JP5221888B2 - Method for producing polyester resin film - Google Patents

Description

  The present invention relates to a method for producing a polyester resin film, and in particular, a method for producing a polyester resin film applied to optical applications having excellent transparency, a polyester resin film produced by this production method, and this polyester resin film. The present invention relates to an antireflection film and a diffusion film used for a substrate.

  In recent years, the spread of personal computers, particularly laptop computers with good portability and space-saving desktop computers, has been remarkable. In addition, liquid crystal televisions are becoming popular as home-use thin large-screen televisions. Along with this, the demand for liquid crystal displays is increasing and the screen is being enlarged.

  As various optical films used for these, a biaxially oriented polyester resin film is used because of having excellent transparency. Moreover, since the optical film is required to have excellent strength and dimensional stability, a relatively thick film is preferably used.

  As a method for producing such a film, a polyester resin is extruded onto a drum (casting drum) having a smooth surface, and the molten resin is cooled on the casting drum to form a film.

  However, since the molten resin is cooled by passing a coolant or the like through the casting drum, the molten resin film surface becomes insufficiently cooled when the thickness of the molten resin film is increased. As a result, crystallization occurred, causing problems of cloudiness of the film and deterioration of transparency (haze). When the transparency is deteriorated, when used as an optical film for a flat panel display (FPD) such as a crystal display device (LCD) or a plasma display panel (PDP), the luminance of the screen is lowered, which is a problem.

In order to solve such a problem, Patent Document 1 describes a method of cooling with air as an auxiliary cooling device in addition to a cooling drum. Patent Document 2 describes a manufacturing method in which the cooling rate is set to 1 sec / 10 ° C. or higher to prevent the generation of optical foreign matters due to partial crystallization.
JP-A-9-204004 JP 2000-229355 A

  As described above, since a particularly excellent strength is required in recent years, a thick film has been used. However, in the methods described in Patent Document 1 and Patent Document 2, since the sheet cooling rate is increased, haze generated in the film can be prevented. However, in order to increase the cooling rate, it is necessary to supply a large amount of cold air. Due to this cold air, the bead cannot fluctuate uniformly to form a film, resulting in uneven thickness. In addition, the rapid cooling causes a difference in the cooling rate between the front and back of the film, causing problems such as curling and wrinkling.

  The present invention has been made in view of such problems, and a method for producing a polyester resin film capable of preventing the occurrence of haze while suppressing the occurrence of curling, sheet unevenness, and wrinkles, and the production thereof. It is an object of the present invention to provide a polyester resin film produced by the method, and an antireflection film and a diffusion film using the polyester resin film as a base material.

According to a first aspect of the present invention, in order to achieve the above object, a polyester resin is melt-extruded into a sheet shape, cooled and solidified on a casting drum to produce a polyester resin sheet, and then subjected to biaxial stretching. In the manufacturing method, the thickness of the polyester resin sheet after the melt extrusion is 1500 μm or more, and at the time of the cooling and solidification, a cold air of 5 ° C. or more and 50 ° C. or less is blown from a cold air generator facing the casting drum. The sheet was forcibly cooled, and the surface temperature of the sheet was 350 ° C./min to 590 ° C./min in the range of (temperature-falling crystallization start temperature + 40 ° C.) to (temperature-falling crystallization end temperature−40 ° C.) of the polyester resin. and it cooled and solidified min following average cooling rate, the cold air outlet shape of the cold air generator, the polyester resin sheet A slit nozzle extending in the width direction of the surface of the slit, the slit nozzle having a slit width of 0.5 mm to 10 mm, the slit nozzle pitch of 10 mm to 100 mm, and the distance between the slit nozzle and the casting drum of 5 mm to 200 mm The manufacturing method of the polyester resin film characterized by the following is provided.

The manufacturing method of the polyester resin film of this invention can be used suitably for manufacture of a thick film. Specifically, the thickness of the polyester resin sheet after melt extrusion is 1500 μm or more. In the manufacturing method of the present invention, cooling is performed by blowing cold air from a cold air generator in addition to cooling with a casting drum. Therefore, it is possible to sufficiently cool a thick sheet. In addition, by setting the cooling rate in the range of 350 ° C./min to 590 ° C./min, it is possible to produce a film that suppresses the generation of haze and generates less wrinkles due to rapid cooling.
Further, by setting the slit width and pitch of the slit nozzle and the distance between the slit nozzle and the casting drum within a predetermined range, there is no occurrence of uneven cooling and cooling at a predetermined cooling rate is possible. If the slit width is smaller than 0.5 mm, the pressure loss is too large to supply a sufficient air volume, the cooling rate becomes slow, and haze may occur. If it is larger than 10 mm, variations occur in the wind coming out of the slits, resulting in uneven cooling on the sheet. Further, even if the pitch of the slit nozzles is smaller than 10 mm, no further cooling effect can be obtained as compared with the case of 10 mm. When the distance is larger than 100 mm, the distance between the slits is too large, which causes undesirable cooling unevenness in the sheet traveling direction. Furthermore, when the distance between the slit nozzle and the casting drum is shorter than 5 mm, the cool air discharged from the nozzle directly hits the sheet, so that the surface shape of the sheet is deteriorated. If it is longer than 200 mm, the cooling effect by the cold air cannot be obtained, and a sufficient cooling rate cannot be obtained.

