JPH07270966A - Photographic support and photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic support superior in mechanical strength and dimensional stability and small in curling tendency after development processing by composing it with a specified polyester. CONSTITUTION:The support is formed out of a polyester film heat treated in a temperature range from 15 deg.C to a temperature 5 deg.C below the glass transition point in a state of water content controlled to be 0.1-1.5%, and it is preferred that this polyester contains ethylene terephthalate units or ethhylene 2, 6-naphthalate units in an amount of >=70weight%, and this polyester film has a multilayer structure of >=2 layers and at least one layer comprises an aromatic dicarboxylic acid having a metal sulfonate group as the copolymer unit, thus permitting winding off of the film to be enhanced in speed at the time of photographing and magnification of a photograph to be enhanced and a photographing device to be reduced in size.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic support having excellent mechanical strength and dimensional stability, which is particularly useful for a photographic light-sensitive material used in the form of a roll film.

[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 sometimes abbreviated as PET film) is
It has excellent transparency, mechanical strength and dimensional stability,
Triacetyl cellulose film, which has been used in the past, has been used in microfilms, which require thin films, printing sensitizers that require dimensional stability, and X-ray films that require transparency and elasticity. The PET film is used instead of the TAC film). However, in a photographic light-sensitive material used in the form of a roll film such as a general negative film, a PET film having no curl recovery property after development processing as seen in a TAC film is hardly used. After the development process, the curl is too strong and it is not easy to handle, and problems such as scratches, defocus, and jamming during transport occur in the process of printing the image on photographic paper after the development process, for example. Because there was a problem that it would end up.

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 abbreviated as Tg).

As a method for making the film less likely to curl, JP-A-51-16358 discloses a method of heat-treating a thermoplastic resin film at Tg-5 ° C. to Tg-30 ° C. for 0.1 to 1500 hours. Is proposed. Further, JP-A-6-35118 proposes a method in which a polyester film having a Tg of 90 to 200 ° C. is undercoated and then heat treated at 50 ° C. to Tg for 0.1 to 1500 hours.

[0006]

However, the PET film obtained by copolymerizing a water-absorbing component is certainly improved in water-absorbing property, but in order to obtain sufficient curl recovery after development processing, the water-absorbing component is used. Need to copolymerize a lot, normal PET
The Tg is considerably lower than that of the film, and the crystallinity is also reduced. Therefore, there is a problem that only a film having very poor heat resistance and mechanical strength can be obtained.
And, a laminated film of a PET film copolymerized with a water-absorbing component and a polyester film having a high Tg is aimed at solving these problems, but a polyester film having a high Tg has no curl recovery property. Therefore, the wound-up recovery property as a laminated film is insufficient, which is a practical problem.

Thermoplastic resin film Tg-5 ℃ ~ Tg-30
The method of heat treatment at 0.1 to 1500 hours at ℃ is a PET film or a polyethylene naphthalate film (hereinafter PEN).
(It may be abbreviated as a film), and has an effect of reducing curling curl of a crystalline or semi-crystalline thermoplastic resin. Although it is not a method of directly improving the curl curl recovery of the film, it is possible to make curl curl itself less likely to curl curl after development, which seems to be 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, generally, a photographic 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. Then, it will be packaged into the final product form.

It is advantageous for this intermediate product to be as wide and long as possible from the viewpoint of shortening the switching time and improving productivity, and the weight of the intermediate product is increasing. As a result, a considerable load is actually applied to the winding core.

By the way, the thermoplastic resin film is
It is well known that the elastic modulus sharply decreases when heated near Tg. Therefore, if a thermoplastic resin film is heat-treated near its Tg for a long time under a heavy load, the film will not withstand the load, and various photographic supports such as wrinkles, folds, and presses will be supported. A surface failure occurs that cannot be used as a body.

The method of undercoating a polyester film having a Tg of 90 to 200 ° C. and then heat treating it at 50 ° C. to Tg for 0.1 to 1500 hours is basically the same as the method described in JP-A-51-16358. This is a method, and therefore, heat treatment in the vicinity of Tg of the film is necessary in order to make it difficult for the film to be rolled up sufficiently. For example, for polyester film with Tg of 90 ° C, 60
If you do not heat-treat above ℃, you will not get sufficient effect,
In the actual situation, a polyester film having a Tg of 120 ° C cannot achieve its full effect unless it is heat-treated at 90 ° C or higher. Further, in this method, the Tg of the film used is high, and since it has to be heat-treated at a very high temperature, in addition to the problem of significantly impairing the quality of the film,
The following new problems arise.

