JP4886314B2 - Method for producing stretched thermoplastic polyester resin sheet having recess and method for producing laminated sheet - Google Patents

Description

The present invention relates to a stretched thermoplastic polyester resin sheet excellent in tensile strength, tensile elastic modulus and heat resistance, and a method for producing a laminated sheet that can be suitably used as an exterior building material using the same.

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 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.

  On the other hand, vinyl chloride resin is widely used as a material for building members because it is excellent in water resistance, flame retardancy, mechanical properties, and the like, and is relatively inexpensive. For example, rain gutters are generally formed by extrusion of a hard vinyl chloride resin.

However, the linear expansion coefficient of hard vinyl chloride resin molding is as large as 7.0 × 10 ^-5 (1 / ° C), so when installing a hard vinyl chloride resin gutter, It was necessary to connect with a joint that can absorb, or to make the end free, but when the length of the rain gutter to be constructed was increased, there was a disadvantage that the joints and outlets increased and the appearance was bad .

For this reason, various studies have been made on rain gutters having a low linear expansion coefficient. For example, it consists of a vinyl chloride resin composition in which 20 to 35 parts by weight of mica, 20 to 40 parts by weight of calcium carbonate, and 5 to 15 parts by weight of processing aids are added to 100 parts by weight of vinyl chloride resin. A rain gutter made of vinyl chloride resin (see, for example, Patent Document 2) is proposed.
Japanese Patent No. 2905260

  The above gutters are made of vinyl chloride resin with mica and calcium carbonate added to lower the linear expansion coefficient of gutters, but are mainly made of vinyl chloride resin, and the amount of mica and calcium carbonate added is low. If the amount is small, the linear expansion coefficient is still high, and if the amount added is large, the impact resistance and durability of the rain gutter are lowered.

In addition, rain gutters impregnated with glass fiber as a reinforcing material or laminated with metal thin plates have been proposed. For example, a composite sheet composed of a thermoplastic resin and reinforcing fibers is shaped to the required cross-sectional shape, and the thermoplastic resin is extrusion-coated on the surface, and the composite sheet is reinforced at least on the shaped part. A composite molded product characterized in that short fibers are randomly oriented (see, for example, Patent Document 3), a metal thin plate as a core material, and a synthetic resin is coated on both surfaces of the core material to form a sheet material, In the rain gutter formed by pressing the bending jig distal end against the sheet material to be bent into a substantially U-shaped cross section, the bending jig distal end is located at the bending position of the synthetic resin on the inner surface side. A rain gutter (see, for example, Patent Document 4) characterized by providing a groove to be guided has been proposed.
Japanese Patent Laid-Open No. 11-19998 Japanese Patent Laid-Open No. 9-297883

  However, the former gutter consists of a thermoplastic resin and reinforcing fibers. A composite sheet in which short fibers are randomly oriented must be created and shaped into the required cross-sectional shape, and then the thermoplastic resin must be extrusion coated on the surface. It was difficult to manufacture, and there was a problem when it was discarded.

  The latter rain gutter is laminated with a thin metal plate as a core material, so that it is heavy and difficult to cut, and the metal thin plate is exposed at the end of the gutter, and rust is generated over time. In addition, there is a drawback that durability is lowered by corrosion.

Further, as a rain gutter having a low linear expansion coefficient without using a core material or glass fiber made of a thin metal plate, for example, an average linear expansion coefficient of 20 to 80 ° C. is 5 × 10 ⁻⁵ (1 / ° C.) or less. The low molecular weight compound that dissolves the polyolefin was adhered to the surface of the stretched polyolefin material, and then the polyolefin stretched material was adhered by pressing and heating, and the average linear expansion coefficient at 20 to 80 ° C. was 5 × 10 ⁻⁵ ( 1 / ° C.) or less polyolefin molded body (see, for example, Patent Document 5), after extruding a thermoplastic resin, the extruded product is further stretched and stretched to orient the molecules in one direction. A synthetic resin rain gutter characterized in that the linear expansion coefficient of the thermoplastic synthetic resin is 6 × 10 ⁻⁵ / ° C. or less and the thickness is greater than 0.5 mm has been proposed (for example, see Patent Document 6). Yes.
JP-A-10-291250 Japanese Patent Laid-Open No. 2002-285685

