JP4762009B2 - Method for producing drawing-drawn thermoplastic polyester resin sheet - Google Patents

Description

  The present invention relates to a method for producing a drawn stretched thermoplastic polyester resin sheet, and more particularly, a drawn stretched thermoplastic polyester in which the drawn drawn stretched thermoplastic polyester resin sheet has a small meandering and can be easily drawn and stretched. The present invention relates to a method for producing a resin sheet.

Conventionally, a method for producing a transparent crystalline polymer sheet having a smooth surface and a high strength and elastic modulus by pultrusion has been studied. For example, crystals such as polyethylene, polypropylene, polyacetal resin, nylon, etc. The temperature of the differential polymer raw sheet is not higher than the deformation starting temperature when the sheet is heated at a rate of temperature increase of 10 ° C./min with a load of 10 MPa and does not exceed the rising temperature of the differential scanning calorimetry melting curve. There has been proposed a method for producing a crystalline polymer sheet, which is drawn through at least a draw ratio of 2.5 times or more through a pair of heated rollers (see, for example, Patent Document 1).
JP 60-15120 A

  However, in order to stretch a polyester resin by the above method for producing a crystalline polymer sheet, the polyester resin is too hard at low temperatures and lacks flexibility necessary for stretching, and relaxation of orientation becomes dominant at high temperatures. Therefore, in order to obtain a stretched sheet having excellent strength and elastic modulus, it is necessary to perform pultrusion molding in the temperature range of the glass transition temperature of the polyester resin -20 ° C to the glass transition temperature + 20 ° C. When it is heated above the temperature, the elastic modulus decreases rapidly.

  Therefore, due to the temperature difference of the polyester-based resin sheet, the high temperature part has a low elastic modulus and becomes easy to be stretched, and the low temperature part has a high elastic modulus and is difficult to be stretched. The stretched polyester resin sheet was unevenly stretched in the width direction of the polyester resin sheet, causing meandering, and could not be uniformly drawn.

As a method for preventing meandering, for example, a plurality of guide rolls for guiding the stretched film are provided, a roll rotation driving device for rotating the guide rolls is provided, and a speed adjustment capable of adjusting the rotation speed of each guide roll is possible. A stretched film production facility provided with means (for example, see Patent Document 2), when a polymer sheet made of an aromatic polyamide containing a solvent is stretched in the vertical axis direction, it is first stretched in the atmosphere and then in a liquid bath A method for producing an aromatic polyamide film characterized in that the film is stretched by a method (for example, see Patent Document 3) has been proposed.
JP 2003-71917 A JP 11-48334 A

  However, since drawing stretching involves grasping one end of the polyester resin sheet and pulling it between the pair of drawing rolls by pulling with a driving roll, the above method can not be applied to drawing stretching of the polyester resin sheet. There wasn't.

  In view of the above-mentioned drawbacks, the object of the present invention is to uniformly heat a polyester resin sheet, draw-draw and stretch without meandering, and draw a stretched thermoplastic polyester resin sheet excellent in tensile strength, tensile elastic modulus and heat resistance. It is in providing the method of manufacturing.

  The method for producing a drawn stretched thermoplastic polyester resin sheet according to the present invention comprises heating an amorphous thermoplastic polyester resin sheet in a heating tank with a heating means and pulling it between a pair of drawn rolls. A method for producing a drawing-drawn thermoplastic polyester resin sheet, in which at least two heating means are provided symmetrically with respect to the feeding direction of the thermoplastic polyester resin sheet, and between a pair of drawing rolls and drive rolls The sheet position detection device is installed in the machine, and the sheet position detection device detects the position of the sheet, sends detection data to the control device, and controls the amount of heat supplied from the heating means according to the data, and is drawn and stretched. Further, the meandering of the thermoplastic polyester resin sheet is controlled.

  Examples of the thermoplastic polyester resin used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyglycolic acid, poly (L-lactic acid), poly (3-hydroxybutyrate), poly ( 3-hydroxybutyrate / hydroxyvalerate), poly (ε-caprolactone), polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate / lactic acid, polybutylene succinate / carbonate, polybutylene succinate Nate / terephthalate, polybutylene adipate / terephthalate, polytetramethylenadipate / terephthalate, polybutylene succinate / adipate / terephthalate, etc. Polyethylene terephthalate is preferable.

