the Tg of the film is high, and the film must be heat-treated at a very high temperature, which causes the following new problem.

That is, in general, the maximum temperature at which a light-sensitive material can be used at any given time is 50 ° C. at most, and use at a higher temperature is limited to a short time. The heat resistance of the undercoat layer composed of various functional layers is usually designed in consideration of the normal temperature condition. Therefore, these undercoat layers cannot withstand heat treatment for sufficiently reducing curling curl of the film, and transfer of additives to the coating film surface such as deterioration and decomposition of the material, bleed-out, coating film It causes various problems such as surface cracking.

As described above, the film has excellent mechanical strength and dimensional stability that enable the film to be unwound at high speed during shooting, the shooting magnification to be high, and the shooting device to be downsized. Further, even if the diameter of the core is reduced, there is no conveyance failure in the press-price process, and a photographic support excellent in sorting workability after the development processing has not been obtained.

[0016]

SUMMARY OF THE INVENTION In view of the above problems, the object of the present invention is to provide excellent mechanical strength and dimensional stability, curl curl is reduced, and even if the diameter of the winding core is reduced, conveyance failure in the press-price step is difficult. Another object of the present invention is to provide a photographic support made of a biaxially stretched polyester film which is free from the above and has excellent sorting workability after the development processing.

[0017]

The above object of the present invention can be achieved by the following constitutions.

1. A photographic support comprising a biaxially stretched polyester film, wherein the biaxially stretched polyester film has a moisture content of 0.1% or more and 1.5% or less.
1. A photographic support characterized by having at least one undercoat layer coated on the surface of the biaxially stretched polyester film after being treated at a temperature of 5 ° C. or higher and Tg-30 ° C. or lower for 0.1 hour or longer. 2. The photographic support according to 1 above, wherein the biaxially stretched polyester film has an ethylene terephthalate unit or an ethylene 2-6 naphthalate unit as a main constituent. The photographic support according to 1 or 2 above, wherein the biaxially stretched polyester film contains an ethylene terephthalate unit or an ethylene 2-6 naphthalate unit in an amount of 70% by weight or more. Hereinafter, the present invention will be described in detail. To do.

The polyester constituting the biaxially stretched 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 component is terephthalic acid, isophthalic acid, phthalic acid, 2-6 naphthalene dicarboxylic acid, 2-7 naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid. , Cyclohexanedicarboxylic acid, diphenyldicarboxylic acid,
Examples thereof include diphenyl thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid and phenylindane dicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4 -Hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol and the like can be mentioned.

Among the polyesters containing these as the main constituents, terephthalic acid and / or 2-6 naphthalenedicarboxylic acid as a dicarboxylic acid component and diol component as a dicarboxylic acid component, from the viewpoints of transparency, mechanical strength, dimensional stability and the like. Polyesters containing ethylene glycol and / or 1-4 cyclohexanedimethanol as main constituents are preferred. Among them, polyester mainly composed of polyethylene terephthalate or polyethylene 2-6 naphthalate, copolymerized polyester composed of terephthalic acid, 2-6 naphthalenedicarboxylic acid and ethylene glycol, and a mixture of two or more of these polyesters are mainly used. Polyester as the preferred constituent is preferred.

When the content of ethylene terephthalate unit or ethylene 2-6 naphthalate unit in the polyester is 70% by weight or more, a film having excellent transparency, mechanical strength and dimensional stability can be obtained. It is well known that a film containing polyethylene 2-6 naphthalate as a main constituent is superior to a film containing polyethylene terephthalate as a main constituent in mechanical strength and heat resistance. On the other hand, polyethylene 2-
The film containing 6-naphthalate as a main component also has disadvantages such as the property of emitting fluorescence and the high price of resin.

Therefore, depending on the purpose of use, a film containing polyethylene terephthalate as a main constituent is usually used, and polyethylene 2 is used particularly when highly thinning is required or when the film is abused at a high temperature. A film containing -6 naphthalate as a main constituent may be used. Further, by mixing the two, the drawbacks of each other can be compensated.

The polyester constituting the biaxially stretched polyester film of the present invention may be further copolymerized with other copolymerization components as long as the effects of the present invention are not impaired, and other polyesters may be mixed. It may be done.
Examples of these include the above-mentioned dicarboxylic acid component and diol component, or polyesters composed of them.

The polyester constituting the biaxially stretched polyester film of the present invention contains an aromatic dicarboxylic acid having a sulfonate group or an ester-forming derivative thereof and a dicarboxylic acid having a polyoxyalkylene group in order to prevent delamination of the film. You may copolymerize an acid or its ester forming derivative, the diol which has a polyoxyalkylene group, etc. Among them, 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo is preferable in view of polymerization reactivity of polyester and transparency of film.
-2,6-naphthalenedicarboxylic acid and compounds obtained by substituting these metals with other metals, such as potassium and lithium, ammonium salts, phosphonium salts or the like, or ester-forming derivatives thereof, polyethylene glycol, polytetramethylene glycol, A polyethylene glycol-polypropylene glycol copolymer and a compound having a carboxyl group by oxidizing the hydroxy groups at both ends thereof are preferable. The proportion of copolymerization for this purpose is preferably 0.1 to 10 mol% based on the difunctional dicarboxylic acid constituting the polyester.

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 1 to 20 mol% based on the difunctional dicarboxylic acid constituting the polyester.
Is preferred.

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 content of the above antioxidant is usually 0.01 to 2% by weight, preferably 0.1 to 0.5%, based on the polyester. By setting the content of the antioxidant in this range, it is possible to prevent the so-called fog phenomenon in which the density of the unexposed portion of the light-sensitive material becomes high, and the haze of the film can be suppressed to a low level, so that the photographic support is excellent in transparency. The body is obtained. In addition,
These antioxidants may be used alone, or
Of course, two or more kinds may be used in combination.

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.