That is, in general, a photographic light-sensitive material has a maximum usable temperature of 50 ° C. at most, and the 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 the heat treatment for making it difficult to wind the film, and transfer or bleedout of additives to the coating film surface, such as deterioration or decomposition of the material, and the coating film. It causes various problems such as surface cracking.

As described above, the film has excellent mechanical strength and dimensional stability that enable unwinding of the film at the time of shooting, high shooting magnification, and downsizing of the shooting apparatus. However, a photographic support having a small curl after development was not obtained.

[0014]

The method proposed in JP-A-51-16358 causes various problems because it requires heat treatment at a high temperature. Therefore, if it is possible to find a method that can effectively prevent the curling of the film even with the heat treatment at a lower temperature, it is possible to reduce the curl curl after the developing treatment. The present invention has been reached.

The object of the present invention is (1) a photographic support comprising a polyester film, wherein the polyester film is conditioned at a water content of 0.1% or more and 1.5% or less and at a temperature of 15 ° C or higher and Tg-5 ° C. A photographic support characterized by being heat treated at a temperature below.

(2) A photographic support comprising a polyester film, wherein the polyester film has a water content of 0.1.
% Or more and 1.5% or less, 15g or more Tg-30
A photographic support characterized by being heat treated at a temperature of less than ° C.

(3) The polyester film contains an ethylene terephthalate unit or an ethylene-2,6-naphthalate unit (1)
Alternatively, the photographic support according to (2).

(4) The polyester film contains an ethylene terephthalate unit or an ethylene-2,6-naphthalate unit in an amount of 70% by weight or more. (1), (2) or (3) Photographic support.

(5) The polyester film has a multilayer structure of two or more layers, and at least one layer is made of polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component (1). ,
The photographic support according to (2), (3) or (4).

(6) A photographic light-sensitive material characterized in that a photographic emulsion layer is provided on at least one side of the photographic support described in any one of (1) to (5).

Was achieved by

The present invention will be described in detail below.

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

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl ethane. Examples thereof include dicarboxylic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketone dicarboxylic acid and phenylindanedicarboxylic acid. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-
(Hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol, etc. . Among the polyesters containing these as the main constituents, terephthalic acid or 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid component and ethylene glycol or 1 as the diol component are used in terms of transparency, mechanical strength, dimensional stability, etc. Polyesters containing 1,4-cyclohexanedimethanol as a main constituent are preferred. Among them, polyethylene terephthalate, polyethylene-2,6-naphthalate, terephthalic acid and 2,
A polyester composed of 6-naphthalenedicarboxylic acid and ethylene glycol and a polyester containing a mixture of two or more of these polyesters as main constituents are preferable. 70 units of ethylene terephthalate unit or ethylene-2,6-naphthalate unit for polyester
When it is contained in an amount of not less than wt%, a film having excellent transparency, mechanical strength, dimensional stability and the like can be obtained.

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

The polyester which constitutes the polyester film of the present invention is obtained by copolymerizing at least one compound having at least one hydrophilic group, so that an appropriate water absorption is obtained, and the film is appropriately subjected to the heat treatment described below. It is preferable because it becomes easy to contain various water.

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 sulphoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and their sodium other metals (eg potassium, lithium etc.) and ammonium Compounds substituted with salts, phosphonium salts, or the like, or ester-forming derivatives thereof, polyethylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol copolymers, and compounds having carboxyl groups obtained by oxidizing the hydroxy groups at both ends thereof Are preferred.

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

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

The number average molecular weight of the compound component having a polyoxyalkylene group is preferably 300 to 20,000, and more preferably 600.
It is preferably in the range of up to 10,000, especially in the range of 1000 to 5000. The copolymerization ratio is preferably 0.5 to 15% by weight based on the polyester of the reaction product.