A second aspect of the present invention is the first aspect of the present invention, wherein the average cooling rate A (° C./min) on the surface of the polyester resin sheet, the refrigerant temperature B (° C.) flowing through the casting drum, and the back surface of the polyester resin sheet from the casting drum. The overall heat transfer coefficient C (J / m ² · s · K) and the glass transition point Tg (° C.) of the polyester resin satisfy the following expression.

30 ≦ C × (300−B) ÷ A ≦ 4000 (1)
0 ≦ B ≦ Tg (2)
The second aspect defines the difference in cooling rate between the front surface and the back surface of the sheet during sheet cooling. If the difference in cooling rate between the front surface and the back surface is large, a difference in physical properties occurs, and curling occurs in the film. On the other hand, when the formula (1) is smaller than 30, it is not preferable since the cooling from the casting drum side is insufficient and haze is generated in the film. Further, if the temperature B of the refrigerant is lower than 0 ° C., condensation occurs on the casting drum, and if it is higher than Tg, the sheet adheres to the drum, which is not preferable.

A third aspect of the present invention is characterized in that, in the first or second aspect, a heat transfer coefficient from the cold air generating device to the surface of the polyester resin sheet is 1 J / m ² · s · K or more and 500 J / m ² · s · K or less. And

According to claim 3, by setting the heat transfer coefficient from the cold air generator to the polyester resin sheet surface within the above range, the sheet is cooled while maintaining a predetermined cooling rate without causing unevenness of the sheet thickness. Can do. When the heat transfer coefficient exceeds 500 J / m ² · s · K, the sheet cannot be cooled uniformly, and the film thickness unevenness deteriorates. On the other hand, if it is less than 1 J / m ² · s · K, cooling is insufficient, the sheet is easily crystallized, and haze is generated.

A fourth aspect of the present invention is characterized in that, in the first to third aspects, the average wind speed of the cold air is 5 m / sec or more and 100 m / sec or less.

According to the fourth aspect, by setting the average wind speed of the cold air within the above range, it is possible to perform cooling while maintaining a predetermined cooling rate without causing uneven thickness. When the wind speed exceeds 100 m / sec , the sheet cannot be cooled uniformly, and the film thickness unevenness deteriorates. On the other hand, if it is less than 5 m / sec , cooling is insufficient, the sheet is easily crystallized, and haze is generated.

  A fifth aspect of the present invention is characterized in that, in the first to fourth aspects, the difference in cooling rate in the width direction of the surface of the polyester resin sheet is 100 ° C./min or less.

  According to the fifth aspect, by setting the difference in cooling rate within the above range, a film having uniform quality can be produced. A difference in cooling rate exceeding 100 ° C./min is not preferable because a difference occurs in quality such as a haze distribution in the width direction of the film.

A sixth aspect of the present invention is characterized in that, in the first to fifth aspects, the number of revolutions of the inverter of the cold air fan is controlled according to the outside air temperature and pressure so that the amount of the cold air outlet of the cold air generator is constant.

According to the sixth aspect , the air volume of the cold air is not affected by the outside air temperature or the outside air pressure, and the cold air can be supplied with a constant air volume. Therefore, it can be manufactured without causing unevenness in quality such as haze distribution in the running direction of the film.

A seventh aspect of the present invention according to any one of the first to sixth aspects, wherein the cool air generating device is provided with an exhaust fan, and a total supply air amount X (m ³ / min) of the cool air and a total exhaust air amount Y of the exhaust fan. (M ³ / min) satisfies the following formula.

0.5 ≦ Y ÷ X ≦ 4 (3)
According to the seventh aspect of the present invention, the cold air generator is provided with an exhaust fan. Therefore, since the cold air supplied from the cold air generator can be exhausted, the atmosphere in the vicinity of the seat can be cooled without being extremely pressurized. When the numerical value of the formula (3) is less than 0.5, the air supply amount increases, so that the beads discharged from the die are shaken by the cold air, and the thickness unevenness of the film is deteriorated. Moreover, if the numerical value of the expression (3) exceeds 4, the exhaust air volume increases, and not only the cold air but also the surrounding air is sucked into the exhaust fan, so that floating foreign matter adheres to the sheet and the transparency of the sheet deteriorates. To do.

An eighth aspect of the present invention is characterized in that in the first to seventh aspects, the cold air generating device is provided with a dustproof filter.

According to the eighth aspect , since the cold air generating device is provided with the dustproof filter, it is possible to prevent foreign matters contained in the cold air from adhering to the film.