As the color tone, gray dyeing is preferable as seen in general light-sensitive materials. As these dyes, there are MACROLEX series manufactured by Bayer, SUMIPLAST series manufactured by Sumitomo Chemical Co., Ltd., and Diaresi manufactured by Mitsubishi Kasei.
From the n series and the like, one kind may be used alone, or two or more kinds of dyes may be mixed and used so as to obtain a necessary color tone. At this time, the spectral transmittance of the film is 400 to 700 nm.
60% or more and 85% or less in the wavelength range of
It is preferable to use the dye so that the difference between the maximum and the minimum of the spectral transmittance is within 10% in the wavelength range of m in order to prevent the light piping phenomenon and obtain a good photographic print.

The biaxially stretched polyester film of the present invention may be provided with slipperiness, if necessary. The means for imparting slipperiness is not particularly limited, but an external particle addition method of adding inert inorganic particles to polyester, an internal particle precipitation method of precipitating a catalyst added at the time of polyester synthesis, or a surfactant is used as a film. The method of applying on the surface is common. Among these, the internal particle deposition method in which the deposited particles can be controlled to be relatively small is preferable because slipperiness can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but Ca and Mn are particularly preferable because high transparency can be obtained. These catalysts may be used alone or in combination of two or more.

The biaxially stretched polyester film of the present invention may have a multilayer structure composed of different kinds of polyester.
For example, when the layer made of polyester having ethylene terephthalate unit or ethylene 2-6 naphthalate unit as a main constituent is A layer and the layer made of other polyester is B layer or C layer, Or a three-layer structure such as A layer / B layer / A layer, A layer / B layer / C layer, B layer / A layer / B layer or B layer / A layer / C layer. . 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 the layer A is preferably 30% or more, and more preferably 50% or more of the total thickness of the polyester film.

By using polyethylene terephthalate, polyethylene naphthalate or other homopolyesters or other copolyesters, which are excellent in transparency, mechanical strength and dimensional stability, as the polyester constituting the B layer or the C layer. , Transparency of the whole film,
Mechanical strength, dimensional stability, etc. can be improved.

Further, when the biaxially stretched polyester film of the present invention has a multi-layered structure, the above-mentioned oxidation prevention, light piping prevention, slipperiness and other functions are added, or various additives other than those mentioned above are added to the surface. Since it is sufficient to perform only the layer, the transparency of the film can be maintained high.

The biaxially stretched polyester film of the present invention can be further prevented from precipitating oligomers on the surface of the film by laminating a layer made of another polyester on both sides thereof. At this time, it is preferable to use the above-mentioned polyester as the polyester constituting the layer composed of another polyester (polyester D) laminated on both sides. The Tg of the polyester D is preferably higher than the Tg of the polyester of the inner layer. The Tg of the polyester D is preferably 5 ° C. or higher, more preferably 15 ° C. or higher than the Tg of the polyester of the inner layer. Further, the thickness of the layer made of polyester D is required to be thin within a certain range in order to maintain the water absorption of the film.
μm is preferred.

The method of synthesizing the polyester as the raw material of the biaxially stretched polyester film of the present invention is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first using a dialkyl ester as a dicarboxylic acid component,
It is possible to use a transesterification method in which an ester exchange reaction is carried out between this and a diol component, and this is heated under reduced pressure to remove an excess diol component and thereby polymerize.
At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. Further, in each process during synthesis, anti-coloring agent, antioxidant, crystal nucleating agent, slip agent, stabilizer, anti-blocking agent, ultraviolet absorber, viscosity modifier, defoaming agent, clarifying agent, antistatic agent, A pH adjuster, dye, pigment, etc. may be added.

The biaxially stretched polyester film of the present invention has a curling curl of 110 as determined by the following method.
It is preferably m ⁻¹ or less. If the curling curl of the film is too large, the transportability in the press-price process and the workability during sorting work will be poor. In addition, it is preferable that the curl has an appropriate curl because it makes it easier to eject the leading end of the film from the film cartridge and is excellent in so-called bellow ejection. Therefore, the more preferable range of the curl of the film is from 5 to 90 m ^-1 .

<Winding curl> A photosensitive material having a width of 35 mm and a length of 1200 mm was conditioned for 1 day under the conditions of 23 ° C. and 55% RH, and the photographic photosensitive layer side was placed inside and the diameter was 7 mm. Fix it so that it does not rewind on the core. Then put the film in a polyethylene cartridge case and
Heat treatment at ℃, 20% RH for 4 hours, then 23
Let stand for 1 hour under the condition of ℃ and 55% RH. Then release the film from the core and pinch it with the clip, with the outer edge of the film roll up, and hang it. In this state, it is further left for 1 hour under the condition of 23 ° C. and 55% RH. After this, the degree of curling curl at the lower end of the film is determined by the reciprocal of the radius of curvature. The unit is m ^-1 .

The thickness of the biaxially stretched 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. Especially when the film is used as a photographic light-sensitive material for color negative, 20
It is preferably 125 μm, particularly 40 to 90 μm. When it is used for medical and printing photographic light-sensitive materials, 50 to 20
It is preferably 0 μm, particularly 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 thick, it is no longer superior to conventional supports for photosensitive materials.

The biaxially stretched polyester film of the present invention is provided with a curl in the width direction so that it is free from problems such as scratches and out-of-focus blur during the printing process on photographic printing paper. It is preferable for obtaining the material. The effect is exhibited when the photographic photosensitive layer is provided on the convex side of the curl of the film and the film is wound with its surface facing inward.

The degree of curl imparted to the film for such a purpose varies depending on the thickness, elastic modulus, hygroscopic expansion coefficient of the photographic photosensitive layer to be provided, and therefore cannot be determined unconditionally. It may be applied so that it is as flat as possible within the range where the photosensitive layer side does not become convex,
Normally, 23 ° C., a 5 m ^-1 50 m ^-1 under the conditions of RH 20%. The degree of curl is a value obtained as follows.

<Curling degree in width direction> 35m width from film
A test piece cut into a size of m and 2 mm in length is 23 ° C, 20% R
After conditioning the humidity for 1 day under the condition of H, the radius of curl of the curl in the width direction of the sample is calculated in meters, and the reciprocal thereof represents the curl degree in the width direction. The unit is m ^-1 .

