JP3451501B2 - Photographic support - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photographic support,
Specifically, it has excellent transparency and mechanical strength, and has a reduced curl curl. In particular, it reduces coating curl during coating of the undercoat layer and film flatness caused by heat treatment in roll form due to curl curl reduction. The present invention relates to a photographic support comprising the biaxially stretched polyester film.

[0002]

2. Description of the Related Art In recent years, the use of photographic light-sensitive materials has been diversified, and the speed of film unwinding at the time of photographing, the increase of photographing magnification, and the downsizing of photographing apparatus have been remarkably advanced. Therefore, a support for a photographic light-sensitive material is required to have properties such as excellent mechanical strength and dimensional stability. Further, the roll film-shaped photographic light-sensitive material is required to have a smaller diameter 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 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 printing sensitive materials, where strictness is required, and in X-ray films where transparency and waist strength are required. However,
PET film does not have the curl curl recovery after development processing as seen in TAC film, and when it is used in roll film type photographic light-sensitive material, curl curl after development processing is too large and handling during sorting work In addition to being inferior in properties, there is a problem that scratches occur, defocus, jamming during transportation, etc. occur in a process of printing an image on photographic printing paper after development processing. Also,
The PET film is more difficult to wind than the TAC film, but it cannot be said to be sufficient when the diameter of the core is reduced.

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, it is possible to reduce curl curl after the development processing, and it is considered that the above various problems can be solved.

From this point of view, as a method for reducing curling curl of a polyester film, Japanese Patent Laid-Open No. 51-16358 has been proposed.
No. 1, thermoplastic resin film at Tg-5 ℃ ~ Tg-30 ℃
A method of heat treatment for 0.1 to 1500 hours has been proposed.
Further, JP-A-6-35118 proposes a method in which a polyester film having a Tg of 90 ° C to 200 ° C is undercoated and then heat treated at 50 ° C to Tg for 0.1 to 1500 hours.

[0007]

The method of heat-treating a thermoplastic resin film at Tg-5 ° C to Tg-30 ° C for 0.1 to 1500 hours is a PET film or a polyethylene naphthalene dicarboxylate film (hereinafter referred to as PEN film). ), And the effect of reducing the curling curl of the crystalline or semi-crystalline thermoplastic resin is effective. However, such a long-time heat treatment at a relatively high temperature has a problem that the quality of the film is significantly impaired.

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

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

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

The method of heat-treating the polyester film having Tg of 90 ° C. to 200 ° C. undercoating at 50 ° C. to Tg for 0.1 to 1500 hours is basically the same as the method described in JP-A-51-16358. It is the same method, and therefore, heat treatment in the vicinity of the Tg of the film is necessary in order to sufficiently reduce the curling curl. For example, a polyester film with a Tg of 90 ° C is not sufficiently effective unless it is heat-treated at 60 ° C or higher, and a polyester film having a Tg of 120 ° C is sufficiently effective unless it is heat-treated at 90 ° C or higher. The reality is that there is none. Therefore, the Tg of the film is high, and the film must be heat-treated at a very high temperature, which causes the following new problem.

That is, in general, 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.

As described above, the film has excellent mechanical strength and dimensional stability that enable unwinding of the film at the time of shooting, high shooting magnification, and downsizing of the shooting apparatus. However, even if the diameter of the winding core is reduced, curling due to curling does not easily occur, and a photographic support having no conveyance failure in the press-price step has not been obtained.

Therefore, the object of the present invention is to provide a photographic support which is excellent in transparency and mechanical strength, has a small curling curl, has few coating failures after coating the undercoat layer, and has excellent flatness. To do.

[0015]

The above object of the present invention has been achieved by the following constitution.

(1) A photographic support comprising a biaxially stretched polyester film, wherein the biaxially stretched polyester film has a longitudinal heat shrinkage of −0.05% or more and 0.20% or less and a transverse heat shrinkage of After being adjusted to a range of 0.0% or more and 0.30% or less, the biaxially stretched polyester film is heat-treated in a roll at a temperature not higher than the glass transition temperature and not lower than 30 ° C. lower than the glass transition temperature. Support.

