JP3496165B2 - Photographic support - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer polyester film having at least one layer composed of a water-absorbent polyester, and particularly to coating failure and coating when a subbing layer is coated on the surface of a curled polyester film. A polyester film with excellent flatness after installation, which is useful as a photographic support for transparency, mechanical strength,
The present invention relates to a polyester film having excellent dimensional stability and curl recovery.

[0002]

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

Biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) has excellent transparency, mechanical strength and dimensional stability. Triacetyl cellulose film (hereinafter TAC) that has been conventionally used in strictly required printing films or X-ray films in which transparency and elasticity are required.
PET film is used instead of (film).

However, in a photographic light-sensitive material used in a roll form such as a general negative film, when a PET film is used, the water absorption is small and there is no curl recovery like a TAC film. Had a problem that the handling property of the film was extremely poor.

As a method for improving the curl-up recovery property of a PET film, for example, JP-A 1-244446 or 4-22 is known.
No. 0329 discloses a PET film in which a water absorbing component is copolymerized, and further, JP-A-4-93937, JP-A-5-69524 and JP-A-5-69524 disclose the same.
Nos. 5-235036 and 5-313302 describe a PET film obtained by copolymerizing these water absorbing components and a glass transition temperature (hereinafter referred to as T
Laminated films with high g) polyester films are disclosed.

Generally, a photographic light-sensitive material has a photographic light-sensitive layer laminated on at least one surface of a film. Since this photographic photosensitive layer contains a hydrophilic colloid layer, the size has a large humidity dependency, and especially under low humidity, the hydrophilic colloid layer contracts and greatly curls toward the photographic photosensitive layer (hydrophilic colloid layer) side. I will end up.

If the curl is too large, problems may occur such as scratches on the negative film, defocusing, or jamming during transport in the process of printing an image on photographic paper. Therefore, a curling process (so-called anti-curl process) opposite to the photosensitive layer side is usually performed so as to cancel the curl of the photosensitive layer.

Conventionally used TAC films can be easily anti-curled by treating one surface with a solvent, but PET films have excellent chemical resistance and solvent resistance. The same method as TAC film cannot be used. Therefore, a method of providing a hydrophilic colloid layer on the surface opposite to the photographic photosensitive layer surface is used. However, since the hydrophilic colloid layer is soft, it has a drawback that it is easily scratched or soiled. Note that P
As a method of anti-curling an ET film, for example, a method of laminating polyesters having different intrinsic viscosities is disclosed in JP-A-50-123420.

However, P obtained by copolymerizing a water-absorbing component
The water absorption of the ET film is certainly improved, but it is necessary to copolymerize a large amount of the water absorption component in order to obtain sufficient curl recovery, and the Tg is considerably lower than that of the ordinary PET film and the crystallinity is high. Will also decrease. Therefore, there is a problem that only a film having extremely poor heat resistance and mechanical strength can be obtained. It should be noted that P obtained by copolymerizing a water absorbing component
The laminated film of the ET film and the polyester film having a high Tg aims to solve these problems, but the polyester film having a high Tg does not have the curl recovery property, so the curl recovery as a laminated film is recovered. The property is deteriorated, which is a problem from the practical point of view.

A polyester film which is anti-curled by laminating polyesters having different intrinsic viscosities is coated with an undercoat layer as compared with a polyester film which is not anti-curled (that is, has no curl). The frequency of coating failures when installed is high,
Further, there is a problem that the film after coating becomes wavy, and the flatness and coatability are poor.

When the film is used as a photographic support, even if a hydrophilic photographic photosensitive layer is directly coated on a hydrophobic polyester film, the required adhesive force cannot be obtained. Therefore, the film is usually coated with an undercoat layer.

As described above, the poor coatability is a fatal drawback, and particularly when the PET film obtained by copolymerizing the water absorbing component as described above is used, the coatability is remarkably poor and it cannot be put to practical use. It was a thing.

Although the cause of the deterioration of the coatability of the curled polyester film is not clear, it is predicted as follows. That is, when the undercoat layer is applied to the film, it is necessary to keep the gap between the film and the coater constant in order to make the coating thickness uniform. Since it is difficult to match the coater with the curl shape of the film, usually hold the film on the back roll or press the coater or metering bar on the film to keep the film flat at least at the moment of applying. It is designed to be. At this time, the film that has been forcibly corrected has fine irregularities, and coating unevenness occurs. If the degree is worse, coating failure will occur.

In the subsequent drying step, unevenness in temperature is generated in the film due to coating unevenness, and the above unevenness is amplified to deteriorate the flatness.

It is expected that the PET film in which the water-absorbing component is copolymerized has more unevenness in water absorption and other unevenness in quality than the ordinary PET film, and the amplification factor of unevenness is further increased.

[0016]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide excellent transparency, mechanical strength and dimensional stability as a photographic support, and to improve curl recovery, coating properties and anti-curl properties. An object is to provide a photographic support made of an excellent polyester film.

[0017]

The objects of the present invention have been achieved by the following.

(1) A polyester film having a multilayer structure having at least one layer of a water-absorbent polyester, the polyester film being uniaxially stretched in the machine direction.
Then, split into two or more within the temperature range of Tg to Tm-20 ° C.
Horizontal stretching while raising the temperature in the stretched area, then heat setting
And are as hereinbefore unevenness transverse curl degree of the curl degree in 5 to 50 m ^-1 of the polyester film is within 10 m ^-1, the longitudinal direction of the heat shrinkage transverse heat shrunk from 0.5 to 3.0% A photographic support comprising a polyester film having a rate of -0.5 to 0.5%.

(2) From the polyester film according to the item (1), which contains an aromatic dicarboxylic acid having a sulfonate group and / or an ester-forming derivative thereof as a dicarboxylic acid component constituting the water-absorbent polyester. Become a photographic support.

(3) The polyester according to item (1) or (2), which comprises an ester-forming compound having a polyoxyalkylene group as a dicarboxylic acid component or a diol component constituting the water-absorbent polyester. A photographic support consisting of a film.

[0021]

( 4 ) Polyester is biaxially stretched in the longitudinal and transverse directions, and then obtained by holding it at a temperature of Tg-40 ° C. or higher for 0.01 to 5 minutes at a temperature not higher than the final transverse stretching temperature ( A photographic support comprising the polyester film described in 1) to ( 3 ).