  Although the thickness of a thermoplastic polyester-type resin sheet is not specifically limited, 0.5-5 mm is preferable. If the thickness is less than 0.5 mm, the sheet thickness after drawing and drawing becomes too thin, and the strength during handling may not be sufficient, and if it exceeds 5 mm, drawing may be difficult.

  In the present invention, the heating means heats the amorphous polyester resin sheet in the amorphous state with hot air at the same temperature in advance in a heating tank, and only at a predetermined position immediately before the drawing roll. Although the sheet temperature may be finely adjusted by heating, hot air is blown and heated from above and / or below the amorphous thermoplastic polyester resin sheet by a hot air supply device and pulled by a driving roll, It is preferable to produce a drawing-drawn thermoplastic polyester resin sheet by drawing between a pair of drawing rolls.

  If there is a temperature distribution in the heated thermoplastic polyester resin sheet, the high temperature part has a low elastic modulus and is easily stretched, and the low temperature part has a high elastic modulus and is difficult to stretch. The pultruded stretch-drawn thermoplastic polyester-based resin sheet varies in stretch ratio in the width direction of the polyester-based resin sheet, causing meandering, and cannot be uniformly pultruded. Therefore, the temperature distribution of the heated thermoplastic polyester resin sheet is preferably as small as possible, and the temperature difference across the entire surface of the thermoplastic polyester resin sheet is preferably within 1 ° C, and preferably within 0.5 ° C.

  Therefore, in the present invention, at least two hot air supply devices are installed in the heating tank symmetrically with respect to the feeding direction of the thermoplastic polyester resin sheet. Moreover, it is only necessary to heat the thermoplastic polyester resin sheet by blowing hot air from above or below with a hot air supply device. However, in order to heat the thermoplastic polyester resin sheet more uniformly, the thermoplastic polyester resin sheet may be used. It is preferable to heat the resin sheet by blowing hot air from above and below with a hot air supply device, and it is preferable to install and heat four or more hot air supply devices. Further, it is preferable to heat the hot air supply device by installing it symmetrically and vertically symmetrical with respect to the feeding direction of the thermoplastic polyester resin sheet.

  The heating temperature of the thermoplastic polyester resin sheet is not particularly limited, but when the temperature is low, the stretched thermoplastic polyester resin sheet is whitened or too hard to be drawn, and when the temperature becomes high, the orientation is high. Since the strength is reduced by relaxation, it is preferably heated to a glass transition temperature or higher of the thermoplastic polyester resin, and a temperature of glass transition temperature + 20 ° C. or lower is preferable.

  In the present invention, the heated thermoplastic polyester resin sheet is pulled with a driving roll, pulled through a pair of drawing rolls, and drawn and stretched. The roll temperature at the time of drawing is not particularly limited, but if it is low, the stretched thermoplastic polyester resin sheet is too hard to be cut and pulled, and if it is high, the thermoplastic polyester resin sheet becomes soft Since the sheet is cut by the tension of pulling out the sheet, it is preferable to pull out the heated thermoplastic polyester resin sheet while cooling, less than the glass transition temperature of the stretched thermoplastic polyester resin, glass transition temperature -20 ° C. The glass transition temperature is preferably less than the glass transition temperature of the thermoplastic polyester resin and the glass transition temperature of the thermoplastic polyester resin of −10 ° C. or higher.

  In addition, when the amorphous polyester resin sheet in an amorphous state is pulled out, the roll does not necessarily rotate. However, particularly when the thermoplastic polyester resin sheet is thick, heat accumulation of the roll due to shearing heat generation occurs. It is preferable to rotate the sheet in the drawing direction because the temperature of the resulting sheet is likely to increase.

  When the rotation speed of the roll is slow, the contact time between the roll and the thermoplastic polyester resin sheet becomes longer, frictional heat is generated, the roll temperature rises, and the effect of cooling the heated thermoplastic polyester resin is reduced. However, when the predetermined drawing and stretching temperature is exceeded and the rotational speed of the roll is increased, only the thermoplastic polyester resin on the surface of the thermoplastic polyester resin sheet flows and cannot be drawn and drawn uniformly. Further, the elastic modulus of the drawn and drawn thermoplastic polyester resin sheet is lowered.

  Accordingly, the rotational speed of the roll is preferably substantially the same or lower than the feeding speed of the sheet before stretching when the thermoplastic polyester resin sheet is pulled out in the state where the roll is not rotating at the same drawing speed. .