  However, the former rain gutter is a sheet obtained by highly stretching a polyolefin stretched material 20 to 40 times, and has a disadvantage that it is easily broken along the stretch direction and has poor impact resistance. When trying to laminate with vinyl resin, AES resin or the like, polyolefin has a lower melting point than these resins, so that the stretched state of the polyolefin collapses and the linear expansion coefficient becomes high.

  Further, since the latter rain gutter is simply a stretched gutter that has been stretched, it has the disadvantage of being easily broken along the stretch direction and having poor impact resistance.

  As a result of various investigations on materials that can eliminate these drawbacks, it was found that stretched thermoplastic polyester resin sheets that were drawn and stretched under specific conditions and then uniaxially stretched have excellent tensile strength, tensile modulus, heat resistance, and the like. It was. However, the adhesiveness between the stretched thermoplastic polyester resin sheet and the thermoplastic resin is low, and a strongly bonded laminated sheet could not be obtained.

An object of the present invention is to provide a method for producing a stretched thermoplastic polyester resin sheet excellent in adhesiveness with a thermoplastic resin, tensile strength, tensile elastic modulus, and heat resistance in view of the above-described drawbacks.
A different object of the present invention is to use the stretched thermoplastic polyester resin sheet, a method for producing a laminated sheet having a low coefficient of linear expansion, light weight, excellent impact resistance, durability, workability, productivity, etc. In particular, it is to provide a method for producing a laminated sheet that can be suitably used as an exterior building material such as rain gutter.

The method for producing a stretched thermoplastic polyester resin sheet according to claim 1, wherein the thermoplastic polyester resin sheet in an amorphous state is obtained from a glass transition temperature of the thermoplastic polyester resin of −20 ° C. to that of the thermoplastic polyester resin. After drawing through a pair of rolls having a glass transition temperature of + 20 ° C. and drawing and drawing, a recess is formed in at least one surface of a stretched thermoplastic polyester resin sheet uniaxially stretched at a temperature higher than the temperature of the roll. It is a manufacturing method of the extending | stretching thermoplastic polyester-type resin sheet which has a recessed part made.

  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.

  If the intrinsic viscosity of the thermoplastic polyester-based resin is too low, drawdown is likely to occur at the time of forming the sheet, and if it is too high, the mechanical strength (particularly the elastic modulus) does not increase even when stretched. 0 is preferred.

  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.

  The thermoplastic polyester resin sheet is in an amorphous state. The thermoplastic polyester resin sheet may be in an amorphous state, and the crystallinity thereof is not particularly limited, but the crystallinity measured by a differential scanning calorimeter is preferably less than 10%, more preferably. Is less than 5%.

  In the present invention, the thermoplastic polyester resin sheet in an amorphous state is drawn through a pair of rolls and drawn and stretched. The temperature of the thermoplastic polyester resin sheet during drawing and drawing is not particularly limited, but is preferably heated to a temperature in the vicinity of the glass transition temperature.

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

  Further, when the amorphous polyester resin sheet in the amorphous state is pulled out, the roll does not necessarily rotate, but may be slightly rotated in the drawing direction in order to make the temperature distribution uniform.

  If the rotation speed of the roll is slow, the thermoplastic polyester resin sheet is rubbed on the roll, frictional heat is generated, the roll temperature rises, and the effect of cooling the heated thermoplastic polyester resin decreases, conversely When the rotation 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, and the elastic modulus of the obtained drawn and drawn thermoplastic polyester resin sheet decreases. To do.

