JP3496166B2 - Photographic support and photographic light-sensitive material using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photographic support having excellent mechanical strength and dimensional stability, and particularly when used in a roll film type photographic light-sensitive material, it can be used in a press-price step before development. The present invention relates to a photographic support that has no conveyance defects and is excellent in workability of sorting films after development processing.

[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 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 core.

A triacetyl cellulose film (hereinafter referred to as a TAC film) has been conventionally used as a roll film type 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.

The biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) has excellent transparency, mechanical strength and dimensional stability, and it is necessary to reduce the thickness of the microfilm and dimensional stability. It is used in rigorously demanded printing materials and X-ray films where transparency and waist strength are required. However, the roll film type photographic light-sensitive material does not have the curl curl recovery after the development processing as seen in the TAC film, and the curl curl after the development processing is too large, which is not only inferior in the handling property during sorting work. For example, in the step of printing an image on a photographic printing paper after the development processing, there are problems that scratches occur, defocus, jamming during transportation, and the like occur. In addition, 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 seems that the above 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.
In the publication, a method is proposed in which a thermoplastic resin film is heat-treated at a temperature 5 ° C to 30 ° C lower than its glass transition point for 0.1 to 1500 hours. Furthermore, in JP-A-6-35118,
After undercoating a polyester film having a glass transition point of 90 ° C to 200 ° C, at 50 ° C to the glass transition point of 0.1 to 1500 hours,
A method of heat treatment has been proposed.

[0007]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The above-mentioned thermoplastic resin film is used in an amount of 0.1-1 at a temperature 5 ° C-30 ° C lower than the glass transition point.
The method of heat treatment for 500 hours is a PET film or a polyethylene naphthalate film (hereinafter referred to as PEN film).
In addition, the effect of reducing the curling curl of the crystalline or semi-crystalline thermoplastic resin was considered 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, in general, 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. 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 from the viewpoint of shortening the switching time and improving the 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, it is well known that when a thermoplastic resin film is heated near its glass transition point, its elastic modulus sharply decreases. Therefore, if a thermoplastic resin film is heat-treated for a long time near its glass transition point under a large load, the film will not withstand the load, and various types of wrinkles, folds, presses, etc. As a result, a surface failure that cannot be used as a support for the product will occur.

After undercoating a polyester film having a glass transition point of 90 ° C to 200 ° C, 0.1 to 150 at the glass transition point of 50 ° C.
In principle, the method of heat treatment for 0 hours is disclosed in JP-A-51-1635.
The method is exactly the same as that described in No. 8, and therefore, heat treatment in the vicinity of the glass transition point of the film is necessary in order to sufficiently reduce curling curl. For example, a polyester film with a glass transition point of 90 ° C will not have sufficient effect unless it is heat-treated at 60 ° C or higher, and a polyester film with a glass transition point of 120 ° C will not have sufficient heat treatment at 90 ° C or higher. The actual situation is that the effect cannot be obtained. Further, in this method, the film used has a high glass transition point and must be heat-treated at a very high temperature, so that the following new problems occur in addition to the problem that the quality of the film is significantly impaired.

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 heat treatment for sufficiently reducing curling curl of the film, and transfer or bleed-out of additives to the coating film surface including deterioration and decomposition of the material,
It causes various problems such as cracks on the surface of the coating film.

Further, a photographic light-sensitive material using the polyester film obtained by these methods as a photographic support is
Although curling curl is certainly reduced compared to those not using these methods, somehow the transport failure in the press price process is not eliminated and the sorting workability after development processing is inferior. It was real.

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. 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.

Therefore, an object of the present invention is to have excellent mechanical strength and dimensional stability, to prevent the conveyance failure in the press-price step even if the diameter of the winding core is reduced, and to improve the sorting workability after the development processing. Another object is to provide an excellent photographic support.

[0015]

The above object of the present invention comprises a biaxially stretched polyester film having a curl curl of 110 m ^-1 or less and an elastic modulus of 500 kg / mm in both the width direction and the length direction. ² or more, the difference between the elastic modulus in the width direction and the elastic modulus in the length direction is 10 kg / mm ² or more, and
Photographic support orientation angle is less than 40 degrees 0 degrees, the curling curl is less 5 m ^-1 or more 90m ^-1, the difference between the width direction of the elastic modulus and the length direction of the elastic modulus is 50 Kg / mm ² or more and an orientation angle of 0 ° or more and 35 ° or less, and the biaxially stretched polyester film contains 70% by weight or more of at least one selected from an ethylene terephthalate unit and an ethylene 2-6 naphthalate unit. Containing, the biaxially stretched polyester film is composed of two or more layers, at least one layer consisting of a polyester containing an aromatic dicarboxylic acid having a metal sulfonate group as a copolymerization component, the biaxially stretched polyester The film is heat-treated at a temperature 5 ° C to 30 ° C lower than its glass transition point, or is 15 ° C or higher with the water content adjusted to 0.1% to 3%. And heat treated at a temperature lower than the glass transition point by 30 ° C. or more for 0.1 to 1500 hours, and the biaxially stretched polyester film is heat treated after providing a hydrophilic colloid layer on at least one side thereof. And a photographic light-sensitive material provided with a photographic emulsion layer on at least one side of these photographic supports.

The present invention will be described in detail below.

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

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2-6 naphthalene dicarboxylic acid, 2-7 naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid. , Cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketone dicarboxylic acid, phenylindanedicarboxylic acid and the like. As the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-
Hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol, etc. . Among the polyesters containing these as the main constituents, terephthalic acid and / or 2-6 naphthalenedicarboxylic acid as the dicarboxylic acid component, ethylene glycol and the diol component as ethylene glycol, from the viewpoints of transparency, mechanical strength, dimensional stability, etc. / Or 1-
Polyesters having 4 cyclohexanedimethanol as a main constituent are preferred. Among them, polyethylene terephthalate, polyethylene 2-6 naphthalate, terephthalic acid, a copolymerized polyester of 2-6 naphthalenedicarboxylic acid and ethylene glycol, and a polyester having a mixture of two or more of these polyesters as main constituents are preferable. When the content of ethylene terephthalate unit 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 2-6
Films containing naphthalate as a main component also have disadvantages such as the property of emitting fluorescence and the high price of resin. Therefore, depending on the purpose for which it is used, a film containing polyethylene terephthalate as the main component is usually used, and polyethylene 2-6 naphthalate is used particularly when highly thinning is required or when the film is abused at high temperatures. A film containing as a main component may be used. When the two are mixed, they have intermediate properties.