( 5 ) After the polyester is biaxially stretched in the longitudinal and transverse directions, the temperature is raised above the final transverse stretching temperature within a temperature range of Tm-20 ° C. or lower in a region divided into two or more. It is characterized by being obtained by heat fixing while (1) ~
A photographic support comprising the polyester film according to item ( 4 ).

( 6 ) Obtained by biaxially stretching the polyester in the longitudinal and transverse directions and heat-setting, and then subjecting the polyester to a transverse relaxation of 0.1 to 10% within a temperature range not higher than the final heat-setting temperature and not lower than Tg. A photographic support comprising the polyester film according to any one of (1) to ( 5 ).

( 7 ) Polyester is biaxially stretched in the machine and transverse directions and heat-set, and then, when cooled from the final heat-set temperature to Tg or less, it is obtained by gradually cooling at a cooling rate of 100 ° C. or less per second. A photographic support comprising the polyester film according to any one of (1) to ( 6 ).

The present invention will be described in detail below.

According to the present invention, a polyester film having at least one water-absorbent polyester layer imparts a curl in the lateral direction to the film, thereby improving the curl recovery which seems to have nothing to do with appearance. It was found that the coating properties can be improved by further reducing the unevenness of the curl degree in the horizontal direction and setting the heat shrinkage ratio in the vertical direction and the horizontal direction within a specific range. It is a thing.

The polyester film according to the present invention is a polyester film having a multi-layer structure and comprises at least 1
Layer water absorbent polyester (hereinafter referred to as polyester A)
With a layer consisting of. Polyester A is a polyester having a film-forming property in which a dicarboxylic acid component and a diol component are main constituents and at least one compound having at least one hydrophilic group is copolymerized.

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl. Examples thereof include thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid and phenylindane dicarboxylic acid. Further, as the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,
2-bis (4-hydroxyethoxyphenyl) propane, bis
Examples thereof include (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone and cyclohexanediol.

Among the polyesters containing these as main constituents, the polyesters containing polyethylene terephthalate, polyethylene naphthalate and cyclohexane dimethylene terephthalate as main constituents are preferred from the viewpoints of transparency, mechanical strength and dimensional stability. preferable.

The hydrophilic group of the compound having at least one hydrophilic group is sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, polyoxyalkylene group, sulfamoyl group, carbamoyl group, acylamino group, sulfonamide. Group, disulfonamide group, ureido group, urethane group, alkylsulfonyl group, alkoxysulfonyl group, and the like, among them, sulfonic acid, sulfinic acid, phosphonic acid, carboxylic acid or a salt thereof, a polyoxyalkylene group, A disulfonamide group is preferred.

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

These compounds having a hydrophilic group may be used alone or in combination of two or more. In particular, it is preferable that both the aromatic dicarboxylic acid component having a sulfonate group and the dicarboxylic acid or diol 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 2 to 7 mol% based on the difunctional dicarboxylic acid constituting the polyester.

The number average molecular weight of the dicarboxylic acid or diol component having a polyoxyalkylene group is preferably 300 to 20000, more preferably 600 to 10000, and particularly preferably 1000 to 5000. The copolymerization ratio is preferably 3 to 15% by weight based on the polyester of the reaction product.

When the copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group, the number average molecular weight of the dicarboxylic acid or diol component having a polyoxyalkylene group, and the copolymerization ratio are within this range, the transparency and mechanical strength of the film are improved. The water absorption can be improved without impairing the water absorption. The polyester A may be copolymerized with other copolymerization components as long as the effect of the present invention is not impaired, and may be a blend of two or more polyesters. Examples of these include the above-mentioned dicarboxylic acid component and diol component, or polyesters comprising the above dicarboxylic acid component and diol component.

The multilayer structure of the polyester film according to the present invention is not particularly limited. For example, when the layer made of polyester A is the A layer and the layer made of another polyester is the B layer or the C layer, a two-layer structure composed of the A layer and the B layer may be used, or A layer / B layer / A layer. , A layer / B layer / C layer, B layer / A layer / B layer, or B layer / A layer / C layer. Further, a structure having four or more layers is of course possible, but it is not preferable in practice because the manufacturing equipment becomes complicated.

The thickness of the layer A is preferably 30% or more of the total thickness of the polyester film,
Furthermore, the thickness is preferably 40 to 70%. In this case, the thickness of the A layer is the thickness of the layer when the A layer is only one layer, and is the sum of the thicknesses when the A layer is 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, the polyester film is excellent in transparency, mechanical strength, dimensional stability, and water absorbency, and thus, is excellent in curl recovery property.

The total thickness of the film is not particularly limited,
It is preferably 20 to 200 μm, preferably 40 to 130 μm, and particularly 55 to 95 μm. If the thickness is less than this range, the required strength may not be obtained in some cases, and if it is thick, the advantage over conventional supports for photographic light-sensitive materials is lost.

The polyester constituting the B layer or the C layer 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 dicarboxylic acid component of the main constituents includes terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, diphenyl sulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, cyclohexane dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl. Examples thereof include thioether dicarboxylic acid, diphenyl ketone dicarboxylic acid and phenylindane dicarboxylic acid. Further, as the diol component, ethylene glycol, propylene glycol,
Tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-
Examples thereof include hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone and cyclohexanediol.

Among the polyesters containing these as the main constituents, the polyesters containing polyethylene terephthalate, polyethylene naphthalate, and cyclohexane dimethylene terephthalate as the main constituents are preferable from the viewpoints of transparency, mechanical strength, dimensional stability and the like. .

Since the polyester A is a copolyester, the transparency, mechanical strength and dimensional stability are inevitably lower than those of the homopolyester. However, this layer has transparency, mechanical strength and dimensional stability. By laminating a polyethylene terephthalate layer having excellent properties, another homopolyester layer, or another copolyester layer, the transparency, mechanical strength, and dimensional stability of the entire film can be improved.

The polyester constituting the B layer or the C layer may be copolymerized with other copolymerization components as long as the effects of the present invention are not impaired, or a blend of two or more polyesters. It may be. Examples of these include the above-mentioned dicarboxylic acid component and diol component,
Or mention may be made of polyester.