(2) The biaxially stretched polyester film is adjusted to have a heat shrinkage in the machine direction in the range of 0.0% or more and 0.15% or less, and then the glass transition temperature of the biaxially stretched polyester film or less and the glass transition temperature of the biaxially stretched polyester film. The photographic support according to (1), which has been heat-treated in a roll form at a temperature not lower than 30 ° C.

(3) After the heat shrinkage of the biaxially stretched polyester film is adjusted to be in the range of 0.05% to 0.25% in the transverse direction, the glass transition temperature of the biaxially stretched polyester film is not higher than the glass transition temperature. The photographic support according to (2), which has been heat-treated in a roll form at a temperature not lower than 30 ° C.

(4) The photographic product according to claim 1, 2 or 3, wherein the biaxially stretched polyester film contains 70% by weight or more of ethylene-2,6-naphthalene dicarboxylate unit. Support.

The present invention will be described in detail below.

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

The main constituent dicarboxylic acid components include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane. Examples thereof include dicarboxylic acid, cyclohexanedicarboxylic acid, diphenyldicarboxylic acid, diphenylthioetherdicarboxylic acid, diphenylketone dicarboxylic acid and phenylindanedicarboxylic acid. Further, as the diol component, ethylene glycol, propylene glycol, tetramethylene glycol, cyclohexanedimethanol, 2,2-bis (4-
Hydroxyphenyl) propane, 2,2-bis (4-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bisphenol full orange hydroxyethyl ether, diethylene glycol, neopentyl glycol, hydroquinone, cyclohexanediol, etc. . Among the polyesters containing these as the main constituents, terephthalic acid and / or 2,6-naphthalenedicarboxylic acid as the dicarboxylic acid component and ethylene glycol as the diol component are used in terms of transparency, mechanical strength, dimensional stability, etc. And / or a polyester having 1,4-cyclohexanedimethanol as a main constituent is preferable. Among them, polyesters containing polyethylene terephthalate or polyethylene-2,6-naphthalenedicarboxylate as a main constituent, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and polyesters of these two Polyesters whose main constituent is a mixture of one or more kinds are preferred. When the content of ethylene-2,6-naphthalene dicarboxylate 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-naphthalenedicarboxylate as a main constituent is superior in mechanical strength and heat resistance to a film containing polyethylene terephthalate as a main constituent. On the other hand, a film containing polyethylene-2,6-naphthalenedicarboxylate as a main constituent component has disadvantages such as a property of emitting fluorescence and a 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 is used especially when highly thinning is required or when the film is abused at high temperatures. -A film containing naphthalene dicarboxylate as a main constituent or a constituent may be used. Further, by mixing the two, the drawbacks of each other can be compensated.

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

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

For the purpose of improving the heat resistance of the film, a bisphenol compound, a compound having a naphthalene ring or a cyclohexane ring can be copolymerized.
The copolymerization ratio of these is preferably 1 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% based on the polyester. By setting the content of the antioxidant within this range, it is possible to prevent the so-called fog phenomenon in which the density of the unexposed portion of the photographic light-sensitive material becomes high, and the haze of the film can be suppressed to a low level, resulting in a highly transparent photograph. A support for use is 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, etc., 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% or more and 85% or less in the wavelength range of 400 to 700 nm, and a difference between the maximum and the minimum of the spectral transmittance of 10% or less in the wavelength range of 600 to 700 nm. Is preferable in order to prevent the light piping phenomenon and to obtain a good photographic print.

The biaxially stretched polyester film of the present invention may be provided with slipperiness, if necessary. The slipperiness imparting means is not particularly limited, but an external particle addition method of adding inert inorganic particles to polyester, an internal particle precipitation method of precipitating a catalyst added at the time of polyester synthesis, or a surfactant is used as a film. The method of applying on the surface is common. Among these, the internal particle deposition method in which the deposited particles can be controlled to be relatively small is preferable because slipperiness can be imparted without impairing the transparency of the film. As the catalyst, various known catalysts can be used, but Ca and Mn are particularly preferable because high transparency can be obtained. These catalysts may be one kind,
You may use 2 or more types together.