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 and diol component, or polyesters composed of them.

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 can be obtained, and the film has an appropriate water absorption property during the heat treatment described later. 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 sulfoterephthalic acid, 4-sodium sulfophthalic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid and these sodiums with other metals (eg potassium, lithium, etc.) and A compound substituted with an ammonium salt, a phosphonium salt, or the like, or an ester-forming derivative thereof, polyethylene glycol, polytetramethylene glycol, a polyethylene glycol-polypropylene glycol copolymer, or a hydroxy group at both ends thereof is oxidized to a carboxyl group. Compounds and the like are preferable.

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

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

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

If 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.
Is. By setting the content of the antioxidant within this range,
A so-called fog phenomenon in which the density of the unexposed portion of the photographic light-sensitive material becomes high can be prevented, and the haze of the film can be suppressed low, so that a photographic support having excellent transparency can be obtained. Incidentally, these antioxidants may be used alone or in combination of two or more.

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.

If desired, the polyester film of the present invention may be provided with slipperiness. 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 kinds.

The polyester film of the present invention may have a multilayer structure composed of different polyesters. For example,
When the layer made of polyester in which at least one compound having a hydrophilic group is copolymerized is the A layer and the layer made of other polyester is the B layer or the C layer, a two-layer constitution of the A layer and the B layer may be used. , 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 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 the layer A 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 layer B or layer C is 5
-60 μm, more preferably 10-50 μm. When the thickness of each layer is within the above range, water absorption can be appropriately imparted without impairing transparency, mechanical strength, and dimensional stability.

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 polyester film of the present invention has a multi-layered structure, the functions such as the above-mentioned oxidation prevention, light piping prevention, slipperiness, etc., or addition of various additives other than those mentioned above is carried out only in the surface layer. Therefore, 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 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 (hereinafter referred to as polyester D) laminated on both sides. The glass transition point of polyester D is preferably higher than that of the polyester of the inner layer. Specifically, it is preferably 5 ° C. or higher, more preferably 15 ° C. or higher. Further, the thickness of the layer made of polyester D needs to be thin within a certain range in order to maintain the water absorption of the film, and is preferably 0.05 to 10 μm.

The method for 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 biaxially stretched polyester film of the present invention has a curling curl of 110 as determined by the following method.
m ^-1 or less.

<Winding curl> A photographic light-sensitive material having a width of 35 mm and a length of 1200 mm is conditioned under the conditions of 23 ° C. and 55% RH for 1 day, and the diameter of the photographic light-sensitive layer side is set to 7 mm. Secure it so that it will not be rewound around the core of. Then put the film in a polyethylene cartridge case and
Heat treatment for 4 hours under the conditions of ℃ and 20% RH, then 23 ℃,
Allow to cool for 1 hour under the condition of 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, 23
Leave for 1 hour under conditions of ℃ 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 . At this time, when the film shows a curled curl as shown in FIG. 1, the curl degrees along both the left and right edges of the film are respectively obtained and averaged.

Here, the length direction means the winding direction. The width direction means a direction perpendicular to the length direction (excluding the film thickness direction). Since the winding direction is long, it is usually preferable to set the machine direction during film production to be the length direction.

If the curling curl of the film is too large, it is not possible to improve the transportability in the press-price process and the workability during sorting work, no matter how the orientation angle or elastic modulus of the film described below is adjusted. . In addition, when the curl curl is moderate, it is easier to let the leading end of the film come out of the film cartridge, and so-called bellows is excellent. Therefore, the more preferable range of curling curl of the film is 5 to 70 m ^-1 .

The biaxially stretched polyester film of the present invention is characterized in that the orientation angle, the elastic modulus in the width direction and the elastic modulus in the length direction, which are obtained by the following methods, are set within specific ranges.

<Orientation Angle> Two polarizing plates are set so that their polarizing axes are orthogonal to each other, and the two polarizing plates are placed so that the width direction and the length direction of the film coincide with the polarizing axes. The film is rotated in the range of 0 to 90 degrees, and the rotated angle θ when the field of view becomes darkest is obtained. The orientation angle is θ when the rotated angle θ is 0 to 45 degrees, and 90 when the rotated angle θ is 45 to 90 degrees.
Represented by -θ. The unit is degrees.

<Elastic Modulus> Film is 10 mm wide and 200 m long
After cutting out to a size of m and controlling the humidity for 12 hours under the condition of 23 ° C and 55% RH, Tensilon (RTA-10 manufactured by Orientec Co., Ltd.)
0), the chuck distance is 100 mm, and the pulling speed is 100 mm
A tensile test is performed at the speed of 1 / min to obtain the elastic modulus.

When various functional layers are coated on the surface of the film, the measurement can be performed after the coated layers are substantially removed by wiping with a solvent or the like. Generally, a biaxially stretched polyester film is excellent in solvent resistance, and thus physical properties do not change if treated for a short time.

The smaller the orientation angle of the film, the better the transportability in the press-price step and the workability in sorting work. However, since the elastic modulus in the width direction of the film is larger than the elastic modulus in the length direction, the The effect is remarkable. These effects cannot be obtained only by making the elastic modulus in the width direction larger than the elastic modulus in the length direction. The larger the difference between the elastic modulus in the width direction and the elastic modulus in the length direction, the greater these effects.However, if the difference is too large, the elastic modulus in the length direction becomes relatively small, and the film is not easily conveyed. It can not stand the tension of and deforms. Therefore, the orientation angle is 0 degree or more and 40
The elastic modulus in the length direction is 500 Kg / mm ² or more, the elastic modulus in the width direction is larger than the elastic modulus in the length direction, and the difference is 10 Kg / mm ² or more. is necessary. More preferably, the orientation angle is 0 degree or more and 35 degrees or less, and the difference between the elastic modulus in the width direction and the elastic modulus in the length direction is
It is 50 kg / mm ² or more.