For example, for the purpose of improving the adhesion between the A layer and the B layer or between the A layer and the C layer, the polyester is constituted as the copolymerization ratio of the aromatic dicarboxylic acid component having a sulfonate group. 0.5 to 5 mol% based on the difunctional dicarboxylic acid is preferred. Further, the number average molecular weight of the dicarboxylic acid or diol component having a polyoxyalkylene group is preferably 300 to 20000, and further 600 to 100
Those in the range of 00, particularly in the range of 1000 to 5000 are preferable. The copolymerization ratio is 0.5 with respect to the reaction product polyester.
It is preferably about 10% by weight. Also, polyester A
Is preferably contained in the B layer or the C layer in an amount of 1 to 50% by weight, particularly 10 to 40% by weight based on the polyester constituting the B layer or the C layer in order to improve the adhesive strength.

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 preferably contains an antioxidant. In particular, the effect becomes remarkable when the polyester contains a compound having a polyoxyalkylene group. The type of the antioxidant to be contained is not particularly limited, and various kinds of antioxidants can be used. Examples include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds. You can 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. When the content of the antioxidant is small, a so-called fog phenomenon in which the density of the unexposed portion of the photographic light-sensitive material becomes high is likely to occur, and when it is too large, haze of the film becomes high and transparency may be deteriorated. In addition, these antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type.

The polyester used in the present invention preferably contains a dye for the purpose of preventing the light piping phenomenon. The dye to be blended for such a purpose is not particularly limited in its type, but in the production of the film, it is necessary that it has excellent heat resistance, and anthraquinone-based or perinone-based dyes may be used. Can be mentioned. Further, as the color tone, gray dyeing is preferable as seen in general photographic light-sensitive materials. Examples of these dyes include MACREX series manufactured by Bayer, SUMIPLAST series manufactured by Sumitomo Chemical Co., Ltd., and Diaresin series manufactured by Mitsubishi Kasei Co., Ltd.
These can be used alone or in combination of two or more kinds of dyes so as to obtain a required color tone. At this time, the spectral transmittance of the film is 60 in the wavelength range of 400 to 700 nm.
% And 85% or less, and using a dye so that the difference between the maximum and the minimum of the spectral transmittance within the wavelength range of 600 to 700 nm is within 10% prevents the light piping phenomenon and also provides good photographic prints. To obtain

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 added at the time of polyester synthesis, or a surfactant or the like on the film surface. It is generally applied to the.

Among these, the internal particle deposition method capable of controlling the deposited particles to be relatively small is preferable because slipperiness can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used,
In particular, Ca and Mn are preferable because high transparency can be obtained. These catalysts may be used alone or in combination of two.

Furthermore, since the polyester film of the present invention has a multi-layered structure, the above-mentioned functions such as antioxidation, light piping prevention, slipperiness and the like, or addition of various additives other than those mentioned above are 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 other polyester layers on both sides of the polyester film. At this time, it is preferable to use the above-mentioned polyester as the polyester constituting the layer made of another polyester (polyester D) laminated on both sides. The Tg of the polyester D is preferably higher than the Tg of the water-absorbing polyester of the present invention (polyester A). The Tg of polyester D is preferably 65 ° C. or higher, more preferably 75 ° 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.
μm is preferred.

The method of synthesizing the polyester as the raw material of the polyester film of the present invention is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first a dialkyl ester is used as a dicarboxylic acid component, and an ester exchange reaction is performed between this and the diol component, and this is heated under reduced pressure. A transesterification method in which the excess diol component is removed to perform polymerization can be used. At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added.
Further, anti-coloring agents, antioxidants, crystal nucleating agents, slip agents, stabilizers, anti-blocking agents, ultraviolet absorbers, viscosity modifiers, defoamers, clarifiers, antistatic agents, pH adjusting agents, dyes, A pigment or the like may be added.

The polyester film of the present invention has a degree of curl in the transverse direction of the film of 5 to 50 as determined by the following method.
m ^-1 , the curl degree unevenness is within 10 m ^-1 , and the heat shrinkage in the longitudinal direction is 0.5 to 3.0%, and the heat shrinkage in the transverse direction orthogonal thereto is -0.5 to 0.5%.

<Curling degree in lateral direction and unevenness of curling degree> The film is slit in the longitudinal direction over the entire width in the lateral direction so as to have a strip shape with a width of 35 mm. Then, a 2 mm sample is cut out from each strip of film in the longitudinal direction at 23 ° C and 55%.
After conditioning the humidity for one day under the condition of RH, the radius of curvature of the curl in the width direction of the sample is calculated in meters, and the reciprocal thereof indicates the curl degree in the lateral direction. The measured value is a value obtained by averaging the values of the curl degree in the lateral direction obtained for each strip. The unevenness of the curl degree is represented by the difference between the maximum and minimum values of the curl degree in the lateral direction obtained for each strip. The unit of each value is m ⁻¹ .

<Heat Shrinkage> A sample of 150 mm × 150 mm was cut out from the film, conditioned under conditions of 23 ° C. and 55% RH for 1 day, and then scored in 100 mm intervals in the vertical and horizontal directions. . And heat treatment at 130 ℃ for 30 minutes,
Further, the distance between the scoring lines is measured after the humidity is controlled for 1 day under the conditions of 23 ° C. and 55% RH. The difference between the intervals of the scoring lines before and after the heat treatment is calculated and expressed as a percentage of the interval before the heat treatment. In addition, the direction of contraction is +, and the direction of expansion is-
And

The term "transverse direction" as used herein means a direction (excluding the film thickness direction) at right angles to the winding direction when the photographic light-sensitive material is used in a roll form. The longitudinal direction means this winding direction. Since the winding direction is long, the machine direction during film production is usually the vertical direction,
It is preferable that the width direction is the lateral direction.

When the degree of curl in the lateral direction of the polyester film is within the above range, excellent curl recovery can be obtained and anticurl useful as a support for photographic light-sensitive materials can be imparted. If the degree of curl in the lateral direction is less than the above range, curl recovery is poor, and if it is more than the above range, the anti-curl is too large, and problems such as scratches and jamming occur during the printing process on photographic printing paper. Occurs. In addition, in the case of improving the wrapping recovery property, the effect is exhibited when the film is wound with the convex side of the curl inside.