The method of imparting curl in the width direction to the film is not particularly limited, and examples thereof include a method of laminating polyesters having different copolymerization components or main constituents, and the same or different polyesters having different intrinsic viscosities. A method of laminating, a method of further changing the thickness of both outer layers with a three-layer structure, a method of changing the stretching conditions of the front and back and heat setting conditions to give a molecular orientation and a crystallinity distribution in the film thickness direction, etc. To be Further, a method of treating with a chemical solution such as resorcin can also be mentioned. Furthermore, it is of course possible to appropriately combine these methods and to impart curl in a layer structure of four or more layers by using these methods.

Among these, a method of laminating polyesters having a two-layer structure and having the same main constituent but different copolymerization components,
Alternatively, a method in which the center layer and both outer layers have a three-layer structure in which polyesters having the same main constituent but different copolymerization components are laminated and the thickness of both outer layers is changed is preferable because the degree of curling can be easily adjusted. When the thickness of both outer layers is changed for this purpose, it is preferable from the viewpoint of film production that 1.1 ≦ d1 / d2 ≦ 10, where d1 and d2 are the thicknesses of both outer layers. If the film does not fall within the above range, stretching may be extremely difficult.

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

The Tg of the biaxially stretched polyester film of the present invention is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. Tg is calculated as an average value of the temperature at which the baseline starts to be biased, which is measured by a differential scanning calorimeter, and the temperature at which the baseline newly returns. When Tg is not less than this value, the film is not deformed in the drying step of the developing processor, and a photosensitive material having a small curling curl after the developing processing can be obtained.

Next, the method for producing the polyester film of the present invention will be described.

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 passed through a plurality of roll groups and / or a heating device such as an infrared heater to change the glass transition temperature (Tg) of the polyester to Tg + 100 ° C.
It is a method of heating in the range of 1 and stretching in a single stage or in multiple stages. The draw ratio is usually in the range of 2.5 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-layer structure, the stretching temperature is set by the Tg of the polyester of each constituent layer.
Of these, it is preferable to use the highest Tg as a reference.

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.

Next, the polyester film uniaxially stretched in the machine direction obtained as described above was treated with Tg to Tm-20.
Within the temperature range of ° C, 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. In the case of the present invention,
The elastic modulus in the width direction is made larger than the elastic modulus in the longitudinal direction. It may be changed according to the purpose of use. At this time,
It is preferable to laterally stretch while sequentially raising the temperature difference in the range of 1 to 50 ° C. in the stretching regions divided into two or more because the distribution of the physical properties in the width direction can be reduced. Further, after the transverse stretching, the film is kept in the range of Tg-40 ° C or higher at 0.01 to below the final transverse stretching temperature.
Holding for 5 minutes is preferable 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 lower, and the clip holding portions at both ends of the film are cut and wound up. At this time, within the temperature range below the final heat setting temperature and above Tg, 0.1 to 1 in the width direction and / or the longitudinal direction.
It is preferable to perform 0% relaxation treatment. 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 means for cooling and relaxing treatment is not particularly limited and can be carried out by conventionally known means, but it is particularly preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film. The cooling rate is T ₁ , the final heat setting temperature, and t is the time required for the film to reach Tg from the final heat setting temperature.
It is a value obtained by (T ₁ −Tg) / t.

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

In the production of the above film, functional layers such as an antistatic layer, a slipping layer, an adhesive layer and a barrier layer may be coated before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be applied as necessary. Further, for the purpose of improving the strength, it is also possible to carry out the stretching used for known stretching films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal transverse stretching, and transverse / longitudinal stretching. Of course, the clip gripping parts on both ends of the cut film are used as raw materials for films of the same type or different types after being pulverized or after being subjected to granulation treatment, depolymerization / repolymerization, etc. as necessary. It may be reused as a raw material for the film.

Since the biaxially stretched polyester film obtained as described above still has a tendency to be easily wound, in the present invention, the biaxially stretched polyester film is further adjusted to have a water content of 0.1% or more and 1.5% or less. 15 in damp
The film is treated for 0.1 hour or more at a temperature of not lower than Tg of the film and not higher than Tg of the film. When the film has a multi-layered structure, one having the lowest Tg value among the polyesters constituting the layer that substantially plays a role in the rigidity of the film is used as a reference.

By incorporating a slight amount of water, which seems to have nothing to do with the appearance, into the hydrophobic polyester film, a sufficient curling curl-reducing effect can be exhibited even by heat treatment at a lower temperature than in the past. is there. If the water content of the film during processing is small, a sufficient curling curl reduction effect cannot be obtained, and if it is too large, coating failure after coating the undercoat layer cannot be improved. The water content and Tg are values obtained as follows.

<Water content> The water content is measured at a drying temperature of 150 ° C. using a trace moisture meter (for example, CA-05 type manufactured by Mitsubishi Kasei Co., Ltd.).

<Glass transition temperature Tg> 10 mg of film,
Melt at 300 ° C. in a nitrogen stream of 300 ml / min, and immediately quench in liquid nitrogen. The quenched sample is set in a differential scanning calorimeter (DSC8230, manufactured by Rigaku Denki Co., Ltd.), heated in a nitrogen stream of 100 ml / min at a heating rate of 10 ° C./min, and Tg is detected. Tg is an average value of the temperature at which the baseline starts to become biased and the temperature at which the baseline newly returns. The measurement start temperature is set to a temperature lower than the measured Tg by 50 ° C. or more.

The higher the treatment temperature is, the shorter the curling effect of curling can be obtained. However, if the treatment temperature is too high, the film tends to be wrinkled, pushed, and broken to improve the coating failure after coating the undercoat layer. Not done. When the treatment temperature is low, a long treatment time is required, but when the treatment temperature is too low, a sufficient curling curling reduction effect cannot be obtained. The treatment time is 0.1 hour or more, and the curling curl reducing effect is recognized, and the longer the time, the higher the effect is obtained, so it can be appropriately set to obtain the desired effect, but if it is too long, the productivity is increased. Since it is inferior to 1, it is usually preferable for up to 1500 hours.