The biaxially stretched polyester film of the present invention may have a multilayer structure composed of different polyesters.
For example, ethylene terephthalate unit or ethylene
-If the layer made of polyester containing 2,6-naphthalenedicarboxylate unit as the main constituent is A layer and the layer made of other polyester is B layer or C layer, two layers consisting of A layer and B layer It may be configured, or layer A / layer B / A
Layer, A layer / B layer / C layer, B layer / A layer / B layer or B layer / A
A three-layer structure such as 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 50% or more of the total thickness of the polyester film.

Polyester terephthalate, polyethylene naphthalene dicarboxylate or other homopolyesters or other copolyesters, which are excellent in transparency, mechanical strength and dimensional stability, are used as the polyester constituting the B layer or C layer. As a result, the transparency, mechanical strength, dimensional stability, etc. of the entire film can be improved.

Further, when the biaxially stretched polyester film of the present invention has a multi-layered structure, the addition of various additives other than the above-mentioned functions such as anti-oxidation, light-piping prevention, slipperiness, etc. Since it is sufficient to perform only the layer, the transparency of the film can be maintained high. The polyester film of the present invention can be highly prevented from precipitating oligomers on the surface of the film by further laminating layers made of another polyester on both sides of the polyester film. At this time, it is preferable to use the above-mentioned polyester as the polyester constituting the layer composed of another polyester (polyester D) laminated on both sides. The Tg of polyester D is preferably higher than the Tg of the polyester of the inner layer. Tg of polyester D is Tg of polyester in the inner layer
It is preferable that the temperature is 5 ° C. or higher, and further 15 ° C. or higher. The thickness of the layer made of polyester D is required to be thin within a certain range in order to maintain the water absorption of the film, and is preferably 0.05 to 10 μm.

The method of synthesizing the polyester as the raw material of the biaxially stretched polyester film of the present invention is not particularly limited, and the polyester can be produced by a conventionally known method for producing polyester. For example, a direct esterification method in which a dicarboxylic acid component is directly esterified with a diol component, first using a dialkyl ester as a dicarboxylic acid component,
It is possible to use a transesterification method in which an ester exchange reaction is carried out between this and a diol component, and this is heated under reduced pressure to remove an excess diol component and thereby polymerize.
At this time, if necessary, a transesterification catalyst or a polymerization reaction catalyst may be used, or a heat stabilizer may be added. 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 curl of 110 m as determined by the following method.
It is preferably ^-1 or less. If the curling curl of the film is too large, the transportability in the press-price process and the workability during sorting work will be poor. In addition, it is preferable that the curl has an appropriate curl because it makes it easier to eject the leading end of the film from the film cartridge and is excellent in so-called bellow ejection. Therefore, the more preferable range of the curl of the film is from 5 to 90 m ^-1 .

<Winding curl> A photographic light-sensitive material having a width of 35 mm and a length of 1200 mm is conditioned for one day under the conditions of 23 ° C. and 55% RH, and the diameter of the photographic light-sensitive layer is 7 mm. Secure it so that it will not be rewound around the core of. Then, put this film in a polyethylene cartridge case,
Heat treatment at 50 ℃, 20% RH for 4 hours, then 23
Let stand for 1 hour under the condition of ℃ and 55% RH. Then release the film from the core and pinch it with the clip, with the outer edge of the film roll up, and hang it. In this state, it is further left for 1 hour under the condition of 23 ° C. and 55% RH. After this, the degree of curling curl at the lower end of the film is determined by the reciprocal of the radius of curvature. The unit is m ^-1 .