When the copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group, the number average molecular weight of the compound component having a polyoxyalkylene group, and the copolymerization ratio are within these ranges, the transparency and mechanical strength of the film will be 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 content of the antioxidant is usually 0.01 to 2% by weight, preferably 0.1 to 0.5% by weight based on the polyester. When the content of the antioxidant is small, a so-called fog phenomenon in which the density of the unexposed portion of the photographic light-sensitive material becomes high is likely to occur, and when it is too large, haze of the film becomes high and transparency may be deteriorated. In addition, these antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type.

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. 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 dye has a spectral transmittance of 60% to 85% in the wavelength range of 400 to 700 nm and a difference between the maximum and the minimum of the spectral transmittance of 10% in the wavelength range of 600 to 700 nm. Is preferable in order to prevent the light piping phenomenon and to obtain a good photographic print.

The polyester film of the present invention may be provided with slipperiness, if necessary. The slipperiness imparting means 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 to be added during the synthesis of polyester,
Alternatively, a method of applying a surfactant or the like on the film surface is generally used. Among these, the internal particle deposition method that can control the deposited particles relatively small,
It 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 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 copolymerized polyester layer. The transparency, mechanical strength, dimensional stability, etc. of the entire film can be improved.

Furthermore, when the polyester film of the present invention has a layer structure, the above-mentioned functions such as antioxidation, light piping prevention, slipperiness, and the like, or addition of various additives other than those mentioned above are applied only to the surface layer. Since it can be performed, the transparency of the film can be maintained high.

The polyester film of the present invention can be highly prevented from precipitating oligomers on the surface of the film by further laminating layers 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 polyester D is preferably higher than the Tg of the polyester of the inner layer. Polyester D Tg
Is 5 ° C or more than the Tg of the inner layer polyester, and 15 ° C
It is more preferable that it is higher than the above. Further, the thickness of the layer made of polyester D is to maintain the water absorption of the film,
It is necessary to be thin within a certain range, and 0.05 to 10 μm is preferable.

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

The thickness of the polyester film of the present invention is not particularly limited. It may be set so as to have a required strength according to the purpose of use. Particularly when the polyester film is used for a 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.

The polyester film of the present invention has a curl degree in the width direction of the film of 5 to 50 m ^-1 determined by the following method.
Is preferred.

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

The width direction as used herein means a direction (excluding the film thickness direction) at right angles to the winding direction when the photographic light-sensitive material is used in the form of a roll. The length direction means this winding direction. Since the winding direction is long, it is usually preferable to set the machine direction during film production to be the length direction.

By setting the degree of curl in the width direction of the polyester film within the above range, curling curl can be made extremely small, and there is no problem such as scratches or jamming during the process of printing on photographic printing paper. A photographic light-sensitive material can be obtained. 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 method of imparting curl in the width direction to the polyester 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 changing the thickness of both outer layers, a method of changing the stretching conditions of the front and back and heat setting conditions to give a distribution of molecular orientation and crystallinity in the thickness direction of the film, etc. Can be mentioned. Further, it is of course possible to appropriately combine these methods or 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, 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 a method of changing the thickness of both outer layers is preferable.

In the method of laminating the same or different polyesters having different intrinsic viscosities, the difference in the intrinsic viscosities is 0.02 to
0.5 (g / dl) is preferable, and in the method of changing the thickness of both outer layers, assuming that the thicknesses of both outer layers are d ₁ and d ₂ , respectively, 1.1 ≦ d ₁ / d ₂ ≦ 10, and further 2 ≦
From the viewpoint of film production, it is preferable that d ₁ / d ₂ ≦ 5.
If the film does not fall within the above range, stretching may be extremely difficult.

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

The method for obtaining an unstretched sheet and the method for uniaxially stretching in the machine direction can be carried out by conventionally known methods. For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled and solidified, and unstretched. Get the sheet. Then, the obtained unstretched sheet is heated 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.
When the sheet has a multi-layer structure, the stretching 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-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.

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

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

The heat-fixed film is usually cooled to Tg or less, and the clip gripping portions at both ends of the film are cut and wound up. At this time, 0.1-10% in the width direction and / or the longitudinal direction within the temperature range below the final heat setting temperature and above Tg.
Relaxation treatment is preferred. Further, for cooling, it is preferable to gradually cool from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. The means for cooling and relaxing treatment is not particularly limited, and it can be performed by a conventionally known means, but it is particularly preferable to perform these treatments while sequentially cooling in a plurality of temperature regions,
It is preferable in terms of improving the dimensional stability of the film. The cooling rate is calculated by setting the final heat setting temperature to T1, and the time from the final heat setting temperature of the film reaching Tg to t,
It is calculated by (T1-Tg) / t.