The method of allowing the polyester film to contain an appropriate amount of water is not particularly limited, but, for example, embossing or bending the end part at any position of the end part or the central part of the film or over the entire length. , A method of partially controlling the film thickness to prevent the films from sticking to each other and controlling the humidity for a necessary period in an air-conditioned room. A method of sandwiching it between the film and the film, a method of blowing humidified air at the time of winding, and the like. Of these, the method of performing embossing is the simplest, reliable, and preferable. Of course, a plurality of these methods may be combined.
For such a purpose, it is preferable that the embossing is usually performed so that irregularities of 10 to 100 μm are formed.

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 is in the 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.

If the roll diameter of the wound film roll is too large, uniform treatment becomes difficult.
It is preferable that it is small to some extent, usually 1000 mm or less,
850 mm or less is preferable.

In order to further secure the effect of the present invention, when heat-treating a film containing an appropriate amount of water, the film roll is made of a material having a water vapor barrier property,
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, further, following the above-mentioned treatment, at least one undercoat layer is applied to the surface of the film so that there is no coating failure and the photographic support is excellent in flatness after application of the undercoat layer. You can get the body. The details of this reason are unknown, but the surface failure of the film is highly suppressed compared to the conventional curl curl reduction method by heat treatment in the vicinity of Tg of the film, and a state where the water content in the film is appropriately adjusted It seems that there is a synergistic effect by coating the undercoat layer.

Generally, even if a hydrophilic photographic emulsion layer is directly coated on a hydrophobic film such as a polyester film, the required adhesive strength cannot be obtained. Therefore, it is usually necessary to coat an undercoat layer on the film surface. The material that can be used for the undercoat layer is not particularly limited, and examples thereof include a copolymer of vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride as a starting material, and polyethyleneimine. , Polyester, polystyrene, polyurethane, epoxy resin, grafted gelatin, nitrocellulose and the like, and mixtures thereof.

In these subbing layers, surfactants, antistatic agents, antihalation agents, crossover cut agents, coloring dyes, pigments, thickeners, coating aids, antifoggants, antioxidants, and ultraviolet absorbers. One or more kinds of various additives such as an agent, an ultraviolet stabilizer, an etching treatment agent, a magnetic powder and a matting agent may be contained.

The method of coating the undercoat layer is not particularly limited, and various conventionally known methods can be used. For example, a method in which a solution or dispersion obtained by dissolving the above materials in a suitable solvent is applied to the film surface using an air knife coater, a dip coater, a curtain coater, a wire bar coater, a gravure coater, an extrusion coater, and the like, and dried. Is mentioned. At this time, if necessary, corona discharge treatment, ultraviolet treatment,
A method of surface activation treatment such as glow discharge treatment, plasma treatment, or flame treatment, or an etching treatment method such as resorcin treatment, phenol treatment, alkali treatment, amine treatment, or trichloroacetic acid treatment may be used. Of these, corona discharge treatment is preferably used. Further, from the viewpoint of working environment, the coating liquid is preferably an aqueous dispersion or an aqueous solution.

The subbing layer may be composed of one layer or two or more layers, and further, an antistatic layer, a slipping layer, a barrier layer, an antihalation layer, a crossover cut layer, an ultraviolet absorbing layer, a magnetic recording layer. Etc. may be included.

The film coated with the undercoat layer as described above is cooled to room temperature, wound up, and stored until it is sent to the next step. At this time, the water content of the film is 0.
Adjusting to 2% or less is preferable because curling due to storage can be prevented.

Next, a method for forming a photosensitive material will be described.

The photographic material is provided with a photographic emulsion layer on at least one side of the photographic support of the present invention, and the photographic emulsion layer can be formed by coating a silver halide emulsion. The photographic emulsion layer can be provided on one side or both sides of the photographic support. The photographic emulsion layer is
One or two or more layers can be provided on each surface. The silver halide emulsion can be coated directly on the photographic support or through another layer, for example, a hydrophilic colloid layer containing no silver halide emulsion. Further, the silver halide emulsion layer may be separately coated on each of the silver halide emulsion layers having different sensitivities, for example, high sensitivity and low sensitivity.
In this case, an intermediate layer may be provided between each silver halide emulsion layer. Further, a hydrophilic colloid layer, a protective layer, an antihalation layer, a backing layer, a masking layer, or the like may be provided on the silver halide emulsion layer or in an intermediate layer, or anywhere between the silver halide emulsion layer and the photographic support. A non-photosensitive layer may be provided.

The silver halide emulsion used in the present invention is
For example, Research Disclosure (hereinafter abbreviated as RD) No. 17643, pages 22 to 23 (December 1979), “1. Emulsion preparation and types”, and R
D No.18716, p. 648, "The Physics and Chemistry of Photography" by Grafkeide, published by P.Glkides, Chemie et Phyziq.
ue Photographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDaffi)
n, Photographic Emulsion Chemistry Focal Press196
6), "Production and coating of photographic emulsions" by Zelikmann et al., Published by Focal Press (VLZelikman et al, Making and coa
Ting Photographic Emulsion, Focal Press 1964) and the like.

The silver halide emulsion used in the present invention is
U.S. Patents 3,574,628 and 3,665,394 and British Patent 1,
Monodisperse emulsions described in 413,748 and the like are also preferable.

The silver halide emulsion used in the present invention can be subjected to physical ripening, chemical ripening and spectral sensitization. The additive used in such a process is RD No.17.
643, RD No. 18716 and RD No. 308119 (hereinafter abbreviated as RD 17643, RD 18716 and RD 308119, respectively). Table 1 shows the location of the description.

[0075]

[Table 1]

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. Table 2 shows the relevant locations.

[0077]

[Table 2]

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used, specific examples of which are described in RD 17643 and RD 308119 below. Table 3 shows the related description.

[0079]

[Table 3]

These additives are also RD 308119 1007
It can be added to the photographic light-sensitive layer by the dispersion method described in page XIV.