The thickness of the biaxially stretched polyester film of the present invention is not particularly limited. It may be set so as to have a required strength according to the purpose of use. Especially when the film is used as a photographic light-sensitive material for color negative, 20
It is preferably 125 μm, particularly 40 to 90 μm. When it is used for 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 photographic light-sensitive material in which curling is imparted in the width direction without causing problems such as scratches and out-of-focus in the process of printing on photographic printing paper. It is preferable in terms of obtaining. 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 of the photographic photosensitive layer provided, the elastic modulus, the coefficient of hygroscopic expansion, etc., but cannot be determined unconditionally. It may be applied so that it is as flat as possible within the range where the photosensitive layer side does not become convex,
Normally, 23 ° C., a 5 m ^-1 50 m ^-1 under the conditions of RH 20%.
The degree of curl is a value obtained as follows.

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

The method 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, or 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 in 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 thickness direction of the film, etc. To be Further, a method of treating with a chemical solution such as resorcin can also be mentioned. Further, 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 central 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, if the thicknesses of both outer layers are d ₁ and d ₂ , respectively,
It is preferable that 1.1 ≦ d ₁ / d ₂ ≦ 10 in terms of film production. 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 a photographic light-sensitive material, the image printed on the photographic printing paper is blurred and unclear. The haze is measured according to ASTM-D1003-52.

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

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

The method for obtaining an unstretched sheet and the method for uniaxially stretching in the machine direction can be carried out by conventionally known methods.
For example, the raw material polyester is molded into pellets, dried with hot air or vacuum dried, melt-extruded, extruded into a sheet from a T-die, adhered to a cooling drum by an electrostatic application method, cooled and solidified, and unstretched. Get the sheet. Then, the obtained unstretched sheet is heated within a 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 draw ratio is
It is usually necessary to set it in a range of 2.5 times to 6 times so that subsequent transverse stretching is possible. When the sheet has a multi-layer structure, the stretching temperature is set to the highest Tg of the polyester Tg of each layer.
Is preferred.

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 a laminate film is melt extruded from the extruder and cooled. Examples thereof include an extrusion laminating method of cooling and solidifying on a drum, and a dry laminating method of laminating a monolayer film or a laminated film constituting a laminate with an anchor agent or an adhesive as required. Of these, the coextrusion method is preferable because it requires few manufacturing steps and has good adhesion between the layers.

Next, the longitudinally uniaxially stretched polyester film obtained as described above is transversely stretched within a temperature range of Tg to Tm-20 ° C. and then heat set. The transverse stretching ratio is usually 3 to 6 times, and the ratio of the longitudinal stretching ratio to the transverse stretching ratio is appropriately adjusted so that the obtained biaxially stretched film has physical properties measured and has desirable characteristics. 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 a temperature not higher than the final transverse stretching temperature thereof, because the distribution of physical properties in the width direction can be further reduced.

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

The heat-fixed film is usually cooled to Tg or lower, cut at the clip holding portions on both ends of the film, and wound into a roll. At this time, below the final heat setting temperature,
Within the temperature range of Tg or higher, 0 in the width direction and / or the longitudinal direction.
It is preferable to perform a relaxation treatment of 1 to 10%. Also, cooling is
It is preferable to gradually cool from the final heat setting temperature to Tg at a cooling rate of 100 ° C. or less per second. The means for cooling and relaxing treatment is not particularly limited and can be carried out by conventionally known means, but it is particularly preferable to perform these treatments while sequentially cooling in a plurality of temperature regions from the viewpoint of improving the dimensional stability of the film. The cooling rate is, the final heat setting temperature T _1, when the film a time from the last heat setting temperature to reach Tg was t, is the value determined by the (T ₁ -Tg) / 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 slippery 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 stretching which is used for known stretched films such as multi-stage longitudinal stretching, re-longitudinal stretching, re-longitudinal transverse stretching and transverse / longitudinal stretching.
Of course, the clip grips on both ends of the cut film are
After being pulverized or after being subjected to a treatment such as granulation treatment or depolymerization / repolymerization as required, it may be reused as a film raw material of the same type or as a film raw material of a different type.