Although the details of the reason why such an effect is obtained are not clear, a polyester film having a reduced curling curl is used as a photographic support, and a photographic light-sensitive material is wound around a core having a smaller diameter than before. By carefully observing the morphology during the sorting process after the price process and development process, the curling curl is equivalent to that of a photographic light-sensitive material that uses a TAC film wound on a core of conventional diameter as a photographic support. It has been found that although it is rather small and good, it often shows a twisted curl curl as shown in FIG. In the photographic light-sensitive material using the support of the present invention, twisted curl curls are hardly observed, and it is speculated that this is related to this.

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 photographic light-sensitive materials for medical and printing, 50
˜200 μm, especially 60 to 150 μm. If it is thinner than this range, the required strength may not be obtained,
If it is thick, it loses its superiority to conventional supports for photographic light-sensitive 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 unconditionally determined. in may be applied as much as possible becomes flat, usually, 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.

<Curl degree in the width direction> 35m width from the 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 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 .

The method for imparting curl in the width direction to the film is not particularly limited. For example, a method in which polyesters having different copolymerization components or main constituents are laminated, and polyesters of the same or different types having different intrinsic viscosities are used. 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 two layers of polyesters having the same main constituent but different copolymerization constituents,
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 ≦ d ₁ / d ₂ ≦ 10, where d ₁ and d ₂ are the thicknesses of both outer layers. If the film does not fall within the above range, stretching may be extremely difficult.

The biaxially stretched polyester film of the present invention preferably has a haze of 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 photographic light-sensitive material,
The image printed on photographic printing paper is blurred and unclear. The haze is measured according to ASTM-D1003-52.

The glass transition point of the biaxially stretched polyester film of the present invention is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. The glass transition point is obtained as an average value of the temperature at which the baseline begins to become eccentric as measured by a differential scanning calorimeter and the temperature at which the baseline newly returns. When the glass transition point is above 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, but the method is not particularly limited.

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

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 subjected to Tg-melting point-20 ° C.
Within the temperature range of 1, the film is transversely stretched and then heat set. The transverse stretching ratio is usually 3 to 6 times, and the ratio of the longitudinal stretching ratio to the transverse stretching ratio is appropriately adjusted so that the obtained biaxially stretched film has physical properties measured and has desirable characteristics. 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, 2
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 three 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 usually carried out at a temperature higher than the final transverse stretching temperature and a melting point of -20 ° C or lower for 0.5 to 300 seconds. At this time, it is preferable to heat-set while sequentially increasing the temperature difference in the range of 1 to 100 ° C. in the region divided into two or more.

The heat-fixed film is usually cooled to Tg or less, and the clip holding portions at both ends of the film are cut and wound up. At this time, 0.1-10% in the width direction and / or the longitudinal direction within the temperature range below the final heat setting temperature and above Tg.
Relaxation treatment is preferred. Further, for cooling, it is preferable to gradually cool from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. The 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. When the final heat setting temperature is T ₁ and the time required for the film to reach Tg from the final heat setting temperature is t, the cooling rate is calculated as
It is calculated 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 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.

Since the biaxially stretched polyester film obtained as described above still has a tendency to be rolled, it is possible to obtain a film which is hard to be rolled by heat treatment at a temperature of Tg or lower. When the film has a multi-layered structure, the lowest Tg among the polyesters constituting the layer that substantially bears the rigidity of the film is used as a reference. The heat treatment conditions may be appropriately determined depending on the material of the film and the material of the layer processed on the surface thereof. That is, if the material used has sufficient heat resistance, heat treatment at high temperature for a short time is performed.If heat resistance is not sufficient, heat treatment is performed at low temperature for a long time to obtain the required curl curl performance. Just do it. Usually, it is 0.1 to 1500 hours at the temperature of Tg-30 ° C or higher and Tg-5 ° C or lower of the film. When heat treatment is performed with the moisture content of the film adjusted to 0.1% or more and 3% or less, the heat treatment effect is accelerated, and a film that is hard to wind even when heat treated at a low temperature near room temperature is obtained. It is preferable because it is possible. The heat treatment condition in this case does not require heat treatment at a very high temperature, and is usually 0.1 to 1500 hours at a temperature of 15 ° C or higher and lower than Tg-30 ° C of the film. The water content of the film is a value obtained by measurement at a drying temperature of 150 ° C. using a trace moisture meter (for example, CA-05 type manufactured by Mitsubishi Kasei Co., Ltd.).

The process of carrying out such heat treatment is not particularly limited, and it is possible after the film is formed and before it is packaged into the form of the final product. Be careful because it disappears when heated to the temperature. Each functional layer that is usually coated on the film surface is formed by coating and drying an aqueous solution or dispersion, so the drying temperature is high and the film temperature may exceed Tg. It is preferable to heat-treat after coating. At this time, it is preferable to provide a layer for preventing sticking of the films from each other on at least one surface of the film. As the layer for preventing sticking, for example, a layer containing an additive that can be expected to have an effect as a slipping agent such as matting agent, wax, surfactant, particles of magnetic powder, or a polymer having a Tg higher than the heat treatment temperature or a heat Examples thereof include a layer made of a polymer having no plasticity. Furthermore, it is efficient and preferable to coat a film comprising a hydrophilic colloid layer on at least one surface of the film in order to allow the film to contain an appropriate amount of water. Examples of the hydrophilic colloid layer include a photographic emulsion layer and a non-photosensitive layer made of gelatin.

Immediately after the film is formed or immediately after the subsequent coating / drying, the film is in an almost dry state, and it is necessary to devise it in order to make the film contain an appropriate amount of water. Although not particularly limited, for example, the film and the film can be formed by embossing the end part or the center part of the film partially or over the entire length, bending the end part, or partially increasing the thickness of the film. To prevent the adherence of the film and to control the humidity for a required period in an air-conditioned room, a method of sandwiching a substance with good hygroscopicity such as paper between the film during winding, and blowing humidified air during 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 this purpose, embossing is usually 10 ~
It is preferable to process so that 100 μm unevenness can be 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 a core part. 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.