  Therefore, the rotation speed of the roll is preferably substantially the same or lower than the drawing speed of the thermoplastic polyester resin sheet, more preferably 50 to 100% of the drawing speed of the thermoplastic polyester resin sheet. .

  In addition, when the thickness of the thermoplastic polyester resin sheet is large, the cooling effect by the roll is reduced, so the rotation speed of the roll is preferably substantially the same as the drawing speed of the thermoplastic polyester resin sheet. When the thickness of the plastic polyester resin sheet is thin, the roll rotating speed may be slow because the cooling effect by the roll is large.

  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 the present invention, the drawn and stretched thermoplastic polyester resin sheet is uniaxially stretched at a temperature higher than the temperature of the roll.

  The polyester resin of the thermoplastic polyester resin sheet that has been drawn and stretched is highly oriented because molecular chains are highly oriented in a state in which isotropic crystallization and orientation due to heat, which is an impediment to stretching, are suppressed. Although the elastic modulus is excellent, since the degree of crystallinity is low, there is a disadvantage that the orientation is easily relaxed and the elastic modulus is lowered when heated.

  However, the uniaxial stretching of the drawn and stretched thermoplastic polyester resin sheet at a temperature higher than the temperature of the roll increases the crystallinity without relaxing the orientation, and the orientation is easy even when heated. A stretched sheet with excellent heat resistance that is not relaxed is 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 a temperature higher than the temperature of the pair of rolls at the time of drawing and stretching, but if it is too high, the drawn and stretched thermoplastic polyester resin sheet is melted and cut. A 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 scanning calorimetry curve measured at a heating rate of 10 ° 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 ° C 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 drawing drawing and uniaxial drawing is preferably 2.5 to 10 times for the same reason.

  The uniaxially stretched stretched thermoplastic polyester resin sheet is preferably heat-set in order to improve heat resistance.

  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 does not improve, and the thermoplastic polyester system in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min. When 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 modulus, tensile strength, etc. decrease, so the uniaxial stretching temperature to the heating rate of 10 ° C./min. The rising temperature of the melting peak of the thermoplastic polyester resin in the measured differential scanning calorimetry curve is preferable.

  Further, when heat-fixing, the stretched thermoplastic polyester resin sheet is stretched if a large tension is applied, and is not tensioned or shrinks in a very small state. It is preferable that the length is not substantially changed, and it is preferable that no pressure is applied to the stretched thermoplastic polyester resin sheet.

  That is, it is preferable to heat-set so that the length of the stretched thermoplastic polyester resin sheet that has been heat-set is 0.95 to 1.1 of the length of the stretched thermoplastic polyester-based resin sheet before heat setting. .

  Therefore, when the stretched thermoplastic polyester resin sheet is heat-set continuously while moving in the heating chamber with a roll such as a pinch roll, the feed rate ratio of the stretched thermoplastic polyester resin sheet on the inlet side and the outlet side is set to 0. It is preferable that the temperature is set to be .95 to 1.1 and heat fixed.

  Moreover, when heat-fixing a short sheet, it is preferable to fix both ends in a state where no load is applied.

  The heating method at the time of heat setting is not particularly limited, and examples thereof include a method of heating with hot air or a heater.

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

  Furthermore, the stretched thermoplastic polyester-based resin sheet that has been heat-fixed has a range of rising temperature of the crystallization peak of the thermoplastic polyester-based resin in a differential scanning calorimetry curve measured at a glass transition temperature to a temperature rising rate of 10 ° C./min. Thus, it is preferable that the annealing is performed in a state where substantially no tension is applied.

  By annealing, the stretched thermoplastic polyester resin sheet has good mechanical properties such as elastic modulus, and even if it is heated to a temperature higher than the glass transition temperature, the mechanical properties such as elastic modulus may decrease. And the shrinkage rate can be kept low.

  In addition, since the stretched thermoplastic polyester resin sheet is stretched when a large tension is applied thereto, it is preferable to anneal the stretched thermoplastic polyester resin sheet in a state where no tension is applied to the stretched thermoplastic polyester resin sheet.