The more optimal 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 preferable properties. It may be determined by

In the production of the above-mentioned 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.

In the present invention, the polyester film obtained as described above is conditioned at a water content of 0.1% or more and 1.5% or less as determined by the following method, at a temperature of 15 ° C. or higher and Tg-5 ° C. of the film. Heat treatment is performed at the following temperature. Preferably 15
Heat treatment is performed at a temperature of not less than ℃ and not more than Tg-30 ° C of the film. When the polyester film has a multi-layer structure, it is the most
The one with a low Tg is used as the standard. By adding a small amount of water, which seems to have nothing to do with the appearance, to the hydrophobic polyester film, it is possible to achieve a sufficient curling curling reduction effect even when heat-treated at a temperature lower than conventional. Since it is not necessary to perform high-temperature treatment as in the conventional case, various problems as described above can be solved, and curl curl after development can be greatly reduced. Furthermore, it has been found that an unexpected effect that the dimensional stability can be improved is also obtained.

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

If the water content of the film is too low, the curling curl reduction effect is not sufficient, and if it is too high, the rigidity of the film decreases, and the surface failure and flatness of the film deteriorate.

The heat treatment time of the film may be appropriately set so that the curl of the heat-treated film is measured and a desired curl curl reduction effect is obtained.

The higher the heat treatment temperature, the shorter the time the effect is obtained, and the lower the temperature, the longer the time is required. However, in the present invention, the film is appropriately heat-treated and heat treated. In comparison, a sufficient effect can be obtained even in a very short time. Of course, the longer the treatment time is, the higher the effect is obtained, but the productivity is remarkably deteriorated. Usually 0.01-1500
Time is the preferred range.

By the way, usually, the film is in an almost dry state immediately after forming the film or immediately after coating and drying each functional layer on the film surface, and is wound in an almost dry state. The film that has been wound is stored in an air-conditioned room for a certain period until it is sent to the next process.When winding, apply sufficient tension to prevent misalignment. Since the film is wound up while being wound, the film adheres well and there is some moisture absorption at the outer circumference and the end of the winding, but there is no moisture up to the inside of the winding and the initial almost dry state is maintained. There is.

Therefore, it is considered that in the conventional method, the water content in the film is heat-treated in an almost dry state, and the heat treatment at a high temperature is necessary in order to bring out the curling effect.

The step of carrying out the heat treatment of the present invention is not particularly limited, and can be performed after the film is formed and before it is packaged into the form of the final product. Since it disappears when exposed to the above temperature, it is preferable to carry out after providing each functional layer on the film surface. Especially after providing a layer for preventing sticking between the film and the film on at least one surface of the film,
It is preferable to carry out before coating the photographic light-sensitive layer. Examples of the layer for preventing sticking include a matting agent, a wax, a surfactant, a lubricant-containing layer such as particles of magnetic powder, and a layer made of a polymer having a sufficiently high Tg or a polymer having no thermoplasticity. Can be mentioned.

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 an arbitrary position in 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. Examples thereof include a method of sandwiching between films, a method of blowing humidified air at the time of winding, and a method of adjusting drying conditions after coating and drying. 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 that does not cause bending even when the film is wound, has an appropriate water vapor permeability, or has a fine unevenness on the surface and the atmosphere has a core portion. 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.

In order to further secure the effect of the present invention, when heat-treating a film moistened with 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.

Next, a method of forming a photographic light-sensitive material will be described.

When a hydrophobic polymer film is used as a photographic support, even if a hydrophilic photographic emulsion layer is directly coated on the polymer film, the required adhesive force cannot be obtained. Therefore, the polymer film usually requires surface treatment.
Surface treatments for such purposes include corona discharge treatment, ultraviolet treatment, glow discharge treatment, plasma treatment, flame treatment and other surface activation treatment, resorcin treatment, phenol treatment, alkali treatment, amine treatment, trichloroacetic acid treatment. And the like, and a method of laminating one or more adhesive layers.
These methods may be used alone or in combination.