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, a copolymer containing vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride 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 slippery 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 production method (Emulsion p
reparation 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 e tal, Making and coating Photographic E
mulsion, 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. Additives used in such a process are RD No. 17643, RD No. 18176 and RD No. 17643.
No.308119 (Respectively, RD17643, RD18176 and RD3
Abbreviated as 08119. )It is described in. Table 1 shows the location of the description.

[0080]

[Table 1]

When the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, the photographic additives that can be used are described in the above RD. Table 2 shows the relevant locations.

[0082]

[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 the following RD17643 and RD308119. Table 3 shows the relevant locations.

[0084]

[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 constituting 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.

To develop the silver halide photographic light-sensitive material of the present invention, for example, "Theory" by TH James.
Of the Photographic Process 4th Edition "(Th
e Theory of The Photografic Process Forth Editio
n) Pages 291-334 and the Journal of the American Chemical Society.
Chemistry Society) Vol. 73, page 3100 (1951), known developers can be used. In addition, the color photographic light-sensitive material is RD1764328-29
Development can be carried out by a usual method described in pages RD18716, page 615 and RD308119, section XIX.

[0089]

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

In the following examples, density, glass transition temperature and melting point, film haze, water content, intrinsic viscosity,
Orientation angle, elastic modulus and rupture strength, thermal shrinkage, coefficient of hygroscopic expansion, curl degree in width direction, curl curl, curl after development, curl curl after development processing, press price transportability, and sorting workability are evaluated. It is obtained by the following.

(1) A film, which was conditioned at a density of 23 ° C. and 55% RH for 8 hours, was placed at 25 ± 0.5 ° C.
Gradient tube (n-heptane-carbon tetrachloride system)
24 hours later, read the scale on the film position.
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 cc / min and immediately quenched in liquid nitrogen.
A differential scanning calorimeter (manufactured by Rigaku Denki Co.,
DSC8230 type), and in a 100cc / min nitrogen stream, every minute
The temperature is raised at a heating rate of 10 ° C and Tg and Tm are detected. Tg was the average value of the temperature at which the baseline began to become eccentric and the temperature at which the baseline newly returned, and Tm was the peak temperature of the endothermic peak. The measurement start temperature is measured from Tg.
The temperature should be lower than 50 ℃.

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

(4) Intrinsic viscosity film or pellets are dissolved in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (weight ratio 60/40), and the concentration is 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
Plot ηsp / C against C and extrapolate the resulting line to zero concentration

[0095]

[Equation 1]

Find The unit is indicated by dl / g.

(5) Orientation angle As mentioned above.

(6) Elastic modulus and breaking strength The breaking strength was also obtained by the tensile test for obtaining the elastic modulus described above.

(7) Heat Shrinkage A 150 mm × 150 mm sample was cut out from the film and 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.

(8) Curling degree in width direction As mentioned above.

(9) Hygroscopic expansion coefficient thermomechanical property measuring device (TM-7000; 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.

(10) 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.

(11) Roll curl As mentioned above.

(12) Press-price transportability Using a photographic light-sensitive material having a curl in the same manner as in the curl curl measurement described above, the core side is placed at the beginning of the Noritsu Press Pricer PS-35-1 ( Noritsu Koki Co., Ltd.). The following criteria were used to rank each level according to the number of occurrences of 10 defective conveyances.

Rank Number of occurrences of conveyance failure ◎ 0 ○ ○ 1 × 2 to 10 (13) Sorting workability A cine-type photosensitive material with a curl was used in the same manner as the curl curl measurement described above. Development processing was performed by 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 ○ Slightly difficult × Very difficult Next, the method for producing the film used here will be described together.

Polyester A to polyester F were prepared as follows.

(Polyester A) 2-6 100 parts by weight of dimethyl naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were used as a transesterification catalyst to prepare calcium acetate hydrate 0.1.
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) 2-6 100 parts by weight of dimethyl naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were used as a transesterification catalyst to prepare calcium acetate hydrate 0.1.
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), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.03 part by weight, 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), antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.03 part by weight, 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) 2-6 Magnesium acetate hydrate as an ester exchange 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-
18 parts by weight of a solution of hydroxyethyl) isophthalic acid in ethylene glycol (concentration: 35% by weight), and 6 parts by weight of polyethylene glycol (number average molecular weight: 3000), 0.05 part by weight of antimony trioxide, 0.03 part by weight of phosphoric acid trimethyl ester, Irganox 0.210 parts by weight of 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 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 3.1 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C in a total transverse stretching ratio of 3.5 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) A film having a thickness of 80 μm was obtained in the same manner as in the method for obtaining film 1, except that the method for obtaining film 1 was changed to a longitudinal draw ratio of 3.3 times and a total transverse draw ratio of 3.3 times.
A biaxially stretched film of was obtained.

(Film 3) 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 3.1 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 of 150 ° C. in a total transverse stretching ratio of 3.5 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 4) 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 3.1 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 155 ° C. in a total transverse stretching ratio of 3.5 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 5) 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 3.1 times in the longitudinal direction at 95 ° C. using a roll type longitudinal stretching 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 3.5 times. Was stretched. Then, it was heat-treated at 70 ° C. for 2 seconds, further heat-set at the first heat-setting zone of 150 ° C. for 5 seconds, and second heat-setting zone of 230 ° C. for 15 seconds.
Then, while being relaxed in the transverse direction by 5%, it was gradually cooled to room temperature over 30 seconds to obtain a biaxially stretched film having a thickness of 90 μm.

(Film 6) 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 stretched in the longitudinal direction at 135 ° C. using a roll-type longitudinal stretching machine.
It was stretched twice.