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned RD 308119 VII-K can be provided.

When the above color photographic light-sensitive material is constructed,
Various layer configurations such as the forward layer, the reverse layer, and the unit configuration described in the above-mentioned RD 308119 VII-K can be adopted.

To develop the photographic light-sensitive material of the present invention, for example, TH James, Theory of the Photographic Process, 4th Edition.
e Photografic Process Forth Edition) pp. 291-33
P. 4 and Journal of the American Chemical Society, 73rd.
The developer known per se, which is described in Vol. 3, page 3,100 (1951), can be used. Further, the color photographic light-sensitive material is the same as the above-mentioned RD 17643, pages 28 to 29, RD 18716.
It can be processed by a conventional method described on page 615 and RD 308119 XIX.

[0084]

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

In the following examples, density, glass transition temperature and melting point, film haze, water content, intrinsic viscosity,
Elastic modulus and rupture strength, thermal shrinkage, coefficient of hygroscopic expansion, curl degree in width direction, curl curl values, coating failure after coating with undercoat layer, flatness, press price transportability, sorting workability Each evaluation rank of is calculated by the following.

(1) Density 23 ° C., 55% RH humidity controlled film for 8 hours, 25 ± 0.5
It is put into a density gradient tube (n-heptane-carbon tetrachloride system) kept at 0 ° C., and after 24 hours, the scale of the film position is read. At the same time, the scale of the position of the standard sphere is read and a calibration curve is created to obtain the density. The unit is g / cm ³ .

(2) 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 ml / min and immediately cooled in liquid nitrogen.
A differential scanning calorimeter (manufactured by Rigaku Denki Co.,
DSC8230 type), and in a 100 ml nitrogen stream per minute, every minute
The temperature is raised at a heating rate of 10 ° C. and Tg and Tm are detected.
Tg was the average temperature Tm of the temperature at which the baseline started to be biased and the temperature at which the baseline newly returned to the baseline, and the peak temperature of the endothermic peak was taken as Tm. The measurement start temperature is set to a temperature lower than the measured Tg by 50 ° C. or more.

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

(4) Intrinsic viscosity A film or pellet was mixed with phenol, 1,1,2,2-
Dissolve in a mixed solvent of tetrachloroethane (weight ratio 60/40) to prepare solutions with concentrations of 0.2 g / dl, 0.6 g / dl, 1.0 g / dl, and use an Ubbelohde viscometer to measure each concentration ( The specific viscosity (ηsp) in C) is determined. Then
Plot ηsp / C against C and extrapolate the resulting line to zero concentration Ask for. The unit is indicated by dl / g.

(5) Elastic Modulus and Breaking Strength The film was cut into a piece having a width of 10 mm and a length of 200 mm.
After conditioning the humidity for 12 hours under the conditions of 3 ° C and 55% RH, Tencilon (RTA-100) manufactured by Orientec Co., Ltd. was used, and the chuck distance was set to 100 mm, and the tensile test was performed at a pulling speed of 100 mm / min for elasticity. The rate and the breaking strength were determined.

(6) Heat Shrinkage A 150 mm × 150 mm sample was cut out from the film and heated at 23 ° C.
After conditioning the humidity for 1 day under the condition of 55% RH, put a scoring line at 100 mm intervals. And heat treatment at 130 ℃ for 30 minutes,
Further, the distance between the scoring lines is measured after the humidity is controlled for 1 day under the conditions of 23 ° C. and 55% RH. The difference between the intervals of the scoring lines before and after the heat treatment is calculated and expressed as a percentage of the interval before the heat treatment. It should be noted that the direction of contraction was + and the direction of expansion was − as compared with before heat treatment.

(7) Curling degree in the width direction A sample having a width of 35 mm and a length of 2 mm was cut out, and the temperature was 23 ° C. and 20% RH.
After conditioning the humidity for one day under the condition of, the radius of curvature of the curl in the width direction of the sample is determined in meters, and the reciprocal thereof indicates the curl degree in the width direction. The unit is m ^-1 .

(8) Hygroscopic expansion coefficient Thermomechanical property measuring device (TM-7000; manufactured by Vacuum Riko Co., Ltd.)
According to, the elongation of the dimension was measured and determined when the humidity was changed from 10% RH to 90% RH at a temperature of 23 ° C. Unit is cm /
It is expressed in cm ·% RH.

(9) Water Content The water content was measured at a drying temperature of 150 ° C. using a trace moisture meter (CA-05 type manufactured by Mitsubishi Kasei Co., Ltd.).

(10) Winding curl A photographic light-sensitive material having a width of 35 mm and a length of 1200 mm was prepared at 23 ° C. and 55
After humidity conditioning for 1 day under the condition of% RH, the photographic photosensitive layer side is placed inside and fixed so as not to be rewound on a core having a diameter of 7 mm. Then, this film is put in a polyethylene cartridge case, heat-treated under the conditions of 50 ° C. and 20% RH for 4 hours, and further left to cool under the conditions of 23 ° C. and 55% RH for 1 hour. Then release the film from the core and pinch it with the clip, with the outer edge of the film roll up, and hang it. In this state, it is further left for 1 hour under the condition of 23 ° C. and 55% RH. After this, the degree of curling curl at the lower end of the film is determined by the reciprocal of the radius of curvature. The unit is m ^-1 .

(11) Coating failure The number of surface failures per 1 m ^{2 of} film was visually evaluated and ranked according to the following criteria. The practicality in this ranking is determined based on the acceptability of the quality of the photosensitive material, and it is necessary that the rank is ◯ or higher.

Rank Number of surface defects ◎ 0 ○ 1 to 3 × 4 or more (12) Flatness The film was conditioned under conditions of 23 ° C and 55% RH for 12 hours and then placed on a flat board. The degree of waviness was visually evaluated and ranked according to the following criteria. The practicality in this ranking is determined based on the acceptability of the quality of the photosensitive material, and it is necessary that the rank is ◯ or higher.