A ninth aspect is characterized in that the polyester resin film obtained by biaxially stretching the polyester resin sheet according to the first to eighth aspects has a thickness of 150 μm or more.

  In the production method of the present invention, since the sheet is cooled by a casting drum from the back side of the sheet and by cold air from the front side of the sheet, even a thick film can be cooled at a predetermined speed. This is particularly effective for thick films.

A tenth aspect is characterized in that, in the first to ninth aspects, the haze of the polyester resin film is 2% or less.

According to the tenth aspect , by setting the haze in the above range, the brightness of the FPD screen is improved and can be suitably used as an optical film.

An eleventh aspect is characterized in that, in the first to tenth aspects, the curl of the polyester resin film is 50 mm or less.

According to the eleventh aspect , by setting the curl within the above range, it is possible to provide a polyester resin film having good processing suitability. Further, a panel without warping can be manufactured.

  According to the present invention, by cooling and solidifying a polyester resin sheet within a predetermined temperature range and a cooling rate range with a cold air from a casting drum and a cold air generator, when producing a thick polyester resin film, It is possible to produce a polyester resin film of good quality that suppresses generation of haze, generation of curls, and generation of wrinkles on the sheet.

  Hereinafter, preferred embodiments of a method for producing a polyester resin film of the present invention will be described in detail with reference to the accompanying drawings.

  FIG. 1 is a diagram showing an outline of an apparatus for producing a polyester resin film. In this figure, 10 is a film forming step for forming a polyester resin film 1, and 20 is a polyester resin formed by the film forming step 10. A longitudinal stretching machine for stretching the film 1 in the longitudinal direction, 30 is a transverse stretching machine for stretching the polyester resin film 1 stretched in the longitudinal direction by the longitudinal stretching machine 20 in the transverse direction, and 40 is a polyester stretched by the transverse stretching machine 30. It is a winder that winds up the resin film 1. The film forming process unit 10 is provided with a die 11, a casting drum 12, and a cold air generator 13, and a longitudinal stretching machine 20. Further, the cold air generator 13 is provided with an air supply fan 14 for supplying cold air and an exhaust fan 15 for exhausting the cold air. Note that the cold air generator illustrated in FIG. 1 is merely representative, and the shape is not particularly limited and can be used.

  Further, in the present invention, the film before the longitudinal stretching step after the film forming step is “polyester resin sheet”, the film after the longitudinal stretching step is “longitudinal stretched polyester resin film”, after the lateral stretching, that is, the longitudinal stretching and the lateral stretching. The film after biaxial stretching is referred to as “polyester resin film”.

[Film forming process]
First, the film forming process will be described. After sufficiently drying the polyester resin, for example, it is melt-extruded into a sheet through an extruder (not shown), a filter (not shown) and a die 11 controlled to a temperature range of melting point +10 to 50 ° C. The polyester resin film 1 is obtained by casting on 12 and rapidly solidifying. Further, when rapidly cooling and solidifying on the casting drum 12, cooling is performed by blowing cold air from a cold air generator 13 provided at a position facing the casting drum 12. Thereby, the back surface of the sheet can be cooled by the casting drum 12 and the surface of the sheet can be cooled by the cold air, so that the sheet can be uniformly cooled at a desired speed.

  The temperature of the cool air blown from the cool air generator 13 to the sheet is supplied with cool air having a temperature of 5 ° C. or more and 50 ° C. or less. Preferably they are 10 degreeC or more and 40 degrees C or less, More preferably, they are 15 degreeC or more and 35 degrees C or less. If the temperature of the cold air is lower than 5 ° C., condensation may occur on the casting drum, and if it exceeds 50 ° C., the cooling effect is reduced, which is not preferable.

Moreover, it is preferable that the average wind speed of cold wind is 5 m / sec or more and 100 m / sec or less. More preferably, they are 10 m / second or more and 90 m / second or less, More preferably, they are 15 m / second or more and 80 m / second or less, More preferably, they are 20 m / second or more and 70 m / second or less. By setting the average wind speed in the above range, a film having a uniform film thickness can be produced while maintaining a predetermined cooling rate. When the average wind speed is slower than 5 m / sec , sufficient cooling is not performed, so that crystallization occurs easily due to insufficient cooling and causes haze. On the other hand, when the speed is higher than 100 m / second , the thickness unevenness of the film is deteriorated, which is not preferable.

  FIG. 2 is a front view of the cold air generator 13 as seen from the casting drum 12 side. The cold air generating device 13 includes a cold air outlet 16 in the traveling direction at the center of the device, and an exhaust nozzle 17 is provided beside the cold air outlet 16.