  That is, it is preferable to anneal so that the length of the annealed stretched thermoplastic polyester resin sheet is 1.0 or less of the length of the stretched thermoplastic polyester resin sheet before annealing.

  Therefore, when the stretched thermoplastic polyester resin sheet is continuously annealed while being moved in a heating chamber by a roll such as a pinch roll, the feed rate ratio of the stretched thermoplastic polyester resin sheet on the inlet side and the outlet side is set to 1. It is preferable to anneal by setting it to be 0 or less.

  Further, when annealing the short sheet, it is preferable to open both ends so that no load is applied.

  The heating method at the time of annealing is not particularly limited, and examples thereof include a method of heating with hot air or a heater.

  The time for annealing is not particularly limited and varies depending on the thickness of the stretched thermoplastic polyester resin sheet and the annealing temperature, but is generally preferably 10 seconds or more, more preferably 30 seconds to 5 minutes, and still more preferably 1-2. Minutes.

In the present invention , a recess is formed in at least one surface of the stretched thermoplastic polyester resin sheet . Needless to say, the concave portions may be formed on both sides of the stretched thermoplastic polyester resin sheet.

  The shape of the recess is not particularly limited, and examples of the surface shape include a circle, an ellipse, a bowl, a triangle, a quadrangle, a pentagon, a hexagon, a heptagon, an octagon, and a star. The shape may be a groove or a specific shape as shown in FIG.

  Also, the shape in the thickness direction is not particularly limited, for example, a cylindrical shape having substantially the same cross-sectional shape, a shape having a tapered portion so that the cross-sectional area as shown in FIG. As shown in FIG. 3, the shape etc. which have a reverse taper part so that a cross-sectional area may become large gradually are mentioned.

  If the depth of the recess is shallow, the effect of improving the adhesive force between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer tends to decrease. If the depth is too deep, the mechanical strength of the stretched thermoplastic polyester resin sheet decreases. Since there is a tendency, 1/3 to 2/3 of the thickness of the stretched thermoplastic polyester resin sheet is preferable.

  Also, if the width of the recess is too narrow, the thermoplastic resin is less likely to invade and the effect of improving the adhesive force between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer tends to be reduced. There is a tendency that the effect of invading and biting into the stretched thermoplastic polyester resin sheet tends to decrease, and the effect of improving the adhesive force between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer tends to decrease, so 2-5 mm is preferable.

  The interval between the recesses and the recesses may be appropriately determined as necessary, but when the number of recesses decreases, the effect of improving the adhesive force between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer tends to decrease, When it increases, the mechanical strength of the stretched thermoplastic polyester resin sheet tends to decrease, so 5 to 10 mm is preferable.

  The method for drilling the recess is not particularly limited, and any conventionally known drilling method may be employed, and examples include a method of drilling with a cutting machine such as a drilling machine or a drilling machine such as a drill. .

The stretched thermoplastic polyester resin sheet of the present invention is economical because it requires a large amount of energy to produce a stretched thermoplastic polyester resin sheet having a linear expansion coefficient smaller than −1.5 × 10 ⁻⁵ / ° C. When the temperature is 0 / ° C. or higher, the linear expansion coefficient of the laminated sheet in which the thermoplastic resin layer is laminated on at least one surface of the stretched thermoplastic polyester resin sheet becomes large. The expansion coefficient is preferably −1.5 × 10 ⁻⁵ / ° C. or more and less than 0 / ° C.

  When the tensile elastic modulus of the thermoplastic polyester resin sheet is less than 8 GPa, the linear expansion coefficient of the laminated molded body in which the thermoplastic resin layers are laminated on both surfaces of the stretched thermoplastic polyester resin sheet is large. Since the impact resistance of the body is lowered, the tensile elastic modulus of the stretched thermoplastic polyester resin sheet is preferably 8 to 15 GPa.