Rank Waviness ◎ Good ◯ ○ If you look closely, you can see the waviness. × Waviness is large. (13) Press-price transportability Using the photographic light-sensitive material with the curl in the same manner as the curl curl measurement described above, It was inserted into a Noritsu Press Splicer PS-35-1 (manufactured by Noritsu Koki Co., Ltd.) so that the core side was the first. The following criteria were used to rank each level according to the number of occurrences of 10 defective conveyances.

Rank Number of occurrences of poor conveyance ◎ 0 ○ ○ 1 × 2 to 10 (14) Sorting workability A cine-type photosensitive material with a curl was used in the same manner as the curl curl measurement described above. Development was carried out with an automatic processor NCV36 (manufactured by Noritsu Koki Co., Ltd.). Each level was developed by 10 pieces, and the negative case was packed in a usual method and ranked according to the following criteria.

Rank Ease of work ◎ No problem ○ Somewhat difficult × Very difficult Polyester A to polyester F were processed as follows.
Prepared.

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

(Polyester B) 100 parts by weight of dimethyl naphthalene dicarboxylate 2-6, 60 parts by weight of ethylene glycol, and calcium acetate hydrate as an ester exchange catalyst.
1 part by weight was added, and the transesterification reaction was performed according to a conventional method. 5-sodium sulfodi (β-
Hydroxyethyl) isophthalic acid in ethylene glycol (concentration 35% by weight) 5 parts by weight, antimony trioxide 0.05
Parts by weight and 0.03 parts by weight of phosphoric acid trimethyl ester were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 290 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.55.

(Polyester C) Dimethyl terephthalate
To 100 parts by weight of ethylene glycol and 65 parts by weight of ethylene glycol, 0.05 part by weight of magnesium acetate hydrate was added as a transesterification catalyst, and transesterification was carried out according to a conventional method. Antimony trioxide (0.05 parts by weight) and phosphoric acid trimethyl ester (0.03 parts by weight) were added to the obtained product. Then, 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) 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. 5 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.03 part by weight, Irga Knox 1010
(Ciba Geigy) 0.2 parts by weight and sodium acetate
0.04 parts by weight was added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 280 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.62.

(Polyester E) 2-6 Magnesium acetate hydrate as a transesterification catalyst in 100 parts by weight of dimethyl naphthalene dicarboxylate and 60 parts by weight of ethylene glycol.
05 parts by weight was added, and transesterification reaction was carried out according to a conventional method. 5-sodium sulfodi (β-
30 parts by weight of a solution of hydroxyethyl) isophthalic acid in ethylene glycol (concentration 35% by weight) and 8 parts by weight of polyethylene glycol (number average molecular weight: 3000), 0.05 parts by weight of antimony trioxide, 0.03 parts by weight of phosphoric acid trimethyl ester, Irganox 1010 0.2 parts by weight (manufactured by Ciba Geigy) and 0.04 parts by weight of sodium acetate were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 290 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.55.

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

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

(Film 1) Using polyester A,
After vacuum-drying at 150 ° C. for 8 hours, the mixture was melt-extruded in layers from a T-die at 300 ° C., adhered on 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 of 155 ° C. in a total transverse stretching ratio of 3.3 times. Was stretched. Then 2 at 100 ℃
It was heat-treated for 2 seconds, further heat-set for 5 seconds at the first heat-setting zone at 200 ° C, and heat-set for 15 seconds at the second heat-setting zone at 240 ° C. Then, while performing a 5% relaxation treatment in the lateral direction, bring it to room temperature 30
The mixture was gradually cooled for 2 seconds to obtain a biaxially stretched film having a thickness of 80 μm.

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

The obtained uniaxially stretched film 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 further 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.

(Film 3) Polyester A and polyester B were vacuum dried at 150 ° C. for 8 hours, respectively,
Using two extruders, 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 two-layer laminated unstretched sheet Got 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 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 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.

(Film 4) Polyester C and polyester D were vacuum dried at 150 ° C. for 8 hours, and
Using two extruders, melt-extruding at 285 ° C, joining in layers in a T-die, adhering to a cooling drum at 30 ° C while applying static electricity, cooling and solidifying, and a laminated unstretched sheet having a two-layer structure. Got 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 100 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 115 ° C., a total transverse stretching ratio of 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%, the mixture was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 90 μm.

(Film 5) Polyester A and polyester E were vacuum dried at 150 ° C. for 8 hours, respectively,
Using two extruders, melt extrude at 300 ° C, join in layers in a T-die, adhere to a cooling drum at 50 ° C while applying static electricity, and cool and solidify to form a three-layer laminated unstretched sheet Got At this time, the extrusion rate of each extruder was adjusted so that the thickness ratio of each layer was 1: 1: 3. This unstretched sheet was longitudinally stretched at 135 ° C using a roll-type longitudinal stretching machine 3.
It was stretched 3 times.

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 further at a second stretching zone of 155 ° C. in a total transverse stretching ratio of 3.6 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.

Each layer of the obtained biaxially stretched film was scraped off, and the intrinsic viscosity, the glass transition temperature and the melting point of each of them were measured. The polymer intrinsic viscosity of the polyester A layer of the film 1 was 0.58 and the glass transition temperature was 123. ℃, melting point 270
℃, the intrinsic viscosity of the polymer of the polyester F layer of film 2 is 0.60, glass transition temperature 105 ℃, melting point 267 ℃ film 3
The intrinsic viscosity of the polymer of the polyester A layer is 0.58, the glass transition temperature is 123 ° C, the melting point is 270 ° C, the intrinsic viscosity of the polymer of the polyester B layer is 0.52, the glass transition temperature is 125 ° C, the melting point is 265.
C, the intrinsic viscosity of the polymer of the polyester C layer of film 4 is 0.63, the glass transition temperature is 76 ° C, the melting point is 260 ° C, the intrinsic viscosity of the polymer of the polyester D layer is 0.60, the glass transition temperature.
85 ° C, melting point 255 ° C, intrinsic viscosity of the polymer of the polyester A layer of film 5 is 0.58, glass transition temperature 123 ° C, melting point 2
70 ° C, the intrinsic viscosity of the polyester E layer polymer is 0.52,
The glass transition temperature was 100 ° C and the melting point was 260 ° C. In addition, since the film 3 showed a curl on the polyester A side, the film 4 on the polyester C side, and the film 5 showed a convex curl on the thinner side of the polyester E layer. I went to

The film obtained as described above was wound around a paper core of 200 mm in diameter and the humidity control time was changed as shown in Tables 4 to 7 under the conditions of 23 ° C. and 55% RH. , It was rewound on a separately prepared 200 mm paper core. At this time,
When the water content was measured by cutting out a piece of film from the leading portion and the trailing portion of the film, the leading portion and the trailing portion showed the same value. The results are shown in Tables 4 to 7.