  As a preferable shape of the cold air outlet 16, as shown in FIG. 2, it is preferable that it is a slit nozzle which spreads in the width direction of the polyester resin sheet surface. By making the cold air outlet shape a slit nozzle, the sheet can be efficiently cooled. The slit width of the slit nozzle is preferably 0.5 mm or more and 10 mm or less, more preferably 0.8 mm or more and 8 mm or less, more preferably 1 mm or more and 6 mm or less, and further preferably 1.2 mm or more and 4 mm or less. A film having a uniform film thickness can be produced while maintaining a sufficient cooling rate by setting the above range. If the slit width is smaller than 0.5 mm, the pressure loss increases and a sufficient air volume cannot be obtained, so that the cooling rate is slow. On the other hand, if it is larger than 10 mm, the cooling air supplied from the slits varies, and thus cooling unevenness may occur.

  Moreover, it is preferable that the pitch of a slit nozzle is 10 mm or more and 100 mm or less. More preferably, they are 20 mm or more and 90 mm or less, More preferably, they are 30 mm or more and 80 mm or less, More preferably, they are 40 mm or more and 70 mm or less. By setting it as the said range, a film with a uniform film thickness can be manufactured at a predetermined cooling rate. Even if the nozzle pitch is smaller than 10 mm, no further cooling effect can be obtained. On the other hand, if it is larger than 100 mm, the distance between the slits becomes too large, and cooling unevenness occurs in the sheet traveling direction, which is not preferable.

  Furthermore, it is preferable that the distance from the slit nozzle 14 of the cold air generator to the casting drum 12 is 5 mm or more and 200 mm or less. More preferably, they are 8 mm or more and 150 mm or less, More preferably, they are 12 mm or more and 100 mm or less, More preferably, they are 15 mm or more and 50 mm or less. By setting it as the said range, a favorable planar film can be manufactured, maintaining a sufficient cooling rate. If the distance between the slit nozzle 14 and the casting drum 12 is shorter than 5 mm, the cold air supplied from the slit nozzle 14 directly hits the sheet, so that the sheet surface is deteriorated. Moreover, since sufficient cooling rate is not obtained as it is 200 mm or more, a haze may generate | occur | produce by crystallization.

  It is preferable to control the rotational speed of the inverter of the cold air fan according to the outside air temperature and pressure so that the outlet air volume of the cold air is always constant. As a method of controlling the number of rotations, after the air supplied by the fan is cooled and temperature controlled between the fan and the slit nozzle of the cold air generator, the air volume is measured with an air speed measuring device or the like, and the air volume becomes constant. A method for controlling the rotational speed of the fan can be mentioned. By controlling the number of revolutions, the exit air volume of the cool air can be made constant, so there is no variation in the air volume of the cool air due to the outside air temperature, outside air pressure, etc. Quality film can be produced.

  Moreover, it is preferable that the cold wind generator 13 is provided with the dustproof filter. By providing the dustproof filter, dust, dust, and the like contained in the cold air can be removed, so that it is possible to supply purified cold air. Therefore, it is possible to manufacture a clean film that is free from adhesion of dust and the like.

The cold air generator 13 preferably includes an exhaust nozzle 17 and an exhaust fan 15 for exhausting the cold air. The cold air generator 13 supplies cold air toward the sheet surface. Therefore, the pressure increases near the surface of the sheet, and cooling unevenness may occur. However, by providing the exhaust nozzle 17 and the exhaust fan 15, since the cool air is exhausted by the exhaust fan 15 through the exhaust nozzle 17, the pressure near the seat surface can be made constant and the occurrence of uneven cooling can be prevented. Further, by providing the exhaust nozzle 17 and the exhaust fan 15, the direction of the cold air can be made constant, so that it becomes easy to blow the cold air toward the seat. In order to prevent the pressure near the seat surface from becoming high and to prevent the surrounding air from being sucked from the exhaust nozzle 17, the total supply air amount X (m ³ / min) of the cold air from the cold air generator and the exhaust gas It is preferable that the total exhaust air flow rate Y (m ³ / min) of the fan satisfies the following formula.

0.5 ≦ Y ÷ X ≦ 4 (3)
The value of formula (3) is more preferably 0.8 or more and 3 or less, further preferably 1 or more and 2.5 or less, and further preferably 1.2 or more and 2 or less. By setting it within the above range, it is possible to produce a film of good quality with a uniform film thickness and less adhesion of dust and dirt. If the formula (3) is smaller than 0.5, the amount of supplied air is too large, and the cold air blown from the cold air generator shakes the bead discharged from the die 11 to deteriorate the thickness unevenness, which is not preferable. Further, if the expression (3) exceeds 4, the amount of exhaust air is increased, and foreign matters floating around are attached to the sheet, which is not preferable.

  The exhaust nozzles 17 are preferably provided on the left and right sides of the cold air outlet 16 of the cold air generator 13. By providing on the left and right sides of the cold air outlet 16, the cold air blown from the cold air outlet 16 hits the sheet and is discharged as it is by the exhaust nozzle 17. Therefore, it is possible to supply and exhaust cold air without the vicinity of the sheet being in a pressurized state.