The manufacturing method of the lamination sheet of Claim 7 is a thermoplastic resin filling a recessed part in the surface which has the recessed part of the extending | stretching thermoplastic polyester-type resin sheet which has a recessed part of any one of Claims 1-6. Thus, a thermoplastic resin layer is laminated .

  The thermoplastic resin is laminated on a stretched thermoplastic polyester resin sheet, and protects the stretched thermoplastic polyester resin sheet from being cracked or cracked along the stretch direction by impact, while the polyester resin is directly rainwater. It is intended to prevent the durability from decreasing due to hydrolysis or deterioration by exposure to sunlight.

  It is preferable to melt the thermoplastic resin and laminate it on the stretched thermoplastic polyester resin sheet. However, if the melting point of the thermoplastic resin is higher than the melting point of the thermoplastic polyester resin, the stretched thermoplastic polyester resin sheet crystals relax. Since the coefficient of linear expansion is high, the thermoplastic resin is preferably a resin having a lower melting point than the thermoplastic polyester resin.

  Examples of the thermoplastic resin include hard vinyl chloride resin, chlorinated vinyl chloride resin, chlorinated polyethylene resin, ABS resin, AES resin, styrene resin, AS resin, methyl methacrylate resin, ethylene resin, and polypropylene resin. .

  The thickness of the thermoplastic resin is not particularly limited and may be appropriately determined depending on the application. However, if the thickness is too thin, the protective effect is reduced, and if the thickness is increased, the thermoplastic resin becomes heavy and low linear expansion of the stretched thermoplastic polyester resin sheet. Since the effect of the coefficient is reduced, 0.1 to 3 mm is preferable.

  The method for laminating the thermoplastic resin layer on the stretched thermoplastic polyester resin sheet is not particularly limited, and any conventionally known laminating method may be adopted, but the stretched thermoplastic polyester resin sheet has a concave surface. A method of laminating the thermoplastic resin in the concave portion by applying a molten thermoplastic resin and laminating the thermoplastic resin layer is preferable.

The manufacturing method of the lamination sheet of Claim 9 is laminated | stacked so that a recessed part may be filled in the surface which has a recessed part of the extending | stretching thermoplastic polyester-type resin sheet which has a recessed part of any one of Claims 1-6. A thermoplastic resin layer is laminated through the adhesive layer.

  As the adhesive, any conventionally known adhesive can be used, for example, from the group consisting of a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive. One type or two or more types of selected liquid adhesives can be used.

  When laminating with a liquid adhesive, a liquid adhesive is applied and laminated on the surface of the stretched thermoplastic polyester resin sheet having a recess so as to fill the recess, and a thermoplastic resin layer is laminated and adhered thereon.

  A hot melt adhesive can also be suitably used as the adhesive. As the hot melt adhesive, hot melt adhesives such as polyester, polyolefin, and polyurethane having a melting point lower than that of the thermoplastic polyester resin can be suitably used.

  The method of adhesive lamination with a hot melt adhesive is not particularly limited, and any conventionally known method may be employed. For example, it is melted on the surface of the stretched thermoplastic polyester resin sheet having a recess. And a method of extruding the hot melt adhesive, filling the recesses with the hot melt adhesive, laminating a hot melt adhesive layer, and laminating a thermoplastic resin layer thereon.

  In addition, a hot melt adhesive layer and a thermoplastic resin layer are sequentially laminated on the surface of the stretched thermoplastic polyester resin sheet having a recess, and the hot melt adhesive is melted by heating and pressurizing. The stretched thermoplastic polyester-based resin sheet and the thermoplastic resin layer may be bonded and laminated by allowing an adhesive to enter the recess.

  As the heating and pressing method, an ultrasonic welder is preferable. As a method of fusing with the ultrasonic welder, any conventionally known method may be employed. For example, the stretched thermoplastic polyester resin sheet, the hot melt adhesive, and the thermoplastic resin layer are laminated, and 15 There is a method of passing between a horn and a knurl which are vibrated at a frequency of ˜40 kHz.