Next, the film wound on the core was double-coated with an aluminum vapor-deposited polyethylene film having a thickness of 20 μm, treated to reduce the curl as shown in Tables 4 to 7, and further at 23 ° C. It was left for 48 hours under the condition of 55% RH.

The obtained film was sampled and measured for each physical property value of the film, and the results are shown in Tables 4 to 7.

Then, an undercoat layer was applied as follows.

8 W / (m ² · min) on one side of the film
Subjected to corona discharge treatment, and then at room temperature and normal humidity,
Subbing coating solution A-1 below was applied at a speed of 50 m / min using a roll-fit coating pan and an air knife and dried at a drying temperature of 90 ° C. for 30 seconds to obtain a subbing layer A having a dry film thickness of 0.8 μm. -1 was formed. The undercoating coating solution B-1 shown below was applied to the other surface of this film by the same method and dried to form an undercoating layer B-1 having a dry film thickness of 0.8 μm.

<Undercoating Liquid A-1> A copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30%). %) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml <Undercoating liquid B-1> 40 wt% butyl acrylate, 20 wt% styrene and glycidyl Acrylate 40% by weight copolymer latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish with water 1000 ml Further undercoat layer A-1 And 8 W / (m ² on the undercoat layer B-1
-Min) corona discharge treatment, and undercoat layer A similarly
-1 is coated with the following subbing coating solution A-2 and dried to form a subbing layer A-2 having a dry film thickness of 0.1 μm.
The undercoating coating solution B-2 shown below was applied onto 1 and dried to form an undercoating layer B-2 having a dry film thickness of 0.8 μm.

<Undercoating Liquid A-2> Gelatin 10 g Compound (UL-1) 0.2 g Compound (UL-2) 0.2 g Compound (UL-3) 0.1 g Silica particles (average particle size: 3 μm) 0.1 g Water Finish with 1000 ml <Undercoating coating liquid B-2> Water-soluble conductive polymer (UL-4) 60 g Latex liquid containing compound (UL-5) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g Curing agent (UL- 6) 12g Polyethylene glycol (weight average molecular weight 600) 6g Finish with water 1000ml Using the film coated with the above undercoat layer, the undercoat layer B-2
A corona discharge of 8 W / (m ² · min) was applied on the above, and the following coating liquid MC-1 was applied so as to have a dry film thickness of 1 μm.

(MC-1) The following components were mixed together with a dissolver and then dispersed with a sand mill to obtain a dispersion liquid.

Nitrocellulose 70 parts by weight Lauric acid 1 part by weight Oleic acid 1 part by weight Butyl stearate 1 part by weight Cyclohexanone 75 parts by weight Methyl ethyl ketone 150 parts by weight Toluene 150 parts by weight Co Deposition γ-Fe ₂ O ₃ (long axis 0.2 μm , Minor axis 0.2 μm, Hc = 650 Oersted) 5 parts by weight Furthermore, the following coating liquid OC-1 was applied on the coating layer of MC-1.
It was applied at 10 ml / m ² .

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml The obtained film was sampled to evaluate coating failure and flatness. The results are shown in Tables 4 to 7.

Here, from film 1, width 35 mm, length 150 m
A sample with a size of m is cut out and the relative temperature is 0, 1 at 23 ° C.
The humidity was controlled for 6 hours under the conditions of 0, 20, 40, 60 and% RH. Then, each sample was placed on a vinyl core of 89 mm in a direct line.
The polyethylene film having a winding thickness of 20 μm was doubly packaged and further left in a room at 23 ° C. and 55% RH for 168 hours.
The sample was released from the core, and after 30 minutes, the degree of curling was determined by the reciprocal of the radius of curvature (unit m ⁻¹ ).

The moisture content and the degree of curling of the film sample after humidity control were as follows.

Humidity control condition (% RH) Water content of film (%) Degree of curl (m ^-1 ) 0 0 2 10 0.05 2 20 0.10 3 40 0.20 5 60 0.25 10 When the film is stored in a roll state, It can be seen that the winding curl can be reduced by setting the water content of the above to 0.2% or less.

<Coating of Photosensitive Photosensitive Layer> The undercoat layer A-2 of the above film was subjected to a corona discharge treatment of 25 W / (m ² / min) to form the following color photographic constituent layers in order. ,
A color photographic light-sensitive material was prepared.

Unless otherwise stated, the quantities shown in the photographic constituent layers shown below are expressed in quantities per 1 m ² .

Also, silver halide and colloidal silver are shown in terms of silver.