  Further, when the thickness of the thermoplastic polyester resin sheet is large (1.5 mm or more), heat generation due to shearing between the roll and the sheet becomes large, and therefore, the rotation speed of the roll is preferably 50 to 100% of the feed speed. . Moreover, when the thickness of the thermoplastic polyester resin sheet is thin, the cooling effect by the roll is great, so the rotation speed of the roll may be slow.

  In addition, a sheet position detection device is installed between the pair of drawing rolls and drive rolls, the sheet position detection device detects the position of the sheet, sends detection data to the control device, and the hot air of the hot air supply device according to the data. By controlling the ejection amount or ejection temperature, the meandering of the drawn and stretched thermoplastic polyester resin sheet is controlled.

That is, when the sheet position is detected by the sheet position detection device, the temperature of the thermoplastic polyester resin sheet before drawing and drawing is high on the side on which the sheet is approached, and the elastic modulus is low and the drawing is performed. Since it is easy to be done, the amount of heat supply from the hot air supply device on the near side is reduced. On the contrary, on the side away from the sheet, the temperature of the thermoplastic polyester resin sheet before drawing and drawing is low, the elastic modulus is high, and the drawing is difficult to draw. Increase the heat supply of the supply device.
Although the control of the heat supply amount may be performed using a temperature-controlled heating roll, it is preferable to control the hot air ejection amount or the ejection temperature.

  The draw ratio of the above-described drawing stretching is not particularly limited. However, if the stretching ratio is low, a sheet excellent in tensile strength and tensile elastic modulus cannot be obtained. If the stretching ratio is high, the sheet tends to break during stretching. 2-9 times is preferable, More preferably, it is 4-8 times.

  The drawing-drawn thermoplastic polyester resin sheet produced by the method for producing a drawing-drawn thermoplastic polyester resin sheet of the present invention has excellent tensile strength, tensile elastic modulus, and heat resistance, and is a building material that requires these performances. Etc. are preferably used.

  The structure of the manufacturing method of the drawing extending | stretching thermoplastic polyester-type resin sheet of this invention is as above-mentioned, Since a thermoplastic polyester-type resin sheet can be drawn and extended without heating and meandering uniformly, tensile strength, tensile A drawing-drawn thermoplastic polyester resin sheet having excellent elastic modulus and heat resistance can be obtained efficiently.

  Next, examples of the present invention will be described with reference to the drawings. However, the present invention is not limited to the following examples.

  FIG. 1 is a schematic side view showing an example of a method for producing a drawn stretched thermoplastic polyester resin sheet of the present invention, and FIG. 2 is a schematic plan view thereof.

  In the figure, 1 is a supply roll for the thermoplastic polyester resin sheet 10, 2 is a heating tank, 3 is a brake roll installed near the inlet of the heating tank 2, 4 is a drawing roll installed near the inlet of the heating tank 2, It is a drive roll installed behind the drawing roll 4. In the heating tank 2, four hot air supply devices 6, 61, 62, 63 are installed above the thermoplastic polyester resin sheet 10, and four hot air supply devices are provided below the thermoplastic polyester resin sheet 10. 64, 65, 66, 67 are installed.

  The hot air supply devices 6 and 61 and the hot air supply devices 62 and 63 are arranged in parallel to the feeding direction of the thermoplastic polyester resin sheet 10, and the hot air supply devices 6 and 62 and the hot air supply devices 61 and 63 are thermoplastic polyester. The system resin sheet 10 is arranged symmetrically with respect to the feeding direction.

  The hot air supply devices 64 and 65 and the hot air supply devices 66 and 67 are arranged in parallel to the feeding direction of the thermoplastic polyester resin sheet 10, and the hot air supply devices 64 and 66 and the hot air supply devices 65 and 67 are hot. The plastic polyester resin sheet 10 is disposed symmetrically with respect to the feeding direction.

  Furthermore, the hot air supply device 6 is installed at 64, the hot air supply device 61 is installed at 65, the hot air supply device 62 is installed at 66, and the hot air supply device 63 is installed vertically 67.

  Further, the hot air supply devices 6, 61, 62, 63, 64, 65, 66, 67 are connected to different heating devices 7, 7,..., And the air heated by the heating devices 7, 7,. Can be sprayed onto the surface of the thermoplastic polyester resin sheet 10.

  On the rear side of the drawing roll 4, the drawing-drawn thermoplastic polyester resin sheet 11 can be measured so that the positions of both end portions of the drawing-drawn thermoplastic polyester resin sheet 11 obtained by drawing and drawing the thermoplastic polyester-based resin sheet 10 can be measured. Sheet position detectors 8 and 8 are installed on both sides of the sheet.