The material that can be used in the method for laminating the adhesive layer is not particularly limited, but, for example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, and maleic anhydride can be used as a starting material. Starting with coalescence, polyethyleneimine, polyester, polystyrene, polyurethane, epoxy resin,
Examples thereof include grafted gelatin, nitrocellulose and the like, and mixtures thereof. In these adhesive layers, surfactants, antistatic agents, antihalation agents, crossover cut agents, coloring dyes, pigments, thickeners, coating aids, antifoggants, antioxidants, UV absorbers, UV stabilizers. One or more kinds of various additives such as an agent, an etching treatment agent, a magnetic powder, and a matting agent may be contained.

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 laminated.

The method of laminating these adhesive layers and the like is not particularly limited, and various conventionally known methods can be used. For example, before or after the biaxial orientation of the polyester film is completed, a coating method such as an air knife coater, a dip coater, a curtain coater, a wire bar coater, a gravure coater, an extrusion coater, or the like may be used when the polyester film is melt-formed. Examples of the method include extrusion and laminating.

The photographic light-sensitive 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. Further, the photographic emulsion layer can be provided in one layer or two or more layers on each surface.

The silver halide emulsion can be coated on the photographic support directly 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 is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643, 22.
Pp. 23 (December 1979), "1. Emulsion preparation method (Emulsion pre
paration and types) ”, and RD No.18716, 648
P.Glkides, Chimie et Physique Photographique, "Physics and Chemistry of Photography" by Graphide
Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDauffin, Photographic Emuls)
ion Chemistry Focal Press 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (V.
L. Zelikman et al, Making and coating Photographic Em
ulsion, Focal Press 1964) and the like.

Emulsions are disclosed in US Pat. Nos. 3,574,628 and 3,665,3.
Monodisperse emulsions described in, for example, 94 and British Patent 1,413,748 are also preferable.

The silver halide emulsion can be subjected to physical ripening, chemical ripening and spectral sensitization. The additives used in such a process are RD No.17643, RD No.18716 and RD No.308119 (hereinafter referred to as RD17643 and RD18716, respectively).
And abbreviated as RD308119. )It is described in. Table 1 shows the location of the description.

[0081]

[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.

[0083]

[Table 2]

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used, and specific examples thereof are described in RD17643 and RD308119 below. Table 3 shows the related description.

[0085]

[Table 3]

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

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

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

Development processing of the silver halide photographic light-sensitive material of the present invention can be carried out, for example, by TH James, Theory.
4th Edition of The Photographic Process
ory of The Photografic Process Forth Edition) No. 29
Pages 1-334 and the Journal of the American Chemica
l Society), Vol. 73, page 3,100 (1951), a developer known per se can be used. Further, the color photographic light-sensitive material is the above-mentioned RD17643 28-29.
Development can be carried out by a usual method described on page RD18716, page 615 and RD308119 XIX.

[0090]

EXAMPLES The present invention will be described in more detail below with reference to examples.

In the following examples, glass transition temperature and melting point, film haze, water content, intrinsic viscosity, elastic modulus and breaking strength, thermal shrinkage, hygroscopic expansion coefficient, curl degree in width direction, surface failure, flatness, The value of curling curl after development processing is determined 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 cm ^{3 /} min and immediately cooled in liquid nitrogen.
A differential scanning calorimeter (manufactured by Rigaku Denki Co.,
DSC8230 type), the temperature is raised at a heating rate of 10 ° C./min in a nitrogen stream of 100 cm ^{3 /} min to detect Tg and Tm. Tg
Is the average value of the temperature at which the baseline begins to become eccentric and the temperature at which the baseline newly returns, and Tm is the peak temperature of the endothermic peak. The measurement start temperature is set to a temperature lower than the measured Tg by 50 ° C or more.

(2) Film haze 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] = lim (ηsp / C) C → 0. The unit is indicated by dl / g.

(4) Elastic Modulus and Breaking Strength The film was 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 55 ° C and 55% RH, Tensilon (RTA-100) manufactured by Orientec Co., Ltd. was used to perform a tensile test at a tensile speed of 100 mm / min with a chuck distance of 100 mm, and an elastic modulus. And the breaking strength was determined.