The method of imparting a lateral curl to the polyester film is not particularly limited, and examples thereof include a method of laminating polyesters having different copolymerization components or main constituents, and the same or different polyesters having different intrinsic viscosities. And a method of changing the thicknesses of both outer layers with a three-layer structure. Further, it is of course possible to appropriately combine these methods and to impart curl using these methods in a layer structure of four layers or more.

Among these, a method of laminating two-layered polyesters having the same main constituent but different copolymerization constituents,
Alternatively, the center layer and both outer layers have a three-layer structure in which polyesters having the same main constituent but different copolymerization components are laminated, and a method of changing the thickness of both outer layers is preferable.

In the method of laminating the same or different polyesters having different intrinsic viscosities, the difference in the intrinsic viscosities is 0.02 to
0.5 (g / dl) is preferable, and in the method of changing the thickness of both outer layers, the thickness of both outer layers is d1.
, D2, 1.1 ≦ d1 / d2 ≦ 10, and further 2 ≦
From the viewpoint of film production, it is preferable that d1 / d2≤5. If the film does not fall within the above range, stretching may be extremely difficult.

Further, in the polyester film of the present invention, the unevenness of the degree of curl in the transverse direction is within 10 m ^-1 , and the heat shrinkage rate in the longitudinal direction is 0.5 to 3.0%. By setting it to −0.5 to 0.5%, excellent coating properties can be obtained.

That is, even if a water-absorbing PET film is manufactured by the same method as that of a normal non-water-absorbing PET film, there may be unevenness in film thickness or other unevenness in quality, probably because of water absorption during manufacturing. Only a film that becomes large and has large unevenness in the degree of curl in the lateral direction can be obtained.

However, by excellently reducing the unevenness of the curl degree in the lateral direction of the film and setting the heat shrinkage rates in the longitudinal direction and the lateral direction within a specific range, excellent coatability can be obtained. . The curl in the lateral direction of the film is uneven
If it is larger than 10 m ^-1 , no good coatability can be obtained no matter how the heat shrinkage ratio in the longitudinal direction and the lateral direction is adjusted.
When the heat shrinkage ratio in the lateral direction exceeds the above range, good coatability cannot be obtained even if the unevenness of the curl degree in the lateral direction of the film is reduced.

As for these characteristic values, the unevenness of the curl degree in the horizontal direction is within 5 m ⁻¹ , and the heat shrinkage ratio in the vertical direction is 0.6 to 2.0.
%, And the heat shrinkage ratio in the transverse direction perpendicular thereto is more preferably -0.3 to 0% from the viewpoint of improving coatability.

The water content of the polyester film of the present invention determined by the following method is preferably 0.5% by weight or more, and more preferably 0.6 to 3.0% by weight.

By setting the water content of the film to 0.5% by weight or more, the curling and curling recovery is improved. If the water content is too high, dimensional stability deteriorates due to moisture absorption, so care must be taken especially when dimensional stability is strictly required.

<Water Content> The film was conditioned at 23 ° C. and 20% RH for 12 hours, then immersed in pure water at 38 ° C. for 15 minutes, and then a trace moisture meter (Mitsubishi Kasei CA- 05 type)
Was measured at a drying temperature of 150 ° C.

The haze of the polyester film of the present invention is preferably 3% or less. More preferably, it is 1% or less. When the haze is more than 3%, when the film is used as a photographic support, the image printed on the photographic printing paper becomes blurry and unclear. The haze is
It is measured according to ASTM-D1003-52.

The Tg of the polyester film of the present invention is
The temperature is preferably 60 ° C or higher, more preferably 70 ° C or higher and 120 ° C or lower. Tg is determined by measuring with a differential scanning calorimeter. If the Tg is lower than 60 ° C, the film may be deformed in the drying process in the developing processor. Also, Tg is 120
If the temperature is higher than 0 ° C, the curl recovery property will be significantly deteriorated.

Next, the method for producing the polyester film according to the present invention will be described, but the present invention is not limited thereto.

As a method for laminating the polyester, a conventionally known method can 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.

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 is subjected to single-stage or multi-stage longitudinal stretching. is there. The draw ratio is usually in the range of 2.5 to 6 times, and it is necessary to set it in a range in which subsequent transverse stretching is possible. The stretching temperature is preferably set based on the highest Tg of Tg of the polyester of each constituent layer.

In the present invention, the polyester film uniaxially stretched in the machine direction obtained as described above is used as Tg to Tm.
Within the temperature range of −20 ° C., it is preferable to carry out transverse stretching while raising the temperature in a stretching region divided into two or more and then heat setting. 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.

The stretching temperature is divided into at least two stages,
Further, the number of steps is preferably three. It may be more than that, but there will be problems such as large equipment. The temperature of each area is set to increase sequentially, and the temperature difference is 1
It is preferably in the range of -50 ° C. Next, heat setting is performed. Before this, it is necessary to maintain the biaxially stretched film at a temperature of Tg-40 ° C. or higher for 0.01 to 5 minutes at a temperature of the final transverse stretching temperature or less in order to enhance the effect of the present invention. preferable.

When heat-fixing a film biaxially stretched in the longitudinal and transverse directions, at a temperature higher than the final transverse stretching temperature,
It is preferable to heat-set while raising the temperature in a region divided into two or more within a temperature range of Tm-20 ° C or lower. The heat setting time is usually 0.5 to 300 seconds.

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, it is preferable to perform a lateral relaxation treatment of 0.1 to 10% within a temperature range of not higher than the final heat setting temperature and not lower than Tg. In addition, it is preferable that the cooling is gradually cooled 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 carried out by a conventionally known means. However, it is particularly preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film. The cooling rate was calculated by setting the final heat setting temperature to T1 and the film from the final heat setting temperature to T
When the time to reach g is t, (T1-Tg)
It is a value calculated by / t. More optimal conditions of these heat setting conditions, cooling, and relaxation treatment conditions differ depending on the polyester constituting the film, so by measuring the physical properties of the obtained biaxially stretched film and adjusting appropriately so as to have preferable properties. Just decide.