  In addition, as a typical example of the cold air generator used in the production method of the present invention, it has been described with reference to FIG. 2, but the polyester resin film is not particularly limited as long as it does not crystallize due to insufficient cooling and no haze is generated. Any device can be used. Also, the position, shape, etc. can be changed as appropriate.

  Next, a mechanism for cooling the sheet will be described.

The polyester resin discharged in a sheet form from the die 11 is cooled and solidified on the casting drum. Cooling is performed by the refrigerant in the casting drum and cold air. The average cooling rate on the surface of the polyester resin sheet is A (° C./min), the refrigerant temperature in the casting drum is B (° C.), and the overall heat transfer coefficient from the casting drum to the back surface of the polyester resin sheet is C (J / m ² · s -When it is set as K), it is preferable to satisfy | fill the following formula | equation.

30 ≦ C × (300−B) ÷ A ≦ 4000 (1)
0 ≦ B ≦ Tg (2)
When the cooling rate difference between the front and back sides of the sheet is large when the sheet is cooled, a difference in physical properties occurs between the front and back sides, so that the film is likely to curl. Therefore, by satisfying the above formula, it is possible to produce a high quality film in which generation of haze and generation of curl are suppressed. If the above formula (1) exceeds 4000, the surface cooling rate is high, and the curl deteriorates, which is not preferable. On the other hand, if it is less than 30, the back surface is not sufficiently cooled, and haze may occur due to crystallization. Further, if the refrigerant temperature is lower than 0 ° C., dew condensation occurs on the casting drum, which is not preferable. Moreover, when Tg (glass transition point) is exceeded, since a sheet adheres to a drum at the time of sheet peeling, it is not preferable. Formula (1) is more preferably 100 or more and 3000 or less, further preferably 200 or more and 2500 or less, and further preferably 300 or more and 2000 or less. Formula (2) is more preferably 5 or more (Tg-10) or less, still more preferably 10 or more (Tg-20) or less, and still more preferably 10 or more (Tg-30) or less.

The heat transfer coefficient from the cold air generator 13 to the sheet surface is preferably 1 J / m ² · s · K to 500 J / m ² · s · K. More preferably, not more than 10J ^{/ m} 2 · s · K or higher ^{400J / m 2 · s · K} , more preferably less 20J ^{/ m} 2 · s · K or higher ^{300J / m 2 · s · K} , further Preferably, it is 30 J / m ² · s · K or more and 200 J / m ² · s · K or less. By setting the heat transfer coefficient within the above range, a film having a uniform film thickness can be produced while maintaining a sufficient cooling rate. When the heat transfer coefficient is less than 1 J / m ² · s · K, crystallization is likely due to insufficient cooling, and haze is observed. On the other hand, if it is larger than 500 J / m ² · s · K, the thickness unevenness of the sheet is deteriorated, so that the thickness unevenness of the film is also deteriorated.

  Moreover, the surface temperature of the polyester resin sheet at the time of cooling is in the range of (temperature-falling crystallization start temperature + 40 ° C.) to (temperature-falling crystallization end temperature−40 ° C.) of the polyester resin. By setting the surface temperature within this range, the polyester resin sheet can be easily crystallized, so that the film can be easily produced.

  The temperature-falling crystallization start temperature and the temperature-falling crystallization end temperature of the polyester resin can be measured by, for example, a differential scanning calorimeter (DSC-50: manufactured by Shimadzu Corporation). The measuring method is as follows: 8 mg of polyester resin pellets weighed in advance are set in a measuring device, heated to 300 ° C. at a heating rate of 10 ° C./min, held at 300 ° C. for 10 minutes, and then 10 ° C./min. The rising temperature of the cooling crystallization peak when cooling at the cooling rate is defined as the cooling crystallization start temperature, and the falling temperature of the peak is defined as the cooling crystallization end temperature. An example of the cooling crystallization peak at the time of measurement is shown in FIG.

  Furthermore, the average cooling rate of the sheet surface is 350 ° C./min or more and 590 ° C./min or less. More preferably, they are 380 degrees C / min or more and 590 degrees C / min or less, More preferably, they are 400 degrees C / min or more and 590 degrees C / min or less. By setting the average cooling rate within this range, it is possible to prevent the haze from being deteriorated by crystallization and to prevent the generation of wrinkles due to rapid cooling. Moreover, it is preferable that the difference of the cooling rate of the sheet | seat surface in the width direction is 100 degrees C / min or less. More preferably, it is 80 degrees C / min or less, More preferably, it is 50 degrees C / min or less, More preferably, it is 30 degrees C / min or less. By setting the difference in cooling rate within the above range, it is possible to produce a film having uniform quality with no haze distribution in the width direction of the sheet. If the difference in cooling rate in the width direction is 100 ° C./min or more, a quality difference occurs in the width direction of the film, which is not preferable.