  In the figure, 9 is a control device, and the control device 9 is electrically connected to the sheet position detection devices 8, 8 and the heating devices 7, 7. Sheet position detection data is sent to the control device 9, and the hot air ejection amount or ejection temperature of the hot air supply devices 6, 61, 62, 63, 64, 65, 66, 67 can be controlled in accordance with the data. .

  Therefore, when the thermoplastic polyester resin sheet 10 wound around the supply roll 1 is pulled by the drive roll 5, the thermoplastic polyester resin sheet 10 is supplied to the heating tank 2 via the brake roll 3, and hot air It is heated by hot air blown from the supply devices 6, 61, 62, 63, 64, 65, 66, 67. The heated thermoplastic polyester resin sheet 10 is further pulled by the driving roll 5, drawn between the pair of drawing rolls 4, and drawn to obtain a drawing drawn thermoplastic polyester resin sheet 11.

  At this time, a sheet position detection device 8 is installed between the pair of drawing rolls 4 and the drive roll 5, the sheet position detection device 8 detects the position of the sheet, and sends detection data to the control device 9. The meandering of the drawn stretched thermoplastic polyester resin sheet 11 that has been drawn and stretched by controlling the hot air ejection amount or ejection temperature of the hot air supply device 6, 61, 62, 63, 64, 65, 66, 67 according to the data. To control.

  That is, when the position of the sheet is detected by the sheet position detecting device 8, the temperature of the thermoplastic polyester resin sheet before drawing and drawing is high on the side where the sheet is approached, and the elastic modulus is low. Since it is easy to be stretched, the hot air ejection amount of the hot air supply device on the approaching side is reduced or the ejection temperature is lowered. On the contrary, on the side away from the sheet, the temperature of the thermoplastic polyester resin sheet before drawing and drawing is low, the elastic modulus is high, and the drawing is difficult to draw. Increase the amount of hot air jetted from the supply device or raise the jetting temperature. By controlling in this way, the temperature distribution of the thermoplastic polyester resin sheet 10 becomes uniform, the meandering of the drawn stretched thermoplastic polyester resin sheet 11 is suppressed, and the drawn stretched thermoplastic polyester resin sheet without meandering. 11 is obtained.

Example 1
A polyethylene terephthalate sheet having a thickness of 3 mm and a width of 200 mm (manufactured by Teijin Chemicals Ltd., trade name “A-PET sheet FR”, crystallinity 4%, glass transition temperature 72 ° C.) 10 is supplied to the drawing and drawing apparatus, and the heating tank 2 is supplied with hot air of 75 ° C. at a speed of 30 m ³ / min, and the speed of the drive roll 5 is set to a speed of 2 m / min between a pair of drawing rolls 4 (roll interval 0.3 mm) heated to 70 ° C. Then, it was drawn and stretched. Further, the sheet position detection device 8 detects the position of the sheet, sends the detection data to the control device 9, and hot air blowout from the hot air supply devices 6, 61, 62, 63, 64, 65, 66, 67 according to the data. The amount was controlled.

  Drawing and stretching were performed for 30 minutes, but the meandering width was stable within 20 mm. Further, the surface temperature in the width direction of the stretched thermoplastic polyester resin sheet immediately before the drawing roll 8 was measured and found to be in the range of 75 ± 0.5 ° C.

When the linear expansion coefficient of the obtained drawn stretched thermoplastic polyester resin sheet was measured in accordance with JIS K 7197, it was −0.4 × 10 ⁻⁵ / ° C., and the tensile modulus was a tensile test of JIS K 7113. It was 10.0 GPa when measured according to the method.

(Comparative Example 1)
The thermoplastic polyester resin sheet was drawn and stretched using the conventional drawing and stretching thermoplastic polyester resin sheet production apparatus shown in FIGS. FIG. 3 is a schematic side view showing an example of a conventional apparatus for producing a drawn stretched thermoplastic polyester resin sheet, and FIG. 4 is a schematic plan view of FIG.

  In the figure, 1 ′ is a supply roll for the thermoplastic polyester resin sheet 10 ′, 2 ′ is a heating tank, 3 ′ is a brake roll installed near the inlet of the heating tank 2 ′, and 4 ′ is installed near the inlet of the heating tank 2 ′. The drawn roll 5 ′ is a drive roll installed behind the drawn roll 4 ′. In the heating tank 2 ', one hot air supply device 6' is installed above the thermoplastic polyester resin sheet 10 ', and directly below the hot air supply device 6' below the thermoplastic polyester resin sheet 10 '. One hot air supply device 6 ″ is installed.