  FIG. 4 is an explanatory view showing an example of a method using an ultrasonic welder. In the figure, reference numeral 1 denotes a stretched thermoplastic polyester resin sheet. A hot melt adhesive sheet 2 is laminated on the surface of the stretched thermoplastic polyester resin sheet 1 having a recess, and a thermoplastic resin layer 3 is further formed thereon. A laminated body 10 is formed by being laminated.

  The laminate 10 is transported while being pressed by the horn 4 and the knurl 5, and is excited by the frictional heat generated by the ultrasonic vibration transmitted from the horn 4 by exciting the horn 4 at a frequency of 15 to 40 kHz. The melt-type adhesive sheet 2 is heated and melted to bond the stretched thermoplastic polyester resin sheet 1 and the thermoplastic resin layer 3 to obtain a laminated sheet 11.

  At this time, the distance between the horn 4 and the knurl 5 is set to be narrower than the thickness of the laminate 10, and the laminate 10 is fused while being pressed by the horn 4 and the knurl 5. In order to pressurize, an air cylinder, a hydraulic cylinder, etc. may be connected to the horn 4 and the horn 4 may be pressed against the knurl 5 via the laminate 10.

  In addition, protrusions (not shown) are formed on the surface of the knurl 5 so that fusion can be performed more efficiently. By changing the arrangement and shape of the protrusions, the arrangement of the fusion parts and the pattern of the shape are changed. can do.

  Further, when fusing with an ultrasonic welder, in order to prevent the orientation state of the stretched thermoplastic polyester resin sheet 1 from being relaxed, tension is applied to the laminate 10 (stretched thermoplastic polyester resin sheet 1). Is preferably loaded.

  The laminated sheet can be formed into a predetermined shape by a forming method such as profile molding or bending, and a laminated molded sheet having a predetermined shape is obtained. In order to improve the weather resistance and design properties of the laminated molded sheet, a different resin layer may be laminated on the surface of the thermoplastic resin layer, or a paint may be applied.

  The laminated sheet of the present invention is suitably used as an exterior building material, particularly as a rain gutter.

  The structure of the manufacturing method of the extending | stretching thermoplastic polyester-type resin sheet of this invention is as the above-mentioned, and the extending | stretching thermoplastic polyester-type resin sheet obtained is excellent in tensile strength, a tensile elasticity modulus, and heat resistance. In particular, a stretched thermoplastic polyester resin sheet that has been heat-fixed after uniaxial stretching and a stretched thermoplastic polyester resin sheet that has been annealed are more excellent in heat resistance.

In addition, the method for producing the laminated sheet of the present invention is as described above, and the obtained laminated sheet has a low linear expansion coefficient and a light weight because a thermoplastic resin is laminated on the stretched thermoplastic polyester resin sheet. Excellent impact resistance, durability, workability, productivity, etc. Therefore, it can be suitably used as an exterior building material such as a rain gutter.

  Next, examples of the present invention will be described, but the present invention is not limited to the following examples.

Example 1
A polyethylene terephthalate sheet having a crystallinity of 1.3% and a thickness of 2.5 mm obtained by rapidly cooling polyethylene terephthalate (manufactured by Unitika, trade name “NEH-2070”, intrinsic viscosity 0.88) after melt extrusion molding is obtained. After feeding to a stretching device (manufactured by Kyowa Engineering Co., Ltd.) and preheating to 80 ° C., a pair of rolls (roll interval 0.6 mm) heated to 74 ° C. is drawn at a speed of 2 m / min, and drawn and stretched. The polyethylene terephthalate sheet surface temperature is heated to 180 ° C. in a hot air heating tank, the outlet speed is set to 2.5 m / min, and the roll is uniaxially stretched. The stretched polyethylene has a stretch ratio of about 5 times and a thickness of 0.6 mm. A terephthalate sheet was obtained.