<Photographic Constituent Layer> First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.15 g UV Absorber (UV-1) 0.20 g Colored Cyan Coupler (CC-1) 0.02 g High Boiling Solvent (Oil-1) ) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average particle size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (Average particle size 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan Coupler (C-1) 0.50g Cyan coupler (C-2) 0.13g Colored cyan coupler (CC-1) 0.07g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g Fourth layer; high-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion ( Average particle size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ ( Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D- 2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g Fifth layer; Intermediate layer (IL-2) Gelatin 0.8 g Sixth layer; Low sensitivity green sensitive emulsion layer (GL) Silver iodobromide Emulsion (average particle size 0.4 μm, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average particle size 0.3 μm, average iodine content 2.0 mol%) 0.2 g Sensitizing dye ^{S-4) 6.7 × 10 -4} ( mol / mole of silver) Sensitizing dye (S-5) 0.8 × 10 -4 ( mol / mole of silver) Magenta coupler (M-1) 0.17 g Magenta coupler (M- 2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02 g High boiling point solvent (Oil-2) 0.7 g Gelatin 1.0 g Seventh layer; High sensitivity green-sensitive emulsion layer (GH) ) Silver iodobromide emulsion (average grain size 0.7 μm, average iodine content 7.5 mol%) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-7 ) 2.0 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04g DIR compound (D-3) 0.004g High boiling point solvent (Oil-2) 0.35g Gelatin 1.0g 8 layers; Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g 9th layer; low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g 10th layer; High-sensitivity blue-sensitive emulsion layer (BH) Iodobromide Silver emulsion (average grain size 0.8 μm, average iodine content 8.5 mol%) 0.5 g Sensitizing dye (S-10) 3 × 10 ^-4 (mol / silver) Sensitizing dye (S-11) 1.2 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) 0.10 g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling point solvent (Oil-1) 0.07g High boiling point solvent (Oil-3) 0.07g Gelatin 0.8g 12th layer; 2nd protective layer ( PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethylmethacrylate (average particle size: 3 μm) 0.02 g Gelatin 0.7 g-Preparation of silver iodobromide emulsion-The silver iodobromide emulsion used for the 10th layer is as follows. Prepared by the method.

A silver iodobromide emulsion was prepared by the double jet method using monodispersed silver iodobromide grains (silver iodide content 2 mol%) having an average grain size of 0.33 μm as seed crystals.

A solution <G-1> having the following composition was heated at 70 ° C. and pA
While maintaining g7.8 and pH 7.0, a seed emulsion corresponding to 0.34 mol was added while stirring well.

(Formation of Internal High Iodity Phase-Core Phase)
Solution <H-1> having the following composition and solution <S-1> having the following composition
While maintaining a flow ratio of 1: 1, and were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining pAg10.1 and pH6.0.
-2> was added at a flow rate accelerated by a flow rate ratio of 1: 1 (the flow rate at the end was 5.2 times the initial flow rate) over 65 minutes.

The pAg and pH during grain formation were controlled using an aqueous potassium bromide solution and a 56% aqueous acetic acid solution. After the particles are formed, they are washed with water by a conventional flocculation method, and then gelatin is added to redisperse them, and the pH is adjusted to 40 ° C.
And pAg were adjusted to 5.8 and 8.0, respectively.

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a distribution width of 12.4% and a silver iodide content of 8.5 mol%.

<G-1> Ocein gelatin 100.0 g 10% by weight ethanol solution of the following compound-1 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml (Compound-I: polyisopropylene) Oxy-polyethylene oxy-di sodium succinate) <H-1> Ocein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% aqueous ammonia solution Equivalent water Finish with 1030.5 ml <H-2> Oscein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finish with water 3776.8 ml <S-2> Silver nitrate 1133.0 g 28% ammonia solution equivalent Finish with water 3776.8 ml 10th layer For silver iodobromide emulsions used in the other emulsion layers, the average grain size of seed crystal, temperature, pAg, p
The above emulsions having different average grain sizes and silver iodide contents were prepared by changing H, flow rate, addition time and halide composition.

All were core / shell type monodisperse emulsions having a distribution width of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and a sensitizing dye, 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercaptotetrazole was added.

The above light-sensitive material further comprises the compound S
U-1, SU-2, viscosity modifier, hardener H-1, H-
2, stabilizer ST-1, antifoggant AF-1, AF-2
(Weight average molecular weight of 10,000 and 1,100,000), dyes AI-1, AI-2 and compound DI-1
(9.4 mg / m ² ) is contained.

The structure of each compound used for forming the above-mentioned multilayer color photographic light-sensitive material is shown below.

[0146]

[Chemical 1]

[0147]

[Chemical 2]

[0148]

[Chemical 3]

[0149]

[Chemical 4]

[0150]

[Chemical 5]

[0151]

[Chemical 6]

[0152]

[Chemical 7]

[0153]

[Chemical 8]

[0154]

[Chemical 9]

[0155]

[Chemical 10]

[0156]

[Chemical 11]

The light-sensitive material obtained as described above has a width of 35 mm.
mm, length 120 mm, and both edges were perforated as described in JIS7519-1982.
The curled curl of the cut photosensitive material was measured, and the press-price transportability and sorting workability were evaluated. The evaluation results are shown in Tables 4 to 7.

[0158]

[Table 4]

[0159]

[Table 5]

[0160]

[Table 6]

[0161]

[Table 7]

As is clear from Tables 4 to 7, the present invention in which the polyester film was treated in a state of containing water in an appropriate amount has a reduced curling curl as compared with the Comparative Example.
It can be seen that the press price suitability and sorting workability are excellent. Also, those treated at high temperature have many curling curls, but many coating failures in the undercoat layer coating,
It can be seen that the flatness is inferior.

[0163]

The photographic support comprising the biaxially stretched polyester film according to the present invention is excellent in mechanical strength and dimensional stability, curling curl is reduced, and even when the diameter of the core is reduced, it can be used in the press-splicing process. There is no conveyance failure, and the workability of sorting after development is excellent.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03C 1/81 1/91 // B29K 67:00

Claims (3)

[Claims] 1. A photographic support comprising a biaxially stretched polyester film, the biaxially stretched polyester film having a moisture content of 0.1% or more and 1.5% or less at 15 ° C.
A photographic support characterized in that at least one undercoat layer is coated on the surface of the biaxially stretched polyester film after being treated at a temperature of Tg-30 ° C or lower for 0.1 hour or longer. 2. The photographic support according to claim 1, wherein the biaxially stretched polyester film has an ethylene terephthalate unit or an ethylene 2-6 naphthalate unit as a main constituent. 3. The photographic support according to claim 1, wherein the biaxially stretched polyester film contains 70% by weight or more of ethylene terephthalate units or ethylene 2-6 naphthalate units. .