In the production of the above film, functional layers such as an antistatic layer, a slipping layer, an adhesive layer and a barrier layer may be coated before and / or after stretching. At this time, various surface treatments such as corona discharge treatment and chemical treatment can be applied as necessary. Further, for the purpose of improving the strength, it is also possible to carry out the stretching used for known stretching films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal transverse stretching, and transverse / longitudinal stretching.

The polyester film obtained as described above has small thickness unevenness, excellent flatness, and very little quality unevenness, so that the effects of the present invention can be maximized.

Since the polyester film of the present invention is excellent in transparency, mechanical strength, dimensional stability and water absorption, it can be used in various transparent film applications, for example, OHP film, packaging film, photographic light-sensitive material support. It is useful for body or cover layer. It is particularly suitable as a support for a photographic light-sensitive material which is used in the form of a roll.

The photographic light-sensitive material can be obtained by providing a photographic emulsion layer on at least one side of a photographic support comprising the polyester film of the present invention. The photographic emulsion layer is
It 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. Also,
A hydrophilic colloid layer as a protective layer may be coated on the silver halide emulsion layer. Further, the silver halide emulsion layers may be separately coated on the respective 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. If necessary, a non-photosensitive hydrophilic colloid layer such as an intermediate layer, a protective layer, an antihalation layer, a backing layer, etc., which is made of other hydrophilic colloid, may be provided.

In providing the photographic emulsion layer on the photographic support, a surface treatment may be carried out. These surface treatments include
Examples thereof include physical treatments such as corona discharge, ultraviolet treatment, plasma treatment, and flame treatment, and chemical treatments such as alkali treatment, amine treatment, trichloroacetic acid treatment, and phenols treatment. Also, an undercoat layer can be provided.

The silver halide emulsion is, for example, Research Disclosure (hereinafter abbreviated as RD) No. 17643, 22.
Page 23 (December 1979), “1. Emulsion production method (Emulsion pr
eparation and types) ”, and RD No.18716, 648
P.Glkides, Chimie et Physique Photographique, Pa.
ul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDauffin, Photographic Emulsio
Chemistry Focal Press 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VLZe
likman etal, Making and coating Photographic Emulsi
on, 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 described in RD No. 17643, RD No. 18716 and RD No. 308119 (hereinafter abbreviated as RD17643, RD18716 and RD308119, respectively). The following shows the location.

[Item] [RD308119] [RD17643] [RD18716] Chemical sensitizer page 996 III-A page 23 648 spectral sensitizer page 996 IV-A, B, C, D pages 23-24 648-9 Page I, J supersensitizer page 996 page IV-AE, J section 23-24 page 648-9 page antifoggant page 998 VI page 24-25 page 649 stabilizer 998 page VI page 24-25 page 649 page When the photographic light-sensitive material of the invention is a color photographic light-sensitive material, photographic additives that can be used are described in the above RD. The following shows the relevant locations.

[Item] [RD308119] [RD17643] [RD18716] Color turbidity inhibitor 1002 page VII-I section 25 page 650 Dye image stabilizer 1001 page VII-J section 25 whitening agent 998 V page 24 UV ray Absorber 1003 VIII-C, pages 25-26 XIII-C Light absorber 1003 VIII 25-26 Light scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 page 651 Static Inhibitor 1006 page XIII 27 page 650 Hardener 1004 page X 26 page 651 Plasticizer 1006 page XII 27 page 650 Lubricant 1006 page XII 27 page 650 Activator / coating aid 1005 page XI 26-27 Page 650 Matting agent Page 1007 XVI Developer (included in light-sensitive material) Page 1011 XX-B Further, when the photographic light-sensitive material of the present invention is a color photographic light-sensitive material, various couplers can be used. Specific examples are described in RD17643 and RD308119 below. The relevant description is shown below.

[Item] [RD308119] [RD17643] Yellow coupler page 1001 VII-D item page 25 VII-C to G item Magenta coupler page 1001 VII-D item page 25 VII-C to G item cyan coupler 100 page VII- Item D Page 25 VII-C to G Colored coupler Page 1002 VII-G Item 25 Page VII-G DIR coupler 1001 Page VII-F Item 25 Page VII-F BAR coupler 1002 Page VII-F Other useful Residue page 1001 VII-F Release coupler Alkali-soluble coupler page 1001 VII-E Also, these additives can be added to the photographic light-sensitive layer by the dispersion method described in RD308119 page 1007 XIV. For the color photographic light-sensitive material, the above-mentioned RD308119 VII
An auxiliary layer such as a filter layer or an intermediate layer described in the section -K can be provided. In the case of constructing a color photographic light-sensitive material, various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned item RD308119 VII-K can be adopted.

To develop the silver halide photographic light-sensitive material of the present invention, for example, T.W. H. James, The Th
eory of The Photografic Process Forth Edition 2nd
Pages 91-334 and Journal of the American Chemica
The developer known per se described in Society, Vol. 73, page 3,100 (1951) can be used. Also,
For color photographic light-sensitive materials, see RD17643, pages 28-29, RD1871.
6 Development can be carried out by a usual method described on page 615 and RD308119XIX.

[0093]

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

The glass transition temperature and melting point, the film haze, the water content, the intrinsic viscosity, used in the evaluation of the examples described below,
Values such as elastic modulus and breaking strength, heat shrinkage, curl degree in the lateral direction and unevenness of curl degree, coating failure, flatness, curl recovery are obtained by the following methods.

(1) Glass transition temperature Tg and melting point Tm 10 mg of film or pellet is melted at 300 ° C. in a nitrogen stream of 300 cc / min and immediately cooled in liquid nitrogen.
A differential scanning calorimeter (manufactured by Rigaku Denki Co., Ltd.
DSC-8230 type) in a 100 cc nitrogen stream per minute,
The temperature is raised at a heating rate of 10 ° C./min to detect Tg and Tm. Tg was the average value of the temperature at which the baseline began to become eccentric and the temperature at which the baseline newly returned, and Tm was the peak temperature of the endothermic peak. The measurement start temperature is set to a temperature lower than the measured Tg by 50 ° C. or more. (2) Film haze Measured according to ASTM-D1003-52.