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 3.7 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 7) A biaxially stretched film having a thickness of 80 μm was obtained in the same manner as in the method of obtaining the above film 1, except that the longitudinal stretching ratio was changed to 2.5 and the total transverse stretching ratio was changed to 4.0. It was

Table 4 shows the results of measuring the intrinsic viscosity, the glass transition temperature and the melting point of each of the biaxially stretched films thus obtained. When the film had a multi-layered structure, each layer was scraped off and the value for each layer was determined.

The film 4 is on the polyester A side,
Film 5 showed convex curl on the side of polyester C and film 6 on the side of the thinner layer of polyester E, so that the subsequent processing was performed so that the convex side became the photographic photosensitive layer side.

[0129]

[Table 4]

(Preparation of Photosensitive Materials 1-5) Film 1
The orientation angle at each position in the width direction of the film was measured, and the orientation angle had a distribution of 0 to 45 degrees in the width direction. Therefore, at each of the positions where the orientation angle shows each value of 0, 30, 35, 40 and 43 degrees, the width was 200 mm so that the position was the center of the width. At this time, width 200
An embossing ring heated to 265 ° C. was pressed on both sides of the mm film while adjusting the pressing pressure so that the height was 30 ± 5 μm, and embossing was performed. Here, the slitter processed films showing the orientation angles of 0, 30, 35, 40 and 43 degrees are respectively film 1-1, film 1-2 and film.
1-3, film 1-4, and film 1-5, and the density, haze, width curl, elastic modulus, and breaking strength were measured for each. The results are shown in Table 5.

<Coating of Undercoat Layer and Back Layer> Using the above film, an undercoat layer and a back layer were coated as follows.

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

(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 liquid B-1) 40 wt% butyl acrylate, 20 wt% styrene and Copolymer latex liquid containing 40% by weight of glycidyl 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 Further undercoat layer A -1 and 8 W / (m ² on the undercoat layer B-1
・ Min) corona discharge treatment, and undercoat layer A-
1 is coated with the following undercoating coating liquid A-2 and dried to form an undercoating layer A-2 having a dry film thickness of 0.1 μm.
The undercoating coating solution B-2 below was applied onto the above and dried to form an undercoating layer B-2 having a dry film thickness of 0.8 μm.

(Undercoating Coating 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 (LU-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 treatment of 8 W / (m ² · min) was performed on the above, and the following coating liquid MC-1 was applied to a dry film thickness of 1 μm.

(MC-1) The following components were mixed together by a dissolver and then dispersed by 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 Coated 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 MC-1 coating layer.
It was applied at 10 ml / m ² .

(OC-1) Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml <Coating of photographic photosensitive layer> Undercoat layer A-2 of the above film
The surface of was subjected to a corona discharge treatment of 25 W / (m ² · min) to sequentially form the following color photographic constituent layers.

Unless otherwise specified, 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 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 point 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 Diameter 0.3 μm, average iodide content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodide 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 size 0.4 μm, average iodide content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average grain size 0.3 μm, average iodide content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 ( Mo Sensitizing dye (S-5) 0.8 × 10 ^-4 (mol / silver 1 mol) 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) 0.004g High boiling point solvent (Oil-2) 0.35g Gelatin 1.0g Eighth layer Yellow filter (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 No. 9 Layer Low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 µm, average iodide 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) Silver iodobromide emulsion (average grain size) 0.8 [mu] m, an 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 ( (Yellow / 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 Eleventh layer First protective layer (PRO-1) Iodine Silver bromide (average particle diameter 0.08 μm) 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 monodisperse 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) After that, the solutions (H-1) and (S-1) having the following compositions were mixed at a ratio of 1: 1.
While maintaining the flow rate ratio of, the flow rate was accelerated (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, while maintaining the pH at 10.1 and the pH at 6.0, (H-2) and (S
-2) and were 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 resulting emulsion had an average grain size of 0.80 μm, a breadth of distribution (coefficient of variation of grain size distribution) of 12.4%, and a silver iodide content rate.
It was a monodisperse emulsion containing 8.5 mol% of octahedral silver iodobromide grains.

(G-1) Ocein gelatin 100.0 g Polyisopropyleneoxy / polyethyleneoxy / sodium disuccinate 10% by weight ethanol solution 25.0 ml 28% aqueous ammonia solution 440.0 ml 56% acetic acid aqueous solution 660.0 ml Finish with water 5000.0 ml (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% ammonia solution equivalent Finish with water 1030.5ml (H-2) Ocein Gelatin 302.1g Potassium bromide 770.0g Potassium iodide 33.3g Finish with water 3776.8ml (S-2) Silver nitrate 1133.0g 28% aqueous ammonia solution equivalent Finish with water 3776.8ml Iodobromide used in emulsion layers other than the 10th layer For silver emulsions, the average grain size of seed crystals, temperature, pAg, p
The H, flow rate, addition time and halide composition were changed to prepare the above emulsions having different average grain sizes and silver iodide contents.

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 to obtain 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 SU.
-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 100,000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg / m ² ).
Contains.

The structure of each compound used is shown below.

[0150]

[Chemical 1]

[0151]

[Chemical 2]

[0152]

[Chemical 3]

[0153]

[Chemical 4]

[0154]

[Chemical 5]

[0155]

[Chemical 6]

[0156]

[Chemical 7]

[0157]

[Chemical 8]

[0158]

[Chemical 9]

[0159]

[Chemical 10]

[0160]

[Chemical 11]

The photographic light-sensitive material thus obtained was wound around a paper core having a diameter of 250 mm for 500 m at 23 ° C. and 55
After conditioning the humidity for 48 hours under the condition of% RH, it was once wound on a separately prepared paper core having a diameter of 250 mm. At this time, when the water content was measured by sampling from the leading portion and the trailing portion of the film, respectively, it was 0.25%.

Then, the film was wound on the core and covered with a polyethylene film having a thickness of 20 μm in a double layer.
Heat treatment was performed at 0 ° C. for 72 hours.

After that, it was gradually cooled for 24 hours under the conditions of 23 ° C. and 55% RH.