(5) Heat Shrinkage A sample of 150 mm × 150 mm was cut out from the film, and was cut at 23 ° C.
After conditioning the humidity for 1 day under the condition of 55% RH, put a scoring line at 100 mm intervals. Then, heat treatment is carried out at 130 ° C. for 30 minutes, and humidity of one day is controlled 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. In addition,
The direction of contraction was +, and the direction of expansion was −, before the heat treatment.

(6) Curling degree in the 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, and then the radius of curvature of the curl in the width direction was measured in meters. The curl degree in the width direction is expressed by the reciprocal thereof. The unit is m ^-1 .

(7) Hygroscopic expansion coefficient Thermo-mechanical property measuring device (TM-7000 type; manufactured by Vacuum Riko Co., Ltd.)
The dimensional elongation was measured and determined when the humidity was changed from 10% RH to 90% RH at a temperature of 23 ° C. The unit is cm / cm
Expressed as% RH.

(8) Water content Using a trace moisture meter (CA-05 type manufactured by Mitsubishi Kasei Co., Ltd.),
It was measured at a drying temperature of 150 ° C.

(9) Surface 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 photographic light-sensitive material, and it is necessary that the rank is ◯ or higher.

Rank Number of surface defects ◎ 0 ○ 1 to 3 × 4 or more (10) Flatness After conditioning the film for 12 hours at 23 ° C and 55% RH, it was 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 tolerance of the quality of the photographic light-sensitive material, and it is necessary that the rank is ◯ or higher.

Rank Waviness ◎ Good ○ Ripple can be seen by looking closely × Waviness is large (11) Curled curl after treatment A film with a sample size of 12 cm × 35 mm is 10 mm in diameter so that the photographic component layer side is inwardly wound. Wrap around core, 55 ℃, 20% RH
It is processed for 3 days under the conditions of, and the curl is attached. After that, it is released from the core, immersed in pure water at 38 ° C. for 15 minutes, and then dried with a hot air dryer at 55 ° C. for 3 minutes while applying a load of 50 g. The load was removed, the sample was suspended vertically, the distance between both ends of the sample was determined, and it was evaluated how much the original distance was restored to 12 cm. The evaluation was performed according to the following criteria.

⊚: 70% or more ◯: 50% or more and less than 70% x: less than 50% It should be noted that if the level is ◯ or more, there is no practical problem.

<Production of Polyester Film> Polyester A to polyester F were prepared as follows.

(Polyester A) 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were added as calcium ester hydrate 0.1 as a transesterification catalyst.
Part by weight was added, and transesterification was performed according to a conventional method. The obtained product, antimony trioxide 0.05 parts by weight,
0.03 parts by weight of phosphoric acid trimethyl ester was 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 polyethylene-2,6-naphthalate having an intrinsic viscosity of 0.60.

(Polyester B) 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were added 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) 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), 0.05 parts by weight of antimony trioxide, 0.03 parts by weight of phosphoric acid trimethyl ester, Irga Knox 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 280 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.62.

(Polyester E) 100 parts by weight of dimethyl 2,6-naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were added to magnesium acetate hydrate as an ester exchange catalyst.
05 parts by weight was added, and transesterification reaction was carried out according to a conventional method. 18 parts by weight of an ethylene glycol solution of 5-sodium sulfodi (β-hydroxyethyl) isophthalic acid (concentration: 35% by weight), and 6 parts by weight of polyethylene glycol (number average molecular weight: 3000), trioxide 0.05 parts by weight of antimony, 0.03 parts by weight of phosphoric acid trimethyl ester, 0.2 parts by weight of Irganox 1010 (manufactured by Ciba Geigy) and 0.04 parts by weight of sodium acetate were added. Then, the temperature was gradually raised and the pressure was reduced, and polymerization was carried out at 290 ° C. and 0.5 mmHg to obtain a polyester having an intrinsic viscosity of 0.55.

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

A film was obtained in the following manner using each of the polyesters obtained as described above.

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

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total lateral stretching ratio using a tenter type lateral stretching machine, and further at a second stretching zone at 155 ° C. in a total lateral 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 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 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.

(Film 3) Polyester A and polyester B were vacuum dried at 150 ° C. for 8 hours, and
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 obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total lateral stretching ratio using a tenter type lateral stretching machine, and further at a second stretching zone at 155 ° C. in a total lateral 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 machine direction at 95 ° C. using a roll-type machine.