(3) Moisture content film was conditioned at 23 ° C. and 20% RH for 12 hours, then immersed in pure water at 38 ° C. for 15 minutes, and then trace moisture meter (CA manufactured by Mitsubishi Kasei Corp.) -05 type) at a drying temperature of 150 ° C.

(4) Intrinsic viscosity Film or pellets were dissolved in a mixed solvent of phenol and 1,1,2,2-tetrachloroethane (weight ratio 60/40),
A solution having a concentration of 0.2 g / dl, 0.6 g / dl, 1.0 g / dl is prepared, and the specific viscosity (η _sp ) at each concentration (C) is determined by an Ubbelohde viscometer at 20 ° C. Then η _sp /
C is plotted against C, and the obtained straight line is extrapolated to zero concentration to obtain the intrinsic viscosity [η] = lim (η _sp / C) C → 0. The unit is indicated by dl / g.

(5) Elastic Modulus and Breaking Strength The film was cut into a piece having a width of 10 mm and a length of 200 mm.
After conditioning the humidity for 12 hours at 55 ° C and 55% RH, using Tensilon (RTA-100) manufactured by Orientec Co., Ltd., the chuck distance was set to 100 mm, and a tensile test was performed at a tensile speed of 100 mm / min. The elastic modulus and breaking strength in the transverse direction are obtained. The values of elastic modulus and breaking strength are expressed by averaging the values in the vertical and horizontal directions.

(6) 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 in each of the vertical and horizontal directions. And 130
The heat treatment is performed at 30 ° C. for 30 minutes, and the scoring line interval is measured after the humidity is controlled for 1 day under the condition of 23 ° C. and 55% RH. The difference between the intervals of the scoring lines before and after the heat treatment is calculated and expressed as a percentage of the interval before the heat treatment. It should be noted that the shrinking direction is + and the extending direction is − as compared to before the heat treatment.

(7) Curling degree in the lateral direction and unevenness of curling degree The film is slit in the longitudinal direction over the entire width in the lateral direction so as to form a short fence having a width of 35 mm. Then, a 2 mm sample was cut out from each short fence film in the longitudinal direction, and 23 ° C, 55% R
After conditioning the humidity for 1 day under the condition of H, the radius of curl of the curl in the width direction of the sample is determined in meters, and the reciprocal thereof represents the curl degree in the lateral direction. The measured value is an average value of the curl values in the lateral direction obtained for each short fence. The unevenness of the curl degree is represented by the difference between the maximum value and the minimum value of the lateral curl value obtained for each short fence. The unit of each value is m ⁻¹ .

(8) Coating failure One side of the film was subjected to a corona discharge treatment of 8 W / (m ² · min), and the undercoating coating liquid A-1 below was applied at 50 m / min at room temperature and normal humidity. Apply at a speed of min using a roll-fit coating pan and air knife, and dry at 90 ° C
And dried for 30 seconds to form an undercoat layer A-1 having a dry film thickness of 0.8 μm. The undercoating coating solution B-1 described below was applied to the other surface of this film by the same method and dried to form an undercoating layer B-1 having a dry film thickness of 0.8 μm.

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

<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 liquid B-2> Water-soluble conductive polymer (UL-4) 60 g Latex liquid containing compound (UL-5) as a component (solid content 20%) 80 g Ammonium sulfate 0.5 g Hardener (UL- 6) 12 g Polyethylene glycol (weight average molecular weight 600) 6 g Finished with water 1000 ml The number of coating failures per 1 m ^{2 of} this film was visually evaluated and ranked according to the following criteria.

Rank Number of coating failures ◎ 0 ○ 1 to 3 × 4 or more The practicability in this ranking was determined based on the acceptability as a photographic support. The above is preferable.

(9) Planarity The film coated with the above-mentioned undercoat layer is cut into 1 m × 1 m, and 23
After conditioning the humidity for 12 hours at 55 ° C. and 55% RH, it was spread on a flat board, the degree of waving was visually evaluated, and ranked according to the following criteria. The practicality in this ranking is determined based on the acceptability as a photographic support, and it is preferable that the rank is ◯ or higher.

Rank Waviness ⊚ Good ○ Waviness is clearly seen × Large waviness (10) Winding recovery property Using the film coated with the above undercoat layer, the undercoat layer B-
Corona discharge of 8 W / (m ² · min) was applied to No. ² and the following coating liquid MC-1 was applied so that the dry film thickness was 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, 10 parts of the following coating liquid OC-1 on the MC-1 coating layer.
It was applied so as to be ml / m ² .

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml Further, a corona discharge of 25 W / (m ² / min) was applied on the undercoat layer A-2 to sequentially form the following photographic constituent layers. , A multilayer color photographic light-sensitive material was prepared.

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

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

<Photographic Constituent Layer> First Layer: Antihalation Layer (HC) Black Colloidal Silver 0.15 g UV Absorber (UV-1) 0.20 g Colored Cyan Coupler (CC-1) 0.02 g High Boiling Solvent (Oil-1) ) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g Second layer; Intermediate layer (IL-1) Gelatin 1.3 g Third layer; Low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (Average grain size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-2) 3.2 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ^-4 (mol / silver 1 mol) Cyan Coupler (C-1) 0.50g Cyan coupler (C-2) 0.13g Colored cyan coupler (CC-1) 0.07g DIR compound (D-1) 0.006g IR 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 iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ^-4 (mol / silver) 1 mol) increase 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 1 mol) Sensitizing dye ( S-8) 0.3 × 10 ^-4 (mol / silver 1 mol) Magenta coupler (M-1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) ) 0.004g High boiling point solvent (Oil-2) 0.35g Gelatin 1.0g 8th layer; Yellow filter layer (YC) Yellow colloidal silver 0.1g addition Agent (HS-1) 0.07g Additive (HS-2) 0.07g Additive (SC-1) 0.12g High boiling solvent (Oil-2) 0.15g Gelatin 1.0g 9th layer; low sensitivity blue-sensitive emulsion layer ( BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.25 g Sensitization 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) 0.006g High boiling point solvent (Oil-2) 0.18g Gelatin 1.3g 10th layer; high-sensitivity blue-sensitive emulsion layer (B-H) Silver iodobromide emulsion (average grain size 0.8 μm, average iodine content 8.5 mol) %) 0.5 g sensitizing dye (S-10) 3 × 10 -4 ( mol / mole of silver) sensitizing dye (S-11) 1.2 × 10 -4 ( mol / mole of silver) yellow coupler (Y- ) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) 0.05 g Gelatin 1.0 g 11th layer; 1st protective layer (PRO-1) Silver iodobromide (average particle size 0.08 μm) 0.3 g UV absorber (UV-1) 0.07g UV absorber (UV-2) 0.10g Additive (HS-1) 0.2g Additive (HS-2) 0.1g High boiling solvent (Oil-1) 0.07g High Boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g 12th layer; Second protective layer (PRO-2) Compound A 0.04 g Compound B 0.004 g Polymethylmethacrylate (average particle size: 3 μm) 0.02 g Gelatin 0.7 g-iodine Preparation of silver bromide emulsion-The silver iodobromide emulsion used in the 10th layer was prepared by the following method.