  The polyethylene terephthalate sheet has a glass transition temperature of 76.7 ° C., a rising temperature of the crystallization peak in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min, 139.8 ° C., and a rising temperature of the melting peak. The temperature was 234 ° C.

  A number of cylindrical recesses were drilled on both sides of the obtained stretched polyethylene terephthalate sheet with a drill. The diameter of the recess was 3 mm, the depth was 0.4 mm, the stretching direction was drilled at intervals of 10 mm, and the direction perpendicular to the stretching direction was drilled at intervals of 5 mm. In addition, the recesses on one surface and the recesses on the other surface were drilled so as to be located between the respective recesses.

  A polyurethane-based hot melt adhesive (product name “Sdyne 9615W” manufactured by Sekisui Fuller Co., Ltd.) was melted at 120 ° C. on both sides of the stretched polyethylene terephthalate sheet having the recesses formed therein, and 0 with a reverse coater (manufactured by Matsushita Kogyo Co., Ltd.). It was applied to a thickness of 0.04 mm, cured at 40 ° C., and moisture-cured until the polyurethane-based hot melt adhesive did not melt at 200 ° C. to obtain an adhesive laminated stretched polyethylene terephthalate sheet. In addition, the polyurethane hot-melt adhesive penetrated into each recess and was buried.

  A vinyl chloride resin (“TS1000R”, manufactured by Tokuyama Sekisui Co., Ltd.) was extrusion coated at 200 ° C. on both sides of the obtained adhesive laminated stretched polyethylene terephthalate sheet, and a vinyl chloride resin layer having a thickness of 0.4 mm was laminated on both sides. A laminated sheet was obtained.

(Example 2)
A polyester hot melt adhesive (product name: Byron GM-913, manufactured by Toyobo Co., Ltd.) melted and molded on both sides of the stretched polyethylene terephthalate sheet having the recesses obtained in Example 1, and a thickness of 0. A 0.4 mm thick vinyl chloride resin sheet obtained by melting and molding a 04 mm hot melt adhesive sheet and a vinyl chloride resin (“TS1000R” manufactured by Tokuyama Sekisui Co., Ltd.) was pressed with a press at 200 ° C. for 30 seconds, A laminated sheet having a vinyl chloride resin layer laminated on both sides was obtained. In addition, when the vinyl chloride resin layer of the obtained laminated sheet was peeled off and visually observed, a polyester-based hot-melt adhesive entered and was buried in each recess.

(Comparative Example 1)
A polyurethane-based hot melt adhesive was laminated on both sides of the stretched polyethylene terephthalate sheet obtained in Example 1 in the same manner as in Example 1, and then a vinyl chloride resin was extrusion coated, and a vinyl chloride resin layer on both sides. Was obtained.

(Comparative Example 2)
A polyester hot melt adhesive sheet and a vinyl chloride resin sheet are laminated and pressed on both sides of the stretched polyethylene terephthalate sheet obtained in Example 1 in the same manner as in Example 2 , and a vinyl chloride resin layer is formed on both sides. A laminated sheet was obtained.

  The physical properties of the obtained stretched polyethylene terephthalate sheet, the stretched polyethylene terephthalate sheet having a recess and a laminated sheet were evaluated by the following evaluation methods. Table 1 shows the tensile strength, tensile elastic modulus, and linear expansion coefficient of the stretched polyethylene terephthalate sheet and the stretched polyethylene terephthalate sheet having the recesses. Table 2 shows the tensile strength, tensile elastic modulus, linear expansion coefficient, Charpy impact value, and peel strength of the laminated sheet.

(1) Tensile strength, tensile modulus Measured according to the tensile test method of JIS K 7113.
(2) Linear expansion coefficient The obtained stretched polyethylene terephthalate sheet was measured based on JIS K7197.

(3) Charpy impact value A length of 80 mm and a width of 10 mm (the width direction is the stretched direction of the stretched polyethylene terephthalate sheet) are cut out from the obtained laminated molded body and processed into a V-notch (depth 2 mm) to obtain JIS K-7111. The Charpy impact value was measured in conformity.