The biaxially stretched polyester film obtained as described above has a property that it is still easily rolled, so in the present invention, the biaxially stretched polyester film is further treated at a temperature of Tg or lower and Tg of -30 ° C. or higher. Heat treatment.
The higher the treatment temperature, the shorter the curling curl reduction effect can be obtained. However, if the treatment temperature is too high, wrinkles, pushing and breaking of the film are likely to occur, and the coating failure after coating the undercoat layer is not improved. When the treatment temperature is low, a long treatment time is required, but when the treatment temperature is too low, a sufficient curling curling reduction effect cannot be obtained. The processing time is not particularly limited, but is 0.
The curling curl reduction effect is recognized from 1 hour or more, and the higher the effect is obtained as the time is longer, it can be appropriately set so as to obtain the desired effect, but if it is too long, the productivity is deteriorated. Up to 1500 hours is realistic.

In the case of heat treatment, adhesion between the film and the film is prevented by embossing the edge or center of the film partially or over the entire length, bending the ends, and partially increasing the thickness of the film. It is preferable. 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 used in the heat treatment and the core to be wound up are not particularly limited, but a material having strength not to cause bending even when the film is wound and withstanding the heat treatment temperature,
It is preferably a structure. The smoother the surface of the core, the better, and the surface roughness (R _MAX ) is preferably 2.0 μm or less. Examples of these include a resin roll, a fiber-reinforced resin roll, a metal roll, and a ceramic coating roll. If the core diameter is too small, wrinkles and the like tend to occur at the core, so it is preferable that the core diameter is large to some extent, usually 75
mm or more, more preferably 200 mm or more. The roll diameter of the wound film roll is preferably too small, because uniform treatment becomes difficult if it is too large.
Usually, it is preferably 1000 mm or less, more preferably 850 mm or less. The width of the film roll is not particularly limited, but it is preferably wide from the viewpoint of productivity, and generally 150 mm or more and 3500 mm or less.

In the present invention, when the above heat treatment for reducing curling curl is performed in a roll form, the longitudinal heat shrinkage of the film is -0.05% to 0.2%, and the transverse heat shrinkage is It is characterized in that it is 0.0% or more and 0.3% or less, more preferably the heat shrinkage in the vertical direction is 0.0% or more and 0.15% or less, and the heat shrinkage in the horizontal direction is 0.05% or more and 0.25% or less. By adjusting the heat shrinkage ratio of the film so as to fall within a specific range, it is possible to obtain a photographic support having good coating failure after coating the undercoat layer and having good film flatness.

It is very difficult to obtain the above-mentioned film characteristics only by the usual method for producing a biaxially stretched film. That is, in the sequential biaxial stretching method using a tenter,
This is because the heat shrinkage ratio in the lateral direction (the film width direction) can be adjusted by narrowing the width of the clip rail, but the longitudinal direction (the film longitudinal direction) has no adjusting mechanism. It can be adjusted in this step if a longitudinal re-stretching device such as a tensilized film mainly composed of thin film is provided, but since the film used for the photographic support is thick, such re-longitudinal stretching is possible. Equipment such as stretching is not normally used. Furthermore, the so-called bowing phenomenon inevitably causes a physical property distribution in the width direction. Therefore, even if the heat shrinkage rate of the film in the widthwise central portion can be adjusted within the above range, the heat shrinkage rate of the film becomes too large at the widthwise end portions of the film.

Therefore, in order to obtain the film of the present invention, a method for adjusting the heat shrinkage rate of the film, especially in the longitudinal direction, is required. The method that can be adopted is, for example, Japanese Patent Publication No. Sho 60-22616.
62-43857, JP-A-61-233523, 62-134244, 62
-158016, etc., but not limited thereto.

In the present invention, after the above-mentioned heat treatment, at least one undercoat layer is further applied on the surface of the film so that there is no coating failure and the photographic support is excellent in flatness after the undercoat layer is applied. You can get the body.