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

A solution <G-1> having the following composition was treated at a temperature of 70 ° C. and pAg
While maintaining the pH at 7.8 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, a solution <H-1> having the following composition and a solution <S-1 having the following composition:
>And> were added at an accelerated flow rate (the flow rate at the end was 3.6 times the initial flow rate) over 86 minutes while maintaining the flow rate ratio of 1: 1.

(Formation of External Low Iodity Phase-Shell Phase) Next, <H-2> and <S-2 while keeping at pHAg10.1 and pH6.0.
> 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 were formed, they were washed with water by a conventional flocculation method, and then gelatin was added to redisperse them, and pH and pAg were adjusted to 5.8 and 8.0 at 40 ° C., respectively.

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

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

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

The above-mentioned light-sensitive material further comprises the compound S
U-1, SU-2, Viscosity modifier, Hardener H-1, H-2, Stabilizer ST-1, Antifoggant AF-1, AF-2 (weight average molecular weight 10,000 and 1,100,000) ), Dye A
It contains I-1, AI-2 and compound DI-1 (9.4 mg / m ² ).

The structure of each compound used for forming the silver halide photographic light-sensitive material is shown below.

[0123]

[Chemical 1]

[0124]

[Chemical 2]

[0125]

[Chemical 3]

[0126]

[Chemical 4]

[0127]

[Chemical 5]

[0128]

[Chemical 6]

[0129]

[Chemical 7]

[0130]

[Chemical 8]

[0131]

[Chemical 9]

[0132]

[Chemical 10]

[0133]

[Chemical 11]

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

A film having a sample size of 12 cm × 35 mm was wound around a core having a diameter of 10 mm so that the side of the photographic constituent layer was the inner roll, and
Treat for 3 days under conditions of ℃ and 20% RH, and apply curl.

After that, the core is released, and the pure water at 38 ° C. is used for 15 minutes.
After soaking for 5 minutes, apply a load of 50g and dry with a hot air dryer at 55 ℃.
Dry for minutes. Remove the load, hang the sample vertically,
The distance between both ends of the sample was obtained, and how much the original distance 12 cm was recovered was evaluated. The evaluation was performed according to the following criteria.

⊚: 70% or more ◯: 50% or more and less than 70% ×: less than 50% If the level is ◯ or more, there is no practical problem.

Example 1 100 parts by weight of dimethyl terephthalate, ethylene glycol 6
0.1 part by weight of calcium acetate hydrate was added to 4 parts by weight as a transesterification catalyst, and transesterification reaction was carried out according to a conventional method. 5-sodium sulfodi (β
-Hydroxyethyl) isophthalic acid solution in ethylene glycol (concentration 35% by weight) 30 parts by weight, and polyethylene glycol (number average molecular weight: 3000) 8 parts by weight, antimony trioxide 0.05 part by weight, phosphoric acid trimethyl ester 0.03 part by weight, Iruga Knox 1010 (Ciba-Geigy) 0.2
Parts by weight and 0.04 parts by weight of sodium acetate were added.

Then, gradually raise the temperature and reduce the pressure to 280 ° C. and 0.5 mm.
Polymerization was carried out with Hg to obtain a copolyester (polyester A) having an intrinsic viscosity of 0.60. The obtained (Polyester A) and a commercially available polyethylene terephthalate having an intrinsic viscosity of 0.65 were blended in a tumbler type mixer in a weight ratio of 20/80. (Polyester B) Each of the obtained polyester A and polyester B was vacuum dried at 150 ° C. for 8 hours, melt-extruded at 280 ° C. using three extruders, and joined in layers in a T-die. Apply static electricity on the cooling drum while adhering it to cool and solidify. 3
A laminated unstretched sheet having a layer structure was obtained. At this time, the extrusion amount of each extruder was adjusted so that the polyester A was both outer layers and the polyester B was the central layer, and the thickness ratio of each layer was 1: 4: 4. This unstretched sheet was stretched 3.5 times in the machine direction at 90 ° C. using a roll-type machine.

The obtained uniaxially stretched film was stretched in a first stretching zone at 100 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and further at a second stretching zone at 120 ° C. in a total transverse stretching ratio of 3.6. It was stretched so as to be doubled. Then, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at 170 ° C. for the first heat-setting zone for 5 seconds, and heat-set at 210 ° C. for the second heat-setting zone 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 85 μm.

Example 2, Example 3, Comparative Example 1 The relaxation ratio in the lateral direction in Example 1 was 3% in Example 2.
A biaxially stretched film having a thickness of 85 μm was obtained in the same manner as in Example 3, except that it was set to 7% and Comparative Example 1 was set to 0%.

Example 4 A film having a thickness of 85 μm was prepared in the same manner as in Example 1 except that the heat setting was changed to a heat treatment in the temperature range of 210 ° C. for 20 seconds.
A biaxially stretched film of was obtained.

Example 5 A biaxially stretched film having a thickness of 85 μm was obtained in the same manner as in Example 1 except that the temperature of the second heat setting zone was changed to 180 ° C.

Comparative Example 2 The film obtained in Example 1 was further passed through an oven at 150 ° C. for 60 seconds. At this time, the peripheral speeds of the rolls on the upstream and downstream sides of the oven were adjusted to perform 1% relaxation treatment in the longitudinal direction.