The uniaxially stretched film thus obtained was stretched in a tenter 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. in 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 three extruders, melt-extruding at 300 ° C, joining in layers in a T-die, adhering to a cooling drum at 50 ° C while applying static electricity, cooling and solidifying, a laminated unstretched sheet of three-layer structure Got At this time, the extrusion rate of each extruder was adjusted so that the thickness ratio of each layer was 1: 3: 3. This unstretched sheet was rolled at a temperature of 135 ° C. in a longitudinal direction of 3.5 by using a roll-type longitudinal stretching machine.
It was stretched twice. Using a tenter type transverse stretching machine, the obtained uniaxially stretched film is stretched in the first stretching zone 145 ° C by 50% of the total transverse stretching ratio, and further in the second stretching zone 155 ° C so that the total transverse stretching ratio is 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.

Embossing rings heated to 250 ° C. were pressed against both ends of each of the biaxially stretched films obtained as described above, and the embossing was performed over the entire length in the longitudinal direction while adjusting the pressing pressure so that the height became 30 μm. Processed.

The characteristic values of each biaxially stretched film thus obtained are shown in Table 4. When the intrinsic viscosity, glass transition temperature and melting point of each of the obtained biaxially stretched films were measured, the intrinsic viscosity of polyester A was 0.
58, glass transition temperature 120 ℃, melting point 270 ℃, polyester B intrinsic viscosity 0.52, glass transition temperature 123 ℃, melting point 265 ℃, polyester C intrinsic viscosity 0.63, glass transition temperature 76 ℃, melting point 260 ° C, polyester D has an intrinsic viscosity of 0.60, glass transition temperature of 85 ° C, melting point of 255 ° C, polyester E has an intrinsic viscosity of 0.52, glass transition temperature of 100
℃, melting point 260 ℃, polyester F intrinsic viscosity 0.60,
The glass transition temperature was 105 ° C and the melting point was 267 ° C.

[0123]

[Table 4]

The film 3 is on the polyester A side,
Since the film 4 showed a curl on the polyester C side and the film 5 on the thin layer side of the polyester E, the subsequent processing was performed so that the convex surface became the photographic photosensitive layer side.

<Coating of undercoat layer and back layer> One side of the film is subjected to a corona discharge treatment of 8 W / (m ² · min), and then the following undercoat coating is carried out at room temperature and normal humidity. Liquid A-
1 at a speed of 50 m / min using a roll-fit coating pan and air knife, and at a drying temperature of 90 ° C.
It was dried for 30 seconds to form an undercoat layer A-1 having a dry film thickness of 0.8 μm. 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 Coating Liquid A-1> Copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, and 25% by weight of 2-hydroxyethyl acrylate (solid content: 30%). %) 270g Compound (UL-1) 0.6g Hexamethylene-1,6-bis (ethyleneurea) 0.8g Finish with water 1000ml <Undercoating solution B-1> 40% by weight butyl acrylate, 20% by weight styrene and glycidyl Copolymer latex liquid containing 40% by weight of acrylate (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.

<Subbing Coating Solution 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 <Subbing 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 The film obtained as above was wound around a paper core of 250mm in diameter for 500m.
Under the condition of 50% RH, Sample No. 16 was rewound on a separately prepared paper core with a diameter of 250 mm after changing the humidity control time as shown in Table 5 under the condition of 23 ° C. and 80% RH. . At this time,
Film pieces were cut out from the front and back of the film and used for the measurement of water content.

Next, the film was covered with a polyethylene film having a thickness of 20 μm in a double-wound state while being wound on the core,
Heat treatment was performed as shown in Table 5.

After that, it was left to stand under the conditions of 23 ° C. and 50% RH for 48 hours.

At this time, sampling was performed to measure the heat shrinkage rate and the hygroscopic expansion coefficient of the film.