Generally, even if a hydrophilic photographic emulsion layer is directly coated on a hydrophobic film such as a polyester film, the required adhesive strength cannot be obtained. Therefore, it is usually necessary to coat an undercoat layer on the film surface. The material that can be used for the undercoat layer is not particularly limited, and examples thereof include a copolymer of vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride as a starting material, and polyethyleneimine. , Polyester, polystyrene, polyurethane, epoxy resin, grafted gelatin, nitrocellulose and the like, and mixtures thereof. In these subbing layers, surfactants, antistatic agents, antihalation agents, crossover cut agents, coloring dyes, pigments, thickeners, coating aids, antifoggants, antioxidants, ultraviolet absorbers, ultraviolet rays, etc. One or more kinds of various additives such as a stabilizer, an etching treatment agent, a magnetic powder and a matting agent may be contained.

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

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

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

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

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. 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, etc. may be provided on the silver halide emulsion layer or in an intermediate layer, or anywhere between the silver halide emulsion layer and the photographic support. A non-photosensitive layer may be provided.

The silver halide emulsion used in the present invention is
For example, Research Disclosure (hereinafter abbreviated as RD) No. 17643, "1. Emulsion preparation and types" of pages 22 to 23 (December 1979), and RD N
o.18716, p. 648, "The Physics and Chemistry of Photography" by Graphide, published by P.Glkides, Chemie et Phyzique Pho.
Tographique, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GFDaffin, Photo
Graphic Emulsion Chemistry Focal Press 1966), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VLZelikman et al, Making and coating Pho
Tographic Emulsion, Focal Press 1964) and the like.

The silver halide emulsion used in the present invention is
U.S. Patents 3,574,628 and 3,665,394 and British Patent 1,41
Monodisperse emulsions described in 3,748 and the like are also preferable.

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

[0067]

[Table 1]

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

[0069]

[Table 2]

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

[0071]

[Table 3]

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

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

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

To develop the photographic light-sensitive material of the present invention, for example, TH James, Theory of the Photographic Process 4th Edition (The Theory of Th).
e Photografic Process Forth Edition) pp. 291-33
Page 4 and the Journal of the American Chemical Society
The developer known per se, which is described in Vol. 73, page 3,100 (1951), can be used. Further, the color photographic light-sensitive material has the above-mentioned RD 17643, pages 28 to 29, RD 18
It can be processed by the usual methods described in 716, page 615 and RD 308119 XIX.

[0076]

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

In the following examples, the values of heat shrinkage, glass transition temperature and melting point, film haze, intrinsic viscosity, elastic modulus and breaking strength, curl curl, coating failure after application of the undercoat layer, and flatness. The respective evaluation ranks of press price transportability are obtained by the following.

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

(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 cm ^{3 /} min and immediately cooled in liquid nitrogen. A differential scanning calorimeter (manufactured by Rigaku Denki Co., D
SC8230 type), the temperature is raised at a heating rate of 10 ° C./min in a nitrogen flow of 100 cc / min, 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) The intrinsic viscosity film or pellet was 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 (ηsp) at each concentration (C) is determined by an Ubbelohde viscometer at 20 ° C. Then η
Plot sp / C against C and extrapolate the resulting line to zero concentration Ask for. The unit is indicated by dl / g.

(5) Elastic Modulus and Breaking Strength The film was cut into a size of 10 mm in width and 200 mm in length, and 23
After conditioning the humidity for 12 hours at 55 ° C and 55% RH, Tensilon (RTA-100) manufactured by Orientec Co., Ltd. was used to perform a tensile test with a chuck distance of 100 mm and a pulling speed of 100 mm / min. And the breaking strength were determined.

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

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

Rank Number of surface failures ◎ 0 ○ 1 to 3 × 4 or more (8) A flat film was conditioned under a condition of 23 ° C. and 55% RH for 12 hours, and then on a flat board. The degree of waviness was visually evaluated and ranked according to the following criteria. The practicality in this ranking is determined based on the tolerance of the quality of the photographic light-sensitive material, and it is necessary that the rank is ◯ or higher.

Rank Waviness ⊚ Good ○ Waviness can be seen by looking closely × Waviness is large (9) Press price transportability Winding is performed using a photographic light-sensitive material having a curl in the same manner as the curl curl measurement described above. It was inserted into Noritz Press Splicer PS-35-1 (manufactured by Noritsu Koki Co., Ltd.) so that the core side was at the top. The following criteria were used to rank each level according to the number of occurrences of 10 defective conveyances.