[Longitudinal stretching process]
Next, the longitudinal stretching process will be described. A longitudinal stretching machine that performs the longitudinal stretching step will be described with reference to FIG. FIG. 4 is a schematic view of a longitudinally extending machine. In addition, a longitudinal stretch machine is not limited to the apparatus described in FIG. 4, The apparatus normally used for the longitudinal stretch of a film can also be used. In FIG. 4, the longitudinal stretching machine 20 is provided with a heating stretching roll 23 and a cooling stretching roll 24 having different peripheral speeds, and a far infrared heater 25 is disposed above the heating stretching roll 23. In the longitudinal stretching step, the unstretched polyester resin sheet is longitudinally stretched and then cooled to the glass transition point or lower.

  The longitudinal stretching process is performed by the longitudinal stretching machine as described above. This longitudinal stretching process uses a far infrared heater as a heating means of the polyester resin sheet, and the longitudinal stretching ratio is 1.5 to 4.5 times. To obtain a vertically stretched polyester resin film.

  The longitudinally stretched polyester resin film that has been longitudinally stretched under the specific conditions as described above is sent to the lateral stretching step and laterally stretched.

[Horizontal stretching process]
Next, the transverse stretching process will be described. A transverse stretching machine that performs the transverse stretching step will be described with reference to FIG. FIG. 5 is a schematic view of a transverse stretching machine. In this figure, 31 is a tenter, and this tenter 31 is composed of a number of zones that can be individually controlled by hot air and divided by a windshield curtain 32. From the entrance, a preheating zone T ₁ and a transverse stretching zone T _{2 are provided.} , T ₃ , T ₄ , T ₅ , heat fixing zones T ₆ , T ₇ , T ₈ , thermal relaxation zones T _{9 to} T _n-3 and cooling zones T _{n-2 to} T _n are arranged.

  The transverse stretching step is performed by the transverse stretching machine as described above. In the transverse stretching step, the longitudinally stretched polyester resin film is passed through the tenter, and the glass transition point (Tg) or higher in the lateral stretching zone. Transverse stretching is performed in the range of + 100 ° C. or lower. Preferably, the glass is stretched in the range of glass transition point (Tg) + 25 ° C. or higher and glass transition point (Tg) + 45 ° C. When the transverse stretching temperature is lower than the glass transition point (Tg), the polyester resin film being stretched is torn. On the other hand, when it exceeds the glass transition point (Tg) + 100 ° C., stretch unevenness occurs in the width direction of the polyester resin film. Further, the transverse stretching ratio in the transverse stretching zone is preferably 2.0 to 5.0 times. When the transverse stretching ratio is less than 2.0 times, the polyester resin film has thickness unevenness, and when it exceeds 5.0 times, the polyester resin film breaks during stretching.

  After transverse stretching in the transverse stretching zone, heat setting treatment is performed in the heat setting zone in the range of melting point (Tm) -30 ° C. or higher and melting point (Tm) -5 ° C. or lower. When the heat setting temperature is less than the melting point (Tm) −30 ° C., the polyester resin film is easily cleaved, so that the optical film is unbearable due to damage or the like caused by processing in the subsequent steps. On the other hand, when the heat setting temperature exceeds the melting point (Tm) −5 ° C., partial sagging occurs during film conveyance, causing a scratch defect, and the production stability is not good.

[Winding process]
As described above, a polyester resin film having a small thickness unevenness and useful as an optical film can be obtained, and this polyester resin film is wound up by a winder.

[Polyester resin material]
Next, the material used for the manufacturing method of the polyester resin film of this invention is demonstrated. The polyester resin used in the present invention is obtained by polycondensation from a diol and a dicarboxylic acid. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, adipic acid, sebacic acid and the like. Examples of the diol include those represented by ethylene glycol, triethylene glycol, tetramethylene glycol, cyclohexanedimethanol and the like. Specific examples include polyethylene terephthalate, polytetramethylene terephthalate, polyethylene-P-oxybenzoate, poly-1,4-cyclohexylenedimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate. These polyesters may be homopolymers, copolymers or blends with monomers having different components. Examples of the copolymer component include diol components such as diethylene glycol, neopentyl glycol, and polyalkylene glycol, and carboxylic acid components such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid. .

  A known catalyst can be used for the esterification reaction and the transesterification reaction in the production of the polyester. The esterification reaction proceeds even without the addition of a catalyst, but since the transesterification reaction takes time, the polymer must be held at a high temperature for a long time, resulting in inconveniences such as thermal degradation. Therefore, the transesterification reaction can be efficiently advanced by adding a catalyst as shown below.

  For example, as a catalyst for transesterification, manganese acetate, manganese acetate tetrahydrate, cobalt acetate, magnesium acetate, magnesium acetate tetrahydrate, calcium acetate, cadmium acetate, zinc acetate, zinc acetate dihydrate, acetic acid Lead, magnesium oxide, lead oxide and the like are generally used. These may be used alone or in combination.

The specific resistance of the polyester resin to be melt-extruded is adjusted to 5 × 10 ^{6 to} 3 × 10 ⁸ Ω · cm. When the specific resistance is less than 5 × 10 ⁶ Ω · cm, yellowishness increases and the generation of foreign substances increases, which is not preferable. When the specific resistance exceeds 3 × 10 ⁸ Ω · cm, air entrainment occurs. The amount becomes large and unevenness is generated on the film surface.

  The specific resistance of the polyester resin is adjusted by adjusting the content of the metal catalyst. In general, the higher the content of the metal catalyst in the polymer, the faster the transesterification reaction and the smaller the specific resistance value. However, if the content of the metal catalyst is too high, the polymer cannot be uniformly dissolved in the polymer, and aggregated foreign matter is generated. Cause.

  Further, the polyester resin may contain phosphoric acid, phosphorous acid and esters thereof and inorganic particles (silica, kaolin, calcium carbonate, titanium dioxide, barium sulfate, alumina, etc.) in the polymerization stage. Further, inorganic particles or the like may be blended with the polymer after polymerization. Further, known heat stabilizers, antioxidants, antistatic agents, lubricants, ultraviolet absorbers, fluorescent brighteners, pigments, light-shielding agents, fillers, flame retardants and the like may be added.

[Polyester resin film]
The thickness of the polyester resin sheet after melt extrusion is 1500 μm or more. Moreover, it is preferable that the thickness of a polyester resin film is 150 micrometers or more. Since the method for producing a polyester resin film of the present invention is effective for producing a thick polyester resin film, it is particularly effective for sheets and films in the above range.

  Moreover, it is preferable that the haze of a polyester resin film is 2.0% or less. When the haze is low, the brightness of the FPD screen is improved and can be suitably used. More preferably, it is 1.0% or less, More preferably, it is 0.8% or less, More preferably, it is 0.5% or less. The curl of the polyester resin film is preferably 50 mm or less. If the curl is small, the processing is good and the warpage of the panel can be suppressed. More preferably, it is 30 mm or less, More preferably, it is 20 mm or less, More preferably, it is 10 mm or less.

  The curl was measured by the following measuring method. The biaxially stretched polyester resin film was cut to a length of 30 cm in length and stored in a room that was conditioned at 25 ° C. and 60% rh for 24 hours. Thereafter, the film was placed on the ground so that the curl direction was upward, and the distance at which the film edge part floated from the ground was determined, and the value was defined as curl.

  The polyester resin film produced by the production method of the present invention can be suitably used as a base material for an antireflection film and a base material for a diffusion film. The anti-reflection film is attached to the front plate (optical filter) of displays such as cathode ray tube display (CRT), LCD, PDP, etc., and uses light interference by the anti-reflection layer to suppress reflection and reflection on the screen surface. It has the effect of reducing light. The diffusion film is one of the materials constituting the liquid crystal backlight, and is a translucent film (sheet or plate) that scatters and diffuses light. It is used to uniformly transmit the light from the fluorescent tube to the front surface of the LCD. The polyester resin produced by the production method of the present invention is thick and strong, and is transparent because it prevents haze deterioration due to crystallization. Therefore, it can be suitably used as a substrate for an optical film, particularly as an antireflection film or a diffusion prevention film.

  Hereinafter, the practical effects of the present invention will be described by way of examples, but the present invention is not limited to these examples. 6-8 show the test conditions and results of the examples of the present invention. FIG. 6 shows the conditions of the resin, sheet and casting drum used in the test. FIG. 7 shows the conditions of the cold air generator and the cooling fan. FIG. 8 shows the evaluation results of the test. In addition, the raw material of the resin A in FIG. 6 is a polyethylene terephthalate, and the raw material of the resin B is a polyethylene naphthalate. Moreover, the evaluation in FIG. 8 was evaluated according to the following criteria.

<Haze>
◎ ・ ・ ・ 0.5% or less ○ ・ ・ ・ 1.0% or less △ ・ ・ ・ 2.0% or less × ・ ・ ・ 2.0%
◎ ・ ・ ・ 10mm or less ○ ・ ・ ・ 20mm or less △ ・ ・ ・ 50mm or less × ・ ・ ・ 50mm or more
○ ・ ・ ・ Good △ ・ ・ ・ Slightly bad, but there is no actual damage and is within the allowable range × ・ ・ ・ There is actual damage <Surface shape>
○ ・ ・ ・ Good △ ・ ・ ・ Slightly bad, but no actual damage, within the allowable range × ・ ・ ・ There is actual damage <wrinkle>
○… Good △… Slightly bad, but no actual damage, but within an allowable range ×… There is actual damage As shown in FIG. 8, the sheet thickness is reduced (Comparative Example 1), and the wind speed of the cold air is increased (Comparison) Example 4) By increasing the exhaust amount of the cooling fan (Comparative Example 7), in the comparative example having a high surface average cooling rate, the surface condition was poor and a practical level film could not be produced. In Comparative Examples 2, 5, and 6 having a low surface average speed, generation of haze was observed. Further, in Comparative Example 3 in which the cooling rate between the front surface and the back surface of the sheet was large, the occurrence of curling was observed.