<Coating of Photosensitive Photosensitive Layer> A corona discharge treatment of 25 W / (m ² / min) was applied to the surface of the undercoat layer A-2 of the above film to sequentially form the following photographic constituent layers, A color photographic light-sensitive material was prepared. In addition, unless otherwise indicated, the quantities shown in the photographic constituent layers shown below are 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 grain size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain 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) 0.50 g Cyan coupler (C-2) 0.13 g Colored cyan coupler (CC-1) 0.07 g 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 grain 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 (mol / silver 1 mol) 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 grain diameter 0.4 .mu.m, the average iodide content of 8.0 mol%) 0.6 g silver iodobromide emulsion (average particle size 0.3 [mu] m, an average iodide content of 2.0 mol%) 0.2 g sensitizing dye (S-4) 6.7 × 10 -4 ( Le / 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) 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) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1.0 g Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1g Additive (HS-1) 0.07g Additive (HS-2) 0.07g Additive (SC-1) 0.12g High boiling solvent (Oil-2) 0.15g Gelatin 1.0g 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 (B-H) Silver iodobromide emulsion (average grain size 0.8 μm, The average iodide content of 8.5 mol%) 0.5 g sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of 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) Odor Silver oxide (average particle size 0.08 μm) 0.3 g Ultraviolet absorber (UV-1) 0.07 g Ultraviolet absorber (UV-2) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g 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 0.04g Compound B 0.004g Polymethylmethacrylate (average particle size) : 3 μm) 0.02 g Gelatin 0.7 g-Preparation of silver iodobromide emulsion-The silver iodobromide emulsion used in the 10th layer was prepared by the following 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 treated at a temperature of 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) Then, a solution <H-1> having the following composition and a solution <S- having the following composition:
1> and 1> were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase) Subsequently, <H-2> and <S> while maintaining pAg10.1 and pH6.0.
-2> and 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-I 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-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 Iodobromide used in non-emulsion layers For emulsions, 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 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 silver halide photographic light-sensitive material is shown below.

[0144]

[Chemical 1]

[0145]

[Chemical 2]

[0146]

[Chemical 3]

[0147]

[Chemical 4]

[0148]

[Chemical 5]

[0149]

[Chemical 6]

[0150]

[Chemical 7]

[0151]

[Chemical 8]

[0152]

[Chemical 9]

[0153]

[Chemical 10]

[0154]

[Chemical 11]

The photographic light-sensitive material obtained as described above was subjected to perforation processing as described in JIS K7519-1982.

At this time, a portion corresponding to the core portion at the time of heat treatment was sampled and used for evaluation of surface failure and flatness. Further, curling curl after processing was evaluated by the obtained photographic light-sensitive material. Table 5 shows the obtained film characteristics and evaluation results.

[0157]

[Table 5]

As is clear from Table 5, the heat-treated polyester film in a state of containing water in an appropriate amount, compared with the heat-treated one in the state of not containing water,
Curling curl after processing is reduced. Furthermore, the hygroscopic expansion coefficient is also reduced. Further, since the heat treatment temperature may be low, even if the film is wound into a roll and subjected to heat treatment, surface failure and flatness are good. Further, it can be seen that when the heat treatment is performed at a high temperature, the effect can be obtained in a very short time.

[0159]

As described in detail above, according to the present invention, the transparency, mechanical strength and dimensional stability are excellent, the curling curl after treatment is small, and the film is wound into a roll and heat-treated. Thus, it was possible to provide a photographic support comprising a polyester film which does not impair surface defects and flatness. Further, since the polyester film of the present invention has the above-mentioned excellent properties, it is useful not only for photographic supports but also for various films used in roll form.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 1/795 1/81

Claims (6)

[Claims] 1. A photographic support comprising a polyester film, which is heat-treated at a temperature of 15 ° C. or higher and lower than Tg-5 ° C. in a state where the moisture content of the polyester film is adjusted to 0.1% or more and 1.5% or less. A photographic support characterized in that 2. A photographic support comprising a polyester film, which is heat-treated at a temperature of 15 ° C. or higher and lower than Tg-30 ° C. in a state where the moisture content of the polyester film is adjusted to 0.1% or more and 1.5% or less. A photographic support characterized in that 3. The photographic support according to claim 1, wherein the polyester film contains an ethylene terephthalate unit or an ethylene-2,6-naphthalate unit. 4. The polyester film according to claim 1, wherein the polyester terephthalate unit or the ethylene-2,6-naphthalate unit is contained in an amount of 70% by weight or more. Photographic support. 5. The polyester film has a multi-layered structure of two or more layers, and at least one layer is made of a polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component. The photographic support according to claim 2, claim 3 or claim 4. 6. A photographic light-sensitive material comprising a photographic support according to claim 1 and a photographic emulsion layer provided on at least one side thereof.