At this time, a portion corresponding to the core portion at the time of heat treatment was sampled and a surface failure was examined. As a result, no wrinkles, folds, rubbing, etc. were found and it was good. In addition, after removing the photographic photosensitive layer of this sample by treating with pancreatin, further wiping each surface-treated layer with acetone to make substantially only the polyester film the orientation angle, the elastic modulus, the breaking strength, and the heat shrinkage rate. , And used for the measurement of hygroscopic expansion coefficient. The obtained results are also shown in Table 5. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation.

The photographic light-sensitive material obtained as described above was cut into a width of 35 mm and a length of 120 mm, and JIS 7519-198 was cut on both edges thereof.
Perforation was applied as described in 2. Table 5 also shows the curl curl of the cut photographic light-sensitive material, and the press-price transportability and sorting workability were evaluated. The standard 135 size color film XG400 (manufactured by Konica Corporation) prepared separately was also evaluated for press price transportability and sorting workability.

[0166]

[Table 5]

(Preparation of Photographic Photosensitive Materials 6 to 10) Film 2
The orientation angle at each position in the width direction of the film was measured, and the orientation angle had a distribution of 0 to 45 degrees in the width direction. Therefore, at each of the positions where the orientation angle shows each value of 0, 30, 35, 40 and 43 degrees, the width was 200 mm so that the position was the center of the width. At this time, width 200
An embossing ring heated to 265 ° C. was pressed on both sides of the mm film while adjusting the pressing pressure so that the height was 30 ± 5 μm, and embossing was performed. Here, the slitter processed films showing the orientation angles of 0, 30, 35, 40 and 43 degrees are respectively film 2-1, film 2-2 and film.
2-3, film 2-4, and film 2-5, and the density, haze, width curl, elastic modulus, and breaking strength were measured for each. The results are shown in Table 6.

Then, an undercoat layer, a back layer and a photographic light-sensitive layer were coated in the same manner as in the case of obtaining the photographic light-sensitive materials 1 to 5. The obtained photographic light-sensitive material was wound around a paper core having a diameter of 250 mm for 500 m, and the humidity was adjusted for 48 hours under the conditions of 23 ° C. and 55% RH, and then once again wound on a separately prepared paper core having a diameter of 250 mm. At this time, the water content was measured by sampling from the beginning and the back of the film, respectively.
It was 0.25%. Next, the film was double-coated with the polyethylene film having a thickness of 20 μm while being wound on the core, and heat-treated at 40 ° C. for 72 hours. After this, 23 ℃, 55%
It was gradually cooled under the condition of RH for 24 hours. Photographic material 1-
In the same manner as in the case of 5, each characteristic value was measured. The results obtained are also shown in Table 6. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion during the heat treatment was sampled and surface defects were examined, it was found to be good without wrinkles, folds, rubbing and the like.

The photographic light-sensitive materials obtained as described above were measured for curl curl in the same manner as in the case of photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are shown. It is also shown in 6.

[0170]

[Table 6]

(Preparation of photographic light-sensitive material 11) Using film 1-1, an undercoat layer, a back layer and a photographic light-sensitive layer were coated in the same manner as in the case of obtaining photographic light-sensitive materials 1 to 5. Then, about the obtained photographic light-sensitive material, 500 on a paper core with a diameter of 250 mm.
I wound up m. At this time, when the water content was measured by sampling from the leading portion and the trailing portion of the film, respectively, it was 0.02%.

Next, while the film was wound on the core, it was heat-treated for 72 hours under the conditions of 40 ° C. and 10% RH, and then gradually cooled under the conditions of 23 ° C. and 55% RH for 24 hours.

Here, each characteristic value was measured in the same manner as in the case of the photographic light-sensitive materials 1 to 5. The results obtained are shown in Table 7. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion during the heat treatment was sampled and surface defects were examined, it was found to be good without wrinkles, folds, rubbing and the like.

The photographic light-sensitive material thus obtained was measured for curl curl in the same manner as in the case of photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are shown. 7 is also shown.

(Preparation of photographic light-sensitive material 12) Film 1-1 was used to form an undercoat layer, a back layer and a photographic light-sensitive layer in the same manner as in the case of obtaining photographic light-sensitive materials 1 to 5. Then, about the obtained photographic light-sensitive material, 500 on a paper core with a diameter of 250 mm.
I wound up m. At this time, when the water content was measured by sampling from the leading portion and the trailing portion of the film, respectively, it was 0.02%.

Further, each characteristic value was measured in the same manner as in the case of the photographic light-sensitive materials 1 to 5. The results obtained are shown in Table 7. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion was sampled and a surface failure was examined, it was found to be good without wrinkles, folds, rubbing and the like.

The photographic light-sensitive materials obtained as described above were measured for curl curl in the same manner as in the case of photographic light-sensitive materials 1 to 5, and the press-price transportability and sorting workability were evaluated. The evaluation results are shown in Table 7.

(Preparation of photographic light-sensitive material 13) Using film 1-1, an undercoat layer, a back layer and a photographic light-sensitive layer were coated in the same manner as in the case of obtaining photographic light-sensitive materials 1 to 5. The obtained photographic light-sensitive material was wound around a paper core having a diameter of 250 mm for 500 m. At this time, the sample was sampled from the beginning and the end of the film respectively, and the water content was measured to be 0.02.
%Met. Then, while the film is still wound on the core, heat-treated at 110 ° C for 24 hours, then 23 ° C, 55% RH
It was gradually cooled under the conditions of 24 hours.

Here, each characteristic value was measured in the same manner as in the case of the photographic light-sensitive materials 1 to 5. The results obtained are shown in Table 7. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion during the heat treatment was sampled and surface defects were examined, wrinkles, folds, rubbing, etc. were found over 50 m from the core portion.

The photographic light-sensitive materials obtained as described above were measured for curl curl in the same manner as in the case of the photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are shown. 7 shows.