  On the contrary, Examples 1 to 4 tested under the conditions of the present invention were able to form a good surface film with less haze, curl, unevenness and wrinkle. Further, Example 5 and Example 6 in which the temperature of the refrigerant flowing through the casting drum was high were slightly bad in surface shape, but were not harmful and were within an allowable range. In Example 7 in which the slit nozzle of the cold air generator is not formed within the preferable numerical range, Example 8 in which the supply amount of the cold air is larger than the exhaust amount, the unevenness and the like can be confirmed due to the influence of the cold air in the vicinity of the seat. However, it was within the allowable range.

It is the schematic of the manufacturing apparatus of a polyester resin film. It is the front view seen from the casting drum side of the cold wind generator. It is a figure explaining the temperature-fall crystallization peak by temperature rising and cooling of a polyester resin. It is the schematic of the longitudinal stretch machine which implements a longitudinal stretch process. It is the schematic of the horizontal extending machine which implements a horizontal extending process. It is a table | surface figure which shows the result of a present Example. It is a table | surface figure which shows the result of a present Example. It is a table | surface figure which shows the result of a present Example.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Polyester resin film, 10 ... Film forming process part, 11 ... Die, 12 ... Casting drum, 13 ... Cold air generator, 14 ... Air supply fan, 15 ... Exhaust fan, 16 ... Cold air outlet (slit nozzle), 17 ... Exhaust nozzle, 20 ... longitudinal stretching machine, 23 ... heating stretching roll, 24 ... cooling stretching roll, 30 ... transverse stretching machine, 31 ... tenter, 32 ... windshield curtain, 40 ... winder

Claims (11)

In a method for producing a polyester resin film, a polyester resin is melt-extruded into a sheet, cooled and solidified on a casting drum to produce a polyester resin sheet, and then subjected to biaxial stretching.
The thickness of the polyester resin sheet after the melt extrusion is 1500 μm or more,
During the cooling and solidification, the sheet is forcibly cooled by blowing cold air of 5 ° C. or more and 50 ° C. or less from a cold air generator facing the casting drum, and the surface temperature of the sheet is set to (temperature-decreasing crystal of the polyester resin). Crystallization start temperature + 40 ° C.) to (cooling crystallization end temperature−40 ° C.) in the range of 350 ° C./min to 590 ° C./min .
The cold air outlet shape of the cold air generator is a slit nozzle that extends in the width direction of the polyester resin sheet surface, the slit width of the slit nozzle is 0.5 mm or more and 10 mm or less, the pitch of the slit nozzle is 10 mm or more and 100 mm or less, A method for producing a polyester resin film, wherein a distance between the slit nozzle and a casting drum is 5 mm or more and 200 mm or less . Average cooling rate A (° C./min) on the surface of the polyester resin sheet, refrigerant temperature B (° C.) flowing through the casting drum, and overall heat transfer coefficient C (J / J) from the casting drum to the back surface of the polyester resin sheet ^{2. The} method for producing a polyester resin film according to claim 1, wherein m ² · s · K) and a glass transition point Tg (° C.) of the polyester resin satisfy the following formula.
30 ≦ C × (300−B) ÷ A ≦ 4000 (1)
0 ≦ B ≦ Tg (2) The polyester according to claim 1 or 2, wherein a heat transfer coefficient from the cold air generator to the surface of the polyester resin sheet is 1 J / m ² · s · K or more and 500 J / m ² · s · K or less. A method for producing a resin film. The method for producing a polyester resin film according to any one of claims 1 to 3, wherein an average wind speed of the cold air is 5 m / sec or more and 100 m / sec or less.   The method for producing a polyester resin film according to any one of claims 1 to 4, wherein a difference in cooling rate in the width direction of the surface of the polyester resin sheet is 100 ° C / min or less. As cold air outlet air volume of the cold air generator is constant, a polyester resin film according to claims 1, characterized in that to control the rotational speed of the cold air fan inverter according to the outside air temperature and pressure 5 either Manufacturing method. The cold air generator includes an exhaust fan,
The total supply air volume X of the cold air (m 3 ^/ min), according to any one of claims 1 to 6, wherein the exhaust fan of the total exhaust air volume Y (m 3 ^/ min) satisfies the following equation Manufacturing method of polyester resin film.
0.5 ≦ Y ÷ X ≦ 4 (3) The method for producing a polyester resin film according to any one of claims 1 to 7, wherein the cold air generator is provided with a dustproof filter. Method for producing a polyester resin film according to claim 1, 8 or the thickness of the polyester resin film and the polyester resin sheet biaxial stretching, characterized in that at 150μm or more. The haze of the said polyester resin film is 2% or less, The manufacturing method of the polyester resin film in any one of Claim 1 to 9 characterized by the above-mentioned. Method for producing a polyester resin film according to claim 1, 10 or, characterized in that the curl of the polyester resin film is less than 50mm.

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