[0087] Rank Number of transport defects ◎ 0 ○ 1 × 2 to 10 A polyester was prepared as follows.

(Polyester A) 100 parts by weight of dimethyl 2,6-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) Dye Macrolex Green G and Macrolex Red 5R manufactured by Bayer Co. were added to polyester A at a ratio of 1: 1 and an extruder was used to prepare master pellets having a dye concentration of 2000 ppm.

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

Polyester A and polyester B were blended in a tumbler type mixer in a weight ratio of 9: 1. After this, vacuum dry at 150 ℃ for 8 hours and then 300 ℃
Was melt-extruded in layers from the T-die, adhered onto a cooling drum at 50 ° C while electrostatically applied, and cooled and solidified to obtain an unstretched sheet. This unstretched sheet was stretched 3.3 times in the longitudinal direction at 135 ° C. using a roll type longitudinal stretching machine.

The uniaxially stretched film thus obtained was stretched in a first stretching zone at 145 ° C. by 50% of the total transverse stretching ratio using a tenter type transverse stretching machine, and then at a second stretching zone at 155 ° C. in a total transverse stretching ratio of 3.3 times. Was stretched. Then, it was heat-treated at 100 ° C. for 2 seconds, further heat-set at 200 ° C. for 5 seconds in the first heat-setting zone, and heat-set at 230 ° C. for 15 seconds in the second heat-setting zone. The film was then relaxed laterally at 230 ° C and then cooled to 80 ° C to release the film from the tenter clip. Further, it was passed through an air-floating oven while maintaining the running tension at 5 kg / m, subjected to a longitudinal relaxation treatment, cooled to room temperature and wound up to obtain a biaxially stretched film having a thickness of 85 μm. At this time,
Films with different heat shrinkage by changing the relaxation rate in the transverse direction, relaxation temperature in the longitudinal direction, and time as shown in Table 4 (levels 1 to 11)
Was produced. The heat shrinkage rate of the obtained film is shown in Table 4.

The film (levels 1 to 11) obtained as described above was slit to a width of 1 m, and embossed with a height of 15 μm and a width of 10 mm while pressing embossing rings on both edges of the film, and then a diameter of 200 mm. S with surface roughness (R _MAX ) 0.8 μm
It was wound around a US-made winding core for 1000 m while changing the tension so that the initial tension was 25 kgf and the final tension was 20 kgf.

Then, while the film was still wound on the core, heat treatment was performed at 110 ° C. for 24 hours to reduce the winding. Each physical property value of the obtained film was measured, and the results are shown in Table 5. The heat treatment was performed by raising the temperature over 24 hours, treating it at a prescribed temperature for a prescribed time, and then cooling it to room temperature over a further 24 hours.

Then, an undercoat layer and a back layer were coated as follows.

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

<Undercoating Liquid A-1> Copolymer latex liquid (solid content: 30% by weight: 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) %) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with water 1000 ml <Undercoating liquid B-1> 40 wt% butyl acrylate, 20 wt% styrene and glycidyl Acrylate 40% by weight copolymer latex liquid (solid content 30%) 270 g Compound (UL-1) 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Finish with water 1000 ml Further undercoat layer A-1 And 8 W / (m ² · on the undercoat layer B-1
min) corona discharge treatment, and undercoat layer A-
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 1000ml <Undercoating liquid B-2> Water-soluble conductive polymer (UL-4) 60g Latex liquid containing compound (UL-5) as a component (solid content 20%) 80g Ammonium sulfate 0.5g Hardener (UL- 6) 12g Polyethylene glycol (weight average molecular weight 600) 6g Finish with water 1000ml Using the film coated with the above undercoat layer, the undercoat layer B-2
A corona discharge of 8 W / (m ² · min) was applied on the above, and the following coating liquid MC-1 was applied so as to have a dry film thickness of 1 μm.

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

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

<OC-1> Carnauba wax 1 g Toluene 700 ml Methyl ethyl ketone 300 ml At this time, the undercoated film was sampled to evaluate coating failure and flatness. The results are shown in Table 6.