  The hot air supply devices 6 ′ and 6 ″ are connected to different heating devices 7 ′ and 7 ″, respectively, and air heated by the heating devices 7 ′ and 7 ″ is blown onto the surface of the thermoplastic polyester resin sheet 10 ′. It is made possible to attach.

A polyethylene terephthalate sheet having a thickness of 1 mm and a width of 200 mm (manufactured by Teijin Chemicals Ltd., trade name “A-PET sheet FR”, crystallinity 4%, glass transition temperature 72 ° C.) 10 ′ is supplied to the drawing and stretching apparatus and heated. A hot air of 75 ° C. is supplied to the tank 2 ′ at a speed of 30 m ³ / min, and the speed of the driving roll 5 ′ is 2 m / min between a pair of drawing rolls 4 ′ (roll interval 0.2 mm) heated to 70 ° C. Was drawn and stretched.

  Drawing and stretching were performed for 30 minutes, but the width of the meander was within 120 mm, and drawing and drawing were difficult. Further, the surface temperature in the width direction of the stretched thermoplastic polyester resin sheet immediately before the drawing roll 8 'was measured and found to be in the range of 75 ± 2.0 ° C.

When the linear expansion coefficient of the obtained drawn stretched thermoplastic polyester resin sheet 11 ′ was measured in accordance with JIS K 7197, it was −0.8 × 10 ⁻⁵ / ° C., and the tensile modulus was JIS K 7113. It was 10.5 GPa when measured according to the tensile test method.

It is a side surface schematic diagram which shows an example of the manufacturing method of the drawing extending | stretching thermoplastic polyester-type resin sheet of this invention. FIG. 2 is a schematic plan view of FIG. 1. It is a side surface schematic diagram which shows an example of the manufacturing apparatus of the conventional drawing extending | stretching thermoplastic polyester-type resin sheet. FIG. 4 is a schematic plan view of FIG. 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Supply roll of thermoplastic polyester-type resin sheet 2 Heating tank 3 Brake roll 4 Pull-out roll 5 Drive roll 6 Hot-air supply apparatus 7 Heating apparatus 8 Sheet position detection apparatus 9 Control apparatus 10 Thermoplastic polyester-type resin sheet 11 Drawing drawing thermoplastic polyester Resin sheet

Claims (6)

  In a heating tank, a thermoplastic polyester resin sheet in an amorphous state is heated by a heating means and pulled by a driving roll, and is a method for producing a drawn stretched thermoplastic polyester resin sheet that is drawn between a pair of drawn rolls, At least two heating means are provided symmetrically with respect to the feeding direction of the thermoplastic polyester resin sheet, and a sheet position detection device is installed between the pair of drawing rolls and the drive roll. Detecting the position of the sheet, sending detection data to a control device, and controlling the amount of heat supplied from the heating means according to the data, thereby controlling the meandering of the drawn and stretched thermoplastic polyester resin sheet. A method for producing a drawn stretch thermoplastic polyester resin sheet.   The heating means blows hot air from above and / or below the thermoplastic polyester resin sheet by the hot air supply device, and the control of the heat supply amount from the heating means is controlled by the hot air blowing amount of the hot air supply device or The method for producing a drawn stretched thermoplastic polyester resin sheet according to claim 1, wherein the method is performed by controlling an ejection temperature.   The method for producing a drawn stretched thermoplastic polyester resin sheet according to claim 1 or 2, wherein the amorphous thermoplastic polyester resin sheet is heated to a temperature equal to or higher than the glass transition temperature of the thermoplastic polyester resin.   The drawing stretch thermoplastic polyester according to any one of claims 1 to 3, wherein the temperature of the pair of drawing rolls is less than the glass transition temperature of the thermoplastic polyester-based resin and a glass transition temperature of -20 ° C or higher. Of manufacturing a resin-based resin sheet.   2. The roll according to claim 1, wherein the roll is rotated in the pulling direction at a speed substantially equal to or less than a feed speed when the sheet is pulled in a state where the roll is not rotated at the same drawing speed. The manufacturing method of the extending | stretching thermoplastic polyester-type resin sheet of any one of -4.   The method for producing a stretched thermoplastic polyester resin sheet according to any one of claims 1 to 5, wherein the stretch ratio is 2 to 9 times.

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