Comparative Example 3 A uniaxially stretched film was obtained in the same manner as in Example 1 up to uniaxial stretching. The obtained uniaxially stretched film was stretched at 100 ° C. using a tenter type transverse stretching machine so that the transverse stretching ratio was 3.6 times. Then, it was heat-set at 210 ° C. for 20 seconds. Then, it was cooled to room temperature while being relaxed in the transverse direction by 5% to obtain a biaxially stretched film having a thickness of 85 μm.

Comparative Example 4 The layer structure of the laminated unstretched sheet in Example 1 was changed so that polyester A was both outer layers and polyester B was the central layer, and the thickness ratio of each layer was 2.5: 4.0: 2.5. Except for the above, a biaxially stretched film having a thickness of 85 μm was obtained in the same manner.

Example 6 A copolymerized polyester (polyester A) obtained in the same manner as in Example 1 and a commercially available polyethylene terephthalate having an intrinsic viscosity of 0.65 were mixed in a tumbler type mixer at a weight ratio of 40/60. Blended (Polyester C).

Each of polyester A and polyester C was vacuum dried at 150 ° C. for 8 hours, melt-extruded at 280 ° C. by using two extruders, joined in layers in a T-die, and placed on a cooling drum. It was brought into close contact while being electrostatically applied to and cooled and solidified to obtain a laminated unstretched sheet having a two-layer structure. At this time, the thickness ratio of the polyester A layer and the polyester C layer is 5: 4.
The extrusion rate of each extruder was adjusted so that Using a roll type longitudinal stretching machine, this unstretched sheet was stretched in the longitudinal direction at 90 ° C. 3.
It was stretched 5 times.

The uniaxially stretched film obtained was transversely stretched, heat-set, relaxed and gradually cooled in the same manner as in Example 1 to give a thickness of 85.
A biaxially stretched film of μm was obtained.

For each biaxially stretched film thus obtained, the respective characteristic values and evaluation results are shown in Table 1. In addition, when each layer of each obtained biaxially stretched film was scraped off and the intrinsic viscosity, the glass transition temperature and the melting point were measured for each, the intrinsic viscosity of the polymer of the polyester A layer was
0.57, glass transition temperature 63 ℃, melting point 250 ℃, polyester B layer polymer intrinsic viscosity 0.60, glass transition temperature 75 ℃, melting point 255 ℃, polyester C layer polymer intrinsic viscosity 0.59, glass transition Temperature is 72 ℃, melting point is 254 ℃
Met. Further, each of the biaxially stretched films of Examples 1 to 5 and Comparative Examples 1 to 3 exhibits a concave curl on the thick side of the polyester A layer, and the biaxially stretched film of Example 6 has a polyester A layer side. Since curling of the concave was shown, the coating failure, flatness, and curl recovery of each of the obtained biaxially stretched films were evaluated so that the convex side was the photographic constituent layer side. The biaxially stretched film of Comparative Example 4 had no curl, and there was no difference between the front and back of the film. The above results obtained are shown in Table 1 below.

[0151]

[Table 1]

As is clear from Table 1, the samples according to the present invention are excellent in transparency, mechanical strength, and dimensional stability, and are improved in curl recovery of the film, thus improving coating failure and flatness. I understand.

[0153]

INDUSTRIAL APPLICABILITY According to the present invention, a photographic support comprising a polyester film having improved transparency, mechanical strength and dimensional stability, excellent curl recovery, flatness, coatability and anti-curl property. I was able to get

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI B29K 67:00 B29K 67:00 (56) References JP-A-5-313302 (JP, A) JP-A-4-93937 (JP , A) JP-A-5-346635 (JP, A) JP-A-6-23929 (JP, A) JP-A-6-258766 (JP, A) International Publication 95/16223 (WO, A1) (58) Survey Areas (Int.Cl. ⁷ , DB name) G03C 1/795 G03C 1/81 B29C 55/00-55/30

Claims (7)

(57) [Claims] 1. A multi-layered polyester film having at least one layer of a water-absorbing polyester, the polyester film being uniaxially stretched in a longitudinal direction.
Then, split into two or more within the temperature range of Tg to Tm-20 ° C.
Horizontal stretching while raising the temperature in the stretched area, then heat setting
And are as hereinbefore unevenness transverse curl degree of the curl degree in 5 to 50 m ^-1 of the polyester film is within 10 m ^-1, the longitudinal direction of the heat shrinkage transverse heat shrunk from 0.5 to 3.0% A photographic support comprising a polyester film having a rate of -0.5 to 0.5%. 2. A photograph comprising a polyester film according to claim 1, wherein the dicarboxylic acid component constituting the water-absorbent polyester contains an aromatic dicarboxylic acid having a sulfonate group and / or an ester-forming derivative thereof. Support. 3. The polyester film according to claim 1 or 2, wherein an ester-forming compound having a polyoxyalkylene group is included as a dicarboxylic acid component or a diol component constituting the water-absorbent polyester. Photographic support. 4. A polyester film is vertically and horizontally arranged in two directions.
After axial stretching, at the final transverse stretching temperature or lower, Tg-40 ° C
Obtained by holding in the above range for 0.01 to 5 minutes
Claim 1, Claim 2 or Claim 3 characterized by
A photographic support made of a polyester film. 5. A polyester film is vertically and horizontally arranged in two layers.
After axial stretching, Tm-20 at a temperature higher than the final transverse stretching temperature.
Within a temperature range of ℃ or below, the temperature rises in the area divided into two or more.
Characterized by being obtained by heat-setting while warming
Claim 1, claim 2, claim 3, or claim 4
A photographic support made of a polyester film. 6. A polyester film is vertically and horizontally arranged in two directions.
After axial stretching and heat setting, below the final heat setting temperature, Tg
Within the above temperature range, 0.1% to 10% relaxation treatment may be performed in the lateral direction.
Claim 1, characterized in that it is obtained by
The polyester film according to claim 3, claim 4, or claim 5.
Photographic support made of film. 7. A polyester film is vertically and horizontally arranged in two directions.
After axial stretching and heat setting, from the final heat setting temperature Tg or less
When cooling to the bottom, at a cooling rate of 100 ° C or less per second
Claim 1, characterized by being obtained by gradual cooling
Claim 2, Claim 3, Claim 4, Claim 5, or Claim 6
A photographic support comprising the polyester film described.