(4) Peel strength A test piece having a width of 25 mm was prepared, and a T-peeling test was performed at a peel rate of 100 mm / min in accordance with JIS K 6854. However, a test piece was prepared by regarding the adhesive laminated stretched polyethylene terephthalate sheet as an adhesive layer.

It is explanatory drawing which shows the example of the planar shape of a recessed part. It is explanatory drawing which shows the example of the cross-sectional shape of a recessed part. It is explanatory drawing which shows the example of the cross-sectional shape of a recessed part. It is explanatory drawing which shows an example of the method of making an extending | stretching thermoplastic polyester-type resin sheet and a thermoplastic resin layer with an ultrasonic welder with a hot-melt-type adhesive agent.

Explanation of symbols

1 Stretched thermoplastic polyester resin sheet 2 Hot melt adhesive sheet 3 Thermoplastic resin layer 4 Horn 5 Knurl 10 Laminate 11 Laminated sheet

Claims (14)

The amorphous polyester resin sheet in an amorphous state is drawn through a pair of rolls having a glass transition temperature of −20 ° C. to a glass transition temperature of the thermoplastic polyester resin + 20 ° C. After that, a method for producing a stretched thermoplastic polyester resin sheet having a recess, comprising forming a recess in at least one surface of the stretched thermoplastic polyester resin sheet uniaxially stretched at a temperature higher than the temperature of the roll. 2. The production of a stretched thermoplastic polyester resin sheet having concave portions according to claim 1, wherein the amorphous polyester resin sheet has a crystallinity of less than 10% as measured by a differential scanning calorimeter. Way . 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 scanning calorimetry curve measured at a heating rate of 10 ° C / min. 2. A method for producing a stretched thermoplastic polyester resin sheet having a recess according to 2. The method for producing a stretched thermoplastic polyester resin sheet having recesses according to any one of claims 1 to 3, wherein the stretch ratio is 3 to 8 times. The stretched thermoplastic polyester having a recess according to any one of claims 1 to 4 , wherein the depth of the recess is 1/3 to 2/3 of the thickness of the stretched thermoplastic polyester resin sheet. Of manufacturing a resin-based resin sheet . Linear expansion coefficient of -1.5 × 10 ^-5 / ° C. or more, 0 / less than ° C., a tensile modulus according to claim 1, characterized in that the 8~15GPa The manufacturing method of the extending | stretching thermoplastic polyester-type resin sheet which has a recessed part. A thermoplastic resin layer is laminated on the surface of the stretched thermoplastic polyester resin sheet having a recess according to any one of claims 1 to 6 so that the thermoplastic resin fills the recess. A method for manufacturing a laminated sheet . The method for producing a laminated sheet according to claim 7 , wherein the thermoplastic resin layer is laminated by applying a molten thermoplastic resin to a surface of the stretched thermoplastic polyester resin sheet having a recess. The surface having the recesses of the oriented thermoplastic polyester resin sheet having a concave portion according to any one of claims 1 to 6, through an adhesive layer laminated so as to fill the recess, a thermoplastic resin layer A method for producing a laminated sheet, characterized by laminating. Applying a liquid adhesive to the surface of the stretched thermoplastic polyester resin sheet having a recess, laminating an adhesive layer so as to fill the recess, and laminating a thermoplastic resin layer thereon Item 10. A method for producing a laminated sheet according to Item 9 . The liquid adhesive is one or more adhesives selected from the group consisting of reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives. The method for producing a laminated sheet according to claim 10 . 10. A laminated sheet according to claim 9 , wherein a hot melt adhesive and a thermoplastic resin layer are laminated on the surface of the stretched thermoplastic polyester resin sheet having a recess, and are fused while being pressed by an ultrasonic welder. Manufacturing method . 13. The method for producing a laminated sheet according to claim 12 , wherein the melting point of the hