JP2007076313A - Manufacturing method for stretched thermoplastic polyester-based resin sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method for a stretched thermoplastic polyester-based resin sheet excellent in tensile strength, tensile modulus and heat resistance by monoaxially stretching a pultruded thermoplastic polyester-based resin sheet. <P>SOLUTION: A manufacturing method for a stretched thermoplastic polyester-based resin sheet comprises steps for stretching an amorphous thermoplastic polyester-based resin sheet by drive rolls, pulling out the sheet between a pair of pull-out rolls, to obtain a stretched thermoplastic polyester-based resin sheet, and successively monoaxially stretching the sheet. In the manufacturing method of the stretched thermoplastic polyester-based resin sheet, monoaxial stretching is carried out after slacks of the pulled-out stretched thermoplastic polyester-based resin sheet are removed by pressing slant rolls against the pulled-out stretched thermoplastic polyester-based resin sheet. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a stretched thermoplastic polyester resin sheet, and more particularly to a method for producing a stretched thermoplastic polyester resin sheet having excellent tensile strength, tensile elastic modulus, and heat resistance.

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 base sheet of the differential polymer calorimetry melting curve is not exceeded the deformation starting temperature when the sheet is heated at a rate of temperature increase of 1 ° C./min with a 10 MPa load applied to the sheet. 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).
Japanese Patent Laid-Open No. 60-15120

  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 within the temperature range of the glass transition temperature of the polyester resin -20 ° C to the glass transition temperature + 20 ° C. The system resin sheet has a drawback in that the elastic modulus rapidly decreases when heated to a temperature higher than the glass transition temperature.

  In addition, when a polyester resin sheet is pultruded, the stretched polyester resin sheet that has been pultruded varies in the stretching ratio in the width direction of the polyester resin sheet, resulting in meandering. For this reason, the pultruded stretched polyester resin sheet could not be continuously uniaxially stretched.

  An object of the present invention is to provide a method for producing a stretched thermoplastic polyester resin sheet excellent in tensile strength, tensile elastic modulus and heat resistance by uniaxially stretching after pultruding a polyester resin sheet in view of the above drawbacks. It is to provide.

  The method for producing a stretched thermoplastic polyester resin sheet according to claim 1 of the present invention is such that the amorphous thermoplastic polyester resin sheet in an amorphous state is pulled with a driving roll, and is drawn between a pair of pulling rolls to draw a stretched thermoplastic polyester. In the manufacturing method of a stretched thermoplastic polyester resin sheet in which a drawn stretched thermoplastic polyester resin sheet is continuously uniaxially stretched after the base resin sheet is manufactured, an inclined roll is pressed against the stretched stretched thermoplastic polyester resin sheet. It is characterized by uniaxially stretching after removing the sag of the drawn stretched thermoplastic polyester resin sheet.

  The method for producing a stretched thermoplastic polyester resin sheet according to claim 2 is such that the drawing and stretching are performed by pulling an amorphous thermoplastic polyester resin sheet with a driving roll, and the glass transition temperature of the thermoplastic polyester resin is -20 ° C. The method for producing a stretched thermoplastic polyester resin sheet according to claim 1, wherein the stretched polyester resin sheet is drawn through a pair of drawing rolls having a glass transition temperature + 20 ° C of the thermoplastic polyester resin. It can be easily drawn and stretched.

  The method for producing a stretched thermoplastic polyester resin sheet according to claim 3, wherein the drawing stretching is performed by pulling an amorphous thermoplastic polyester resin sheet with a driving roll, and a temperature equal to or higher than a glass transition temperature of the thermoplastic polyester resin. 2. The stretching method according to claim 1, wherein the stretching is performed by drawing through a pair of drawing rolls having a temperature of less than the glass transition temperature of the thermoplastic polyester resin and a glass transition temperature of −20 ° C. or higher after being heated. This is a method for producing a thermoplastic polyester resin sheet, which can be drawn and stretched easily.

  The method for producing a stretched thermoplastic polyester resin sheet according to claim 4 is characterized in that the stretched thermoplastic polyester resin sheet according to claim 2 or 3 is uniaxially stretched at a temperature higher than the temperature of the pair of drawing rolls. Production Method A stretched thermoplastic polyester resin sheet excellent in tensile strength, tensile modulus and heat resistance can be obtained.

  6. The method for producing a stretched thermoplastic polyester resin sheet according to claim 5, wherein the uniaxial stretching temperature is the rising temperature of the crystallization peak of the thermoplastic polyester resin in the differential operation calorimetric curve measured at a heating rate of 1 ° C./min. It is the rising temperature of the melting peak. The method for producing a stretched thermoplastic polyester resin sheet according to claim 4, wherein the stretched thermoplastic polyester resin sheet can be suitably uniaxially stretched.

  The method for producing a stretched thermoplastic polyester resin sheet according to claim 6, wherein the stretched thermoplastic polyester resin sheet stretched uniaxially is heat-set at a temperature higher than the uniaxial stretch temperature. It is a manufacturing method of the extending | stretching thermoplastic polyester-type resin sheet of any one of Claim 1, Furthermore, the extending | stretching thermoplastic polyester-type resin sheet excellent in tensile strength, tensile elasticity modulus, and heat resistance is obtained.

  The method for producing a stretched thermoplastic polyester resin sheet according to claim 7, wherein the heat setting temperature is a melting peak of the thermoplastic polyester resin in a differential operation calorimetric curve measured at a uniaxial stretching temperature to a heating rate of 1 ° C / min. The stretched thermoplastic polyester resin sheet production method according to claim 6, wherein the heat setting can be performed stably and reliably.

  The method for producing a stretched thermoplastic polyester resin sheet according to claim 8 is characterized in that heat setting is performed in a state in which the stretched thermoplastic polyester resin sheet that has been uniaxially stretched is fixed so as not to shrink due to heat. Item 8. The method for producing a stretched thermoplastic polyester resin sheet according to Item 6 or 7, wherein heat setting can be performed more stably and reliably.

  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, 0.5-4 mm is preferable. If it is less than 0.5 mm, the thickness of the sheet after stretching becomes too thin, and the strength during handling may not be sufficient, and if it exceeds 4 mm, stretching may be difficult.

  In the present invention, the amorphous polyester resin sheet in the amorphous state is pulled with a driving roll and pulled through a pair of drawing rolls, and is drawn and drawn, but the drawing drawing method is not particularly limited. The drawn thermoplastic polyester resin sheet in a state is pulled with a driving roll, and a pair of drawing rolls having a glass transition temperature of −20 ° C. of the stretched thermoplastic polyester resin to a glass transition temperature of the stretched thermoplastic polyester resin of + 20 ° C. There is a method of drawing and drawing through the space.

  When the temperature of the pair of drawing rolls during drawing and drawing is low, the drawn thermoplastic polyester resin sheet is too hard to be drawn, and when the temperature is high, the thermoplastic polyester resin sheet becomes soft and pulls out the sheet. Since the sheet is cut by tension, the glass transition temperature of the stretched thermoplastic polyester resin is −20 ° C. to the glass transition temperature of the stretched thermoplastic polyester resin + 20 ° C., more preferably the stretch thermoplastic. The glass transition temperature of the polyester-based resin to the glass transition temperature of the stretched thermoplastic polyester-based resin + 10 ° C.

  Further, as a different drawing / drawing / stretching method, an amorphous thermoplastic polyester resin sheet is pulled with a driving roll and heated to a temperature equal to or higher than the glass transition temperature of the thermoplastic polyester resin. Examples of the stretching method include drawing between a pair of drawing rolls having a temperature lower than the glass transition temperature and a glass transition temperature of −20 ° C. or higher.

  If the temperature of the thermoplastic polyester resin sheet during drawing and drawing is low, the drawn thermoplastic polyester resin sheet is whitened or too hard to be drawn, and when it becomes high, the thermoplastic polyester resin sheet Since the sheet is cut by the tension that pulls out the sheet and becomes soft, it is heated in advance to the glass transition temperature of the thermoplastic polyester resin or more before drawing and stretching, and is preferably the glass transition temperature + 20 ° C. or less.

  When the temperature of the pair of drawing rolls during the drawing and drawing is low, the thermoplastic polyester resin sheet is rapidly cooled and crystallizes and becomes difficult to pull out. When the temperature is high, the thermoplastic polyester resin sheet becomes soft and the sheet is pulled out. Since the sheet is cut by tension, the temperature is lower than the glass transition temperature of the thermoplastic polyester resin, that is, the temperature of the thermoplastic polyester resin sheet or less, and the glass transition temperature of the thermoplastic polyester resin is -20 ° C or higher. 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.

  Further, when pulling out the amorphous polyester resin sheet in an amorphous state, the pair of pulling rolls need not rotate, but may be slightly rotated in the pulling direction in order to make the temperature distribution uniform.

  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.

  In order to improve the physical properties such as tensile strength, tensile elastic modulus, heat resistance, etc., the thermoplastic polyester resin sheet drawn and stretched in the present invention is uniaxially stretched at a temperature higher than the temperature of the drawing roll. The thermoplastic polyester resin sheet has slack (meander) because the stretch ratio is not constant and the length is not uniform due to a partial defect of the thermoplastic polyester resin sheet which is the raw material. .

  Therefore, in the present invention, before the uniaxial stretching, the slanting (meandering) of the drawn stretched thermoplastic polyester resin sheet is removed by pressing the inclined roll against the drawn stretched thermoplastic polyester resin sheet.

  Specifically, the slanting (meandering) of the drawn stretched thermoplastic polyester resin sheet is performed by pressing the inclined roll against the drawn stretched thermoplastic polyester resin sheet that has been drawn and stretched between the drawn roll and the drive roll. Remove.

  The inclined roll is a roll that is mechanically held so as to be movable in the advancing direction, the upward direction, etc. of the drawn stretched thermoplastic polyester resin sheet in which the shafts at both ends of the roll are drawn and stretched, and the drawn stretched thermoplastic polyester According to the state of slack (meandering) of the resin-based resin sheet, the sheet is moved in the advancing direction, the upward direction, etc., and the sheet is pressed to stretch the stretch-drawn thermoplastic polyester resin sheet where there is slack (meandering). Remove.

  When this inclined roll is used, a position measuring device for the drawn and stretched thermoplastic polyester resin sheet is installed in front of the inclined roll, and the slack (sheet position deviation) is measured by the position measuring device. It is preferable to control the position (pressed state) of the inclined roll.

  Also, examples of different inclined rolls are rolls in which the shafts at both ends of the roll are independently urged by springs or the like in the direction of advance or upward of the drawn stretched thermoplastic polyester resin sheet. The portion of the drawn stretched thermoplastic polyester resin sheet with (meandering) is pressed and stretched to remove sagging (meandering).

  The polyester resin of the drawn stretched thermoplastic polyester resin sheet that has been drawn and drawn has high strength because the molecular chains are highly oriented with isotropic crystallization and orientation suppressed by heat, which is a hindrance to stretching. Although the elastic modulus is excellent, the degree of crystallinity is low. Therefore, when heated, the orientation is easily relaxed and the elastic modulus is lowered.

  However, the stretched thermoplastic polyester resin sheet that has been drawn and stretched is uniaxially stretched at a temperature higher than that of the roll, so that the degree of crystallinity is increased without relaxation and the orientation is easy even when heated. Thus, a stretched sheet having excellent heat resistance that is not relaxed can be obtained.

  As the uniaxial stretching method, a roll stretching method is preferably used. The roll stretching method is a method in which a stretched raw fabric is sandwiched between two pairs of rolls having different speeds, and the stretched raw fabric is pulled while being heated, and the molecular orientation can be strongly oriented only in a uniaxial direction. In this case, the speed ratio of the two pairs of rolls becomes the draw ratio.

  The temperature at the time of the uniaxial stretching may be higher than the temperature of the pair of rolls at the time of drawing and drawing, but if it is too high, the drawn and stretched thermoplastic polyester resin sheet is melted and cut. The temperature range from the rising temperature of the crystallization peak of the thermoplastic polyester resin to the rising temperature of the melting peak in the differential operation calorie curve measured at a heating rate of 1 ° C./min is preferable.

  The rising temperature of the crystallization peak of polyethylene terephthalate is about 120 ° C., and the rising temperature of the melting peak is about 230 ° C. Accordingly, when the polyethylene terephthalate sheet is uniaxially stretched, it is preferably uniaxially stretched at about 120 to about 230 ° C.

  The stretching ratio of the uniaxial stretching is not particularly limited, but 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. 1.1-3 times are preferable, More preferably, it is 1.2-2 times. Moreover, the total draw ratio of primary stretching and uniaxial stretching is preferably 2.5 to 10 times for the same reason.

  Furthermore, it is preferable to heat-set in order to improve the heat resistance of the uniaxially stretched stretched thermoplastic polyester resin sheet.

  If the heat setting temperature is lower than the uniaxial stretching temperature, the crystallization of the thermoplastic polyester resin does not proceed, so the heat resistance is not improved, and the thermoplastic polyester system in the differential operation calorimetric curve measured at a heating rate of 1 ° C./min. If the temperature rises above the rise temperature of the melting peak of the resin, the thermoplastic polyester resin dissolves and the stretching (orientation) disappears, and the tensile elastic modulus, tensile strength, etc. decrease. The rising temperature of the melting peak of the thermoplastic polyester resin in the measured differential operation calorimetric curve is preferred.

  In addition, when heat-fixed, the stretched thermoplastic polyester resin sheet is stretched if a load is applied, and contracts in a free state. Therefore, the stretched thermoplastic polyester resin sheet is not loaded but is shrunk by heat. It is preferable to carry out in the state fixed so that it may not carry out, and it is preferable that the stretched thermoplastic polyester-type resin sheet is not pressurized. For example, it is preferable to heat-set in a state where both ends of the stretched thermoplastic polyester resin sheet are held with a pinch roll or the like so as not to be loaded. Therefore, heating is preferably performed with hot air, a heater, or the like.

  The time for heat setting is not particularly limited, and is generally 10 seconds to 5 minutes, although it varies depending on the thickness of the stretched thermoplastic polyester resin sheet and the heat setting temperature.

  The stretched thermoplastic polyester resin sheet produced by the method for producing a stretched thermoplastic polyester resin sheet of the present invention is excellent in tensile strength, tensile elastic modulus, and heat resistance. Preferably used.

  The stretched thermoplastic polyester resin sheet may be used by being laminated, or other unstretched thermoplastic polyester resin sheet, stretched polyolefin resin sheet, polyolefin resin, vinyl chloride resin, You may laminate | stack with thermoplastic resin sheets, such as ABS resin, AES resin, AS resin, and acrylate resin.

  The structure of the method for producing the stretched thermoplastic polyester resin sheet of the present invention is as described above, and the drawn stretched thermoplastic polyester resin sheet is supplied to the uniaxial stretching step and uniaxially stretched without sagging (meandering). The drawn stretched thermoplastic polyester resin sheet is uniaxially stretched without meandering, and a stretched thermoplastic polyester resin sheet excellent in tensile strength, tensile elastic modulus, and heat resistance can be obtained efficiently. Moreover, the stretched thermoplastic polyester resin sheet heat-fixed after uniaxial stretching is further excellent in heat resistance.

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

  In the figure, 1 is a supply roll for a thermoplastic polyester resin sheet, 3 is a brake roll, 4 is a preheating device, 5 is a drawing roll, and 8 is a drive roll.

  The thermoplastic polyester resin sheet 2 wound around the supply roll 1 is pulled by the drive roll 8 while being braked by the brake roll 3, heated to a predetermined temperature by the preheating device 4, and then the predetermined temperature is reached. The pair of drawing rolls 5 that have been set is drawn out to obtain a drawn stretched thermoplastic polyester resin sheet 6.

  An inclined roll 7 is installed between the drawing roll 5 and the driving roll 8, and a position measuring device 9 is installed on information between the drawing roll 5 and the inclined roll 7. The inclined roll 7 is installed below the drawing-drawn thermoplastic polyester resin sheet 6 in FIG. 1, and the shafts at both ends of the roll are independently moved in the direction of travel of the drawing-drawn thermoplastic polyester resin sheet 6 (right direction in the figure). ) Is held freely. Further, the shafts at both ends of the position measuring device 9 and the inclined roll 7 are independently connected to a control device (not shown), and the deflection (displacement) of the drawn stretched thermoplastic polyester resin sheet 6 is positioned. The tilting roll 7 is moved by the data measured by the measuring device 9 and the deflection of the drawing stretched thermoplastic polyester resin sheet 6 pressed by the tilting roll 7 is removed.

  That is, the pultruded drawn stretched thermoplastic polyester resin sheet 6 is bent as shown by a broken line in FIG. (Slip) occurs, and the drawn stretched thermoplastic polyester resin sheet 6 is pressed in the advancing direction by the inclined roll 7 to remove sagging (slack), and the drawn stretched thermoplastic polyester resin sheet as shown by the solid line. The traveling direction of 6 is controlled to be parallel to the traveling direction.

  In the figure, reference numeral 10 denotes a heating furnace for uniaxial stretching, and a plurality of stretching rolls 11 are installed in the heating furnace 10. A cooling roll 12, a driving roll 13, and a winder 15 are installed on the outlet side of the heating furnace 10.

  The drawn stretched thermoplastic polyester resin sheet 6 from which slack has been removed is supplied to a heating furnace 10 and heated and stretched by stretching rolls 11, 11. The stretched thermoplastic polyester resin sheet 14 that has been stretched is pulled by the drive roll 13, discharged from the outlet of the heating furnace 10, cooled by the cooling roll 12, and wound by the winder 15.

Example 1
A polyethylene terephthalate sheet (made by Teijin Chemicals, trade name “A-PET sheet FR”) 2 having a thickness of 2 mm and a width of 200 mm is supplied to the stretching device, preheated to 75 ° C. by the preheating device 4, and then heated to 80 ° C. The pair of heated drawing rolls (roll interval 0.2 mm) is drawn and drawn by setting the speed of the driving roll 8 to 2 m / min, and then the surface temperature of the polyethylene terephthalate sheet is set to 170 in the heating furnace 10. The film was heated to ° C., and the speed of the driving roll 13 was set to 2.5 m / min and roll-stretched to obtain a stretched polyethylene terephthalate sheet having a stretch ratio of 5 times (± 0.2 times).

  At this time, when the drawn and stretched polyethylene terephthalate sheet 6 was stretched with tension by the inclined roll 7, the meandering level was stable within ± 5 mm.

  The polyethylene terephthalate sheet has a glass transition temperature of 72 ° C., a rising temperature of a crystallization peak in a differential operating calorimetry curve measured at a heating rate of 1 ° C./min, about 118 ° C., and a rising temperature of a melting peak is about It was 230 ° C.

(Comparative Example 1)
When a stretched polyethylene terephthalate sheet was obtained in the same manner as in Example 1 except that the inclined roll 7 was not used, the drawn stretched polyethylene terephthalate sheet 6 meandered by 50 mm or more, and stretching was difficult.

It is explanatory drawing which shows an example of the manufacturing method of the extending | stretching thermoplastic polyester-type resin sheet of this invention. It is a top view which shows the state of a drawing extending | stretching thermoplastic polyester-type resin sheet.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Supply roll of thermoplastic polyester-type resin sheet 2 Thermoplastic polyester-type resin sheet 3 Brake roll 4 Preheating apparatus 5 Drawing roll 6 Drawing drawing thermoplastic polyester-type resin sheet 7 Inclination roll 8 Drive roll 9 Heating furnace 10 Position measuring apparatus 11 Stretch roll 12 Cooling roll 13 Drive roll 14 Stretched thermoplastic polyester resin sheet 15 Winder

Claims (8)

  The amorphous thermoplastic polyester resin sheet in an amorphous state is pulled with a drive roll, and a pair of drawing rolls is drawn to produce a drawn stretched thermoplastic polyester resin sheet. Subsequently, the drawn stretched thermoplastic polyester resin sheet is continuously drawn. In the method for producing a stretched thermoplastic polyester resin sheet that is uniaxially stretched, after the slack of the stretched stretched thermoplastic polyester resin sheet is removed by pressing an inclined roll on the stretched stretched thermoplastic polyester resin sheet, uniaxial stretching is performed. A method for producing a stretched thermoplastic polyester resin sheet, which is characterized.   Drawing and drawing are performed by pulling an amorphous thermoplastic polyester resin sheet with a driving roll, and a pair of glass transition temperature of the thermoplastic polyester resin −20 ° C. to glass transition temperature of the thermoplastic polyester resin + 20 ° C. The method for producing a stretched thermoplastic polyester resin sheet according to claim 1, wherein the stretched method is a stretching method in which the sheet is drawn through a plurality of drawing rolls.   After drawing and drawing, the amorphous polyester resin sheet in an amorphous state is pulled with a drive roll and heated to a temperature equal to or higher than the glass transition temperature of the thermoplastic polyester resin, and then less than the glass transition temperature of the thermoplastic polyester resin. The method for producing a stretched thermoplastic polyester resin sheet according to claim 1, wherein the stretched thermoplastic polyester resin sheet is drawn through a pair of drawing rolls having a glass transition temperature of −20 ° C. or higher.   The method for producing a stretched thermoplastic polyester resin sheet according to claim 2 or 3, wherein the stretch is uniaxially stretched at a temperature higher than the temperature of the pair of drawing rolls.   The uniaxial stretching temperature is from a rising temperature of a crystallization peak of a thermoplastic polyester resin to a rising temperature of a melting peak in a differential operation calorie curve measured at a heating rate of 1 ° C / min. Method for producing a stretched thermoplastic polyester resin sheet.   The method for producing a stretched thermoplastic polyester resin sheet according to any one of claims 1 to 5, wherein the stretched thermoplastic polyester resin sheet that has been uniaxially stretched is heat-set at a temperature higher than the uniaxial stretching temperature.   The heat of stretching according to claim 6, wherein the heat setting temperature is a rising temperature of a melting peak of the thermoplastic polyester resin in a differential operation calorimetric curve measured at a uniaxial stretching temperature to a heating rate of 1 ° C./min. A method for producing a plastic polyester resin sheet.   The method for producing a stretched thermoplastic polyester resin sheet according to claim 6 or 7, wherein the heat setting is performed in a state where the stretched thermoplastic polyester resin sheet that has been uniaxially stretched is fixed so as not to shrink by heat.

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