[0181]

[Table 7]

(Preparation of Photographic Photosensitive Materials 14 to 18) Film 3
The orientation angle at each position in the width direction of the film was measured, and the orientation angle had a distribution of 0 to 45 degrees in the width direction. Therefore, at each of the positions where the orientation angle shows each value of 0, 30, 35, 40 and 43 degrees, the width was 200 mm so that the position was the center of the width. At this time, width 200
An embossing ring heated to 265 ° C. was pressed on both sides of the mm film while adjusting the pressing pressure so that the height was 30 ± 5 μm, and embossing was performed. Here, the slitter processed films showing the orientation angles of 0, 30, 35, 40 and 43 degrees are respectively film 3-1, film 3-2 and film.
3-3, film 3-4, and film 3-5, and the density, haze, width curl, elastic modulus, and breaking strength were measured for each. The results are shown in Table 8.

Then, in the same manner as in obtaining the photographic light-sensitive materials 1 to 5, an undercoat layer, a back layer and a photographic light-sensitive layer were coated. The obtained photographic light-sensitive material was wound around a paper core having a diameter of 250 mm for 500 m. At this time, when the water content was measured by sampling from the leading portion and the trailing portion of the film, respectively, it was 0.27%. Next, while the film was still wound around the core, the film was double-coated with a polyethylene film having a thickness of 20 μm and heat-treated at 40 ° C. for 72 hours. Then, the mixture was gradually cooled under the conditions of 23 ° C. and 55% RH for 24 hours. Here, each characteristic value was measured in the same manner as in the case of the photographic light-sensitive materials 1 to 5. The obtained results are shown in Table 8. Orientation angle,
The elastic modulus and breaking strength were the same as those measured after film formation. In addition, when sampling the portion corresponding to the core during heat treatment and examining surface defects, wrinkles, folds,
It was good without scratches.

The photographic light-sensitive materials obtained as described above were measured for curl curl in the same manner as in the case of the photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are shown. 8 shows.

[0185]

[Table 8]

(Preparation of Photographic Photosensitive Materials 19 to 23) Film 4
The orientation angle at each position in the width direction of the film was measured, and the orientation angle had a distribution of 0 to 45 degrees in the width direction. Therefore, at each of the positions where the orientation angle shows each value of 0, 30, 35, 40 and 43 degrees, the width was 200 mm so that the position was the center of the width. At this time, width 200
260 mm on both sides of the film from the polyester B layer side
The embossing ring heated to ℃ was pressed while adjusting the pressing pressure so that the height was 30 ± 5 μm, and embossing was performed. Here, the slitter processed films showing the orientation angles of 0, 30, 35, 40 and 43 degrees are respectively film 4-
1, film 4-2, film 4-3, film 4-4, film
For each of these, the density, haze, width curl, elastic modulus, and breaking strength were measured. The results are shown in Table 9.

Then, an undercoat layer, a back layer and a photographic light-sensitive layer were coated in the same manner as in the case of obtaining the photographic light-sensitive materials 1 to 5. The obtained photographic light-sensitive material was wound around a paper core having a diameter of 250 mm for 500 m. At this time, when the water content was measured by sampling from the leading portion and the trailing portion of the film, respectively, it was 0.6%. Next, while the film was still wound around the core, the film was double-coated with a polyethylene film having a thickness of 20 μm and heat-treated at 40 ° C. for 72 hours. Then, the mixture was gradually cooled under the conditions of 23 ° C. and 55% RH for 24 hours. Table 9 also shows the results of measuring the respective characteristic values in the same manner as in the case of the photographic light-sensitive materials 1 to 5. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion during the heat treatment was sampled and surface defects were examined, it was found to be good without wrinkles, folds, rubbing and the like.

The photographic light-sensitive materials obtained as described above were measured for curl curl in the same manner as in the case of the photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are also shown. 9 shows.

[0189]

[Table 9]

(Preparation of Photosensitive Materials 24-28) Film 5
The orientation angle at each position in the width direction of the film was measured, and the orientation angle had a distribution of 0 to 45 degrees in the width direction. Therefore, at each of the positions where the orientation angle shows each value of 0, 30, 35, 40 and 43 degrees, the width was 200 mm so that the position was the center of the width. At this time, width 200
250 mm from both sides of the polyester D layer side of the film
The embossing ring heated to ℃ was pressed while adjusting the pressing pressure so that the height was 30 ± 5 μm, and embossing was performed. Here, the slitter-processed films showing the orientation angles of 0, 30, 35, 40, and 43 degrees are respectively film 5-
1, film 5-2, film 5-3, film 5-4, film
5-5, and the density, haze, width curl, elastic modulus, and breaking strength were measured for each. The results are shown in Table 10.

Then, an undercoat layer, a back layer and a photographic light-sensitive layer were coated in the same manner as in the case of obtaining the photographic light-sensitive materials 1 to 5. The obtained photographic light-sensitive material was wound around a paper core having a diameter of 250 mm for 500 m. At this time, when the water content was measured by sampling from the leading portion and the trailing portion of the film, respectively, it was 0.5%. Next, while the film was still wound around the core, the film was double-coated with a polyethylene film having a thickness of 20 μm and heat-treated at 40 ° C. for 72 hours. Then, the mixture was gradually cooled under the conditions of 23 ° C. and 55% RH for 24 hours. Table 10 also shows the results of measuring the respective characteristic values in the same manner as in the case of the photographic light-sensitive materials 1 to 5. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion during the heat treatment was sampled and surface defects were examined, wrinkles, folds, rubbing and the like were slightly generated, but they were tolerable to use.

The photographic light-sensitive materials obtained as described above were measured for curl curl in the same manner as in the case of the photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are also shown. Shown in 10.

[0193]

[Table 10]

(Production of Photosensitive Materials 29 to 33) Film 6
The orientation angle at each position in the width direction of the film was measured, and the orientation angle had a distribution of 0 to 45 degrees in the width direction. Therefore, at each of the positions where the orientation angle shows each value of 0, 30, 35, 40 and 43 degrees, the width was 200 mm so that the position was the center of the width. At this time, width 200
250 mm from both sides of the polyester D layer side of the film
The embossing ring heated to 0 ° C. was pressed while adjusting the pressing pressure so that the height was 30 ± 5 μm, and embossing was performed. Here, the slitter processed films showing the orientation angles of 0, 30, 35, 40 and 43 degrees are respectively film 6-
1, film 6-2, film 6-3, film 6-4, film
6-5, and the density, haze, width curl, elastic modulus, and breaking strength were measured for each. The results are shown in Table 11.