<Coating of Photosensitive Photosensitive Layer> A corona discharge treatment of 25 W / (m ² / min) was applied to the surface of the undercoat layer A-2 of the above film to sequentially form the following photographic constituent layers, A color photographic light-sensitive material was prepared. In addition, the display of the quantities in the photographic constituent layers shown below is the quantity per 1 m ² unless otherwise specified.

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

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

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

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

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

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

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

The obtained emulsion was a monodisperse emulsion containing octahedral silver iodobromide grains having an average grain size of 0.80 μm, a broad distribution 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> Oscein gelatin 82.4g Potassium bromide 151.6g Potassium iodide 90.6g Finish with water 1030.5ml <S-1> Silver nitrate 309.2g 28% aqueous ammonia solution Equivalent water Finishing 1030.5 ml <H-2> Ocein gelatin 302.1 g Potassium bromide 770.0 g Potassium iodide 33.2 g Finishing with water 3776.8 ml <S-2> Silver nitrate 1133.0 g 28% ammonia solution equivalent Finishing with water 3776.8 ml Other than the 10th layer The same procedure applies to the silver iodobromide emulsion used in the emulsion layer, 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 width 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 1,100,000), dyes AI-1, AI-2 and compound DI-1 (9.4 mg /
m ² ) is contained.

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

[0115]

[Chemical 1]

[0116]

[Chemical 2]

[0117]

[Chemical 3]

[0118]

[Chemical 4]

[0119]

[Chemical 5]

[0120]

[Chemical 6]

[0121]

[Chemical 7]

[0122]

[Chemical 8]

[0123]

[Chemical 9]

[0124]

[Chemical 10]

[0125]

[Chemical 11]

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. The curled curl of the cut photographic light-sensitive material was measured and the press-price transportability was evaluated. The results are shown in Table 6.

[0127]

[Table 4]

[0128]

[Table 5]

[0129]

[Table 6]

As is clear from Tables 4 to 6, after the heat shrinkage ratio of the film is set within the range of the present invention, heat treatment for reducing curling curl is applied after coating the undercoat layer. It can be seen that the failure and flatness are improved, and the transparency, strength, curling curl, and press-price suitability are also excellent.

[0131]

As described in detail above, according to the present invention, the transparency and mechanical strength are excellent, the curling curl is small, the coating failure after coating the undercoat layer is small, and the flatness is excellent. A photographic support could be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Makoto Honda Makoto Sakura, Hino City, Tokyo 1 Konica Co., Ltd. (56) Reference JP-A-7-253638 (JP, A) International Publication 94/19722 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 1/795 G03C 1/81

Claims (4)

(57) [Claims] 1. A photographic support comprising a biaxially oriented polyester film, wherein the biaxially oriented polyester film has a longitudinal heat shrinkage of −0.05% or more and 0.20% or less and a transverse heat shrinkage of 0.0. % Or more and 0.30% or less, and then heat-treated in roll form at a glass transition temperature of the biaxially stretched polyester film or less and a temperature 30 ° C. lower than the glass transition temperature or more. body. 2. The biaxially stretched polyester film,
After adjusting the heat shrinkage ratio in the longitudinal direction in the range of 0.0% or more and 0.15% or less, the glass transition temperature of the biaxially stretched polyester film or less, heat-treated in a roll form at a temperature 30 ° C or more lower than the glass transition temperature. The photographic support according to claim 1, characterized in that 3. The biaxially stretched polyester film,
After the heat shrinkage in the transverse direction is adjusted to be in the range of 0.05% to 0.25%, the glass transition temperature of the biaxially stretched polyester film is lower than the glass transition temperature, and the heat treatment is performed in a roll shape at a temperature 30 ° C lower than the glass transition temperature. The photographic support according to claim 2, wherein 4. The biaxially stretched polyester film comprises ethylene-2,6-naphthalene dicarboxylate units.
The content of 0% by weight or more,
The photographic support according to item 2 or 3.