Then, an undercoat layer, a back layer and a photographic light-sensitive layer were coated in the same manner as in the case of obtaining the photographic light-sensitive materials 1 to 5. The obtained photographic light-sensitive material was wound around a paper core having a diameter of 250 mm for 500 m. At this time, when the water content was measured by sampling from the leading portion and the trailing portion of the film, respectively, it was 0.5%. Next, while the film was still wound around the core, the film was double-coated with a polyethylene film having a thickness of 20 μm and heat-treated at 40 ° C. for 72 hours. Then, the mixture was gradually cooled under the conditions of 23 ° C. and 55% RH for 24 hours. Table 11 also shows the results of measuring the respective characteristic values in the same manner as in the case of the photographic light-sensitive materials 1 to 5. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion during the heat treatment was sampled and surface defects were examined, wrinkles, folds, rubbing and the like were slightly generated, but they were tolerable to use.

The photographic light-sensitive material thus obtained was measured for curl curl in the same manner as in the case of photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are also shown. Shown in 11.

[0197]

[Table 11]

(Preparation of Photosensitive Materials 34 to 38) Film 7
The orientation angle at each position in the width direction of the film was measured, and the orientation angle had a distribution of 0 to 45 degrees in the width direction. Therefore, at each of the positions where the orientation angle shows each value of 0, 30, 35, 40 and 43 degrees, the width was 200 mm so that the position was the center of the width. At this time, width 200
An embossing ring heated to 265 ° C. was pressed on both sides of the mm film while adjusting the pressing pressure so that the height was 30 ± 5 μm, and embossing was performed. Here, the slitter processed films showing the orientation angles of 0, 30, 35, 40 and 43 degrees are respectively film 7-1, film 7-2 and film.
7-3, film 7-4, and film 7-5, and the density, haze, width curl, elastic modulus, and breaking strength were measured for each. The results are shown in Table 12.

Then, an undercoat layer, a back layer and a photographic light-sensitive layer were coated in the same manner as in obtaining the photographic light-sensitive materials 1 to 5. The obtained photographic light-sensitive material was wound around a paper core having a diameter of 250 mm for 500 m, and the humidity was adjusted for 48 hours under the conditions of 23 ° C. and 55% RH, and then once again wound on a separately prepared paper core having a diameter of 250 mm. At this time, the water content was measured by sampling from the beginning and the back of the film, respectively.
It was 0.25%. Next, the film was double-coated with the polyethylene film having a thickness of 20 μm while being wound on the core, and heat-treated at 40 ° C. for 72 hours. After this, 23 ℃, 55%
It was gradually cooled under the condition of RH for 24 hours. Photographic material 1-
In the same manner as in the case of 5, each characteristic value was measured. The results obtained are also shown in Table 12. The orientation angle, elastic modulus, and breaking strength were the same as those measured after film formation. Further, when a portion corresponding to the core portion during the heat treatment was sampled and surface defects were examined, it was found to be good without wrinkles, folds, rubbing and the like.

The photographic light-sensitive material obtained as described above was measured for curl curl in the same manner as in the case of photographic light-sensitive materials 1 to 5, and the results of evaluation of press-price transportability and sorting workability are shown. It is also shown in 12. During the evaluation of the sorting workability, the photographic light-sensitive materials 34 to 36 were significantly deformed and wavy, so the evaluation was stopped.

[0201]

[Table 12]

As is clear from the above results, it is not dependent on the type of polymer or the heat treatment method for reducing curling,
When the curling curl, elastic modulus and orientation angle of the film were within the scope of the present invention, good results were obtained in press-price transportability and sorting workability.

[0203]

As described above in detail, according to the present invention, the mechanical strength and the dimensional stability are excellent, and since the curling curl is not exhibited, the transportability in the press-splicing process and the post-developing It was possible to provide a photographic support excellent in sorting workability. Further, since the biaxially oriented polyester film of the present invention has the above-mentioned excellent properties, it is useful not only for a photographic support but also for various film applications used in a roll form.

[Brief description of drawings]

FIG. 1 is an explanatory view of a twisted curl curl.

Claims (8)

(57) [Claims] 1. A biaxially stretched polyester film, which has a curl of 110 m ^-1 or less and a modulus of elasticity in both the width direction and the length direction of 500 Kg / mm ² or more,
The difference between the elastic modulus in the width direction and the elastic modulus in the length direction is 10 kg / mm ²
The photographic support having the above-mentioned orientation angle of 0 degree or more and 40 degrees or less. Wherein said curling curling is less 5 m ^-1 or more 90m ^-1, the difference between the width direction of the elastic modulus and the length direction of the elastic modulus
The photographic support according to claim 1, wherein the photographic support is 50 kg / mm ² or more and the orientation angle is 0 degree or more and 35 degrees or less. 3. The biaxially stretched polyester film comprises 70% by weight of at least one selected from an ethylene terephthalate unit and an ethylene 2-6 naphthalate unit.
The photographic support according to claim 1 or 2, which contains the above. 4. The biaxially stretched polyester film is composed 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. To the photographic support according to claim 3. 5. The biaxially stretched polyester film,
The photographic support according to any one of claims 1 to 4, wherein the photographic support is heat-treated at a temperature 5 ° C to 30 ° C lower than its glass transition point. 6. The biaxially stretched polyester film comprises:
The heat treatment is performed at a temperature of 15 ° C. or more and 30 ° C. or more lower than its glass transition point for 0.1 to 1500 hours in a state where the water content is adjusted to 0.1% or more and 3% or less. To the photographic support according to claim 4. 7. The biaxially stretched polyester film comprises:
The photographic support according to claim 6, which is heat-treated after providing a hydrophilic colloid layer on at least one side thereof. 8. A photographic light-sensitive material having a photographic emulsion layer on at least one side of the photographic support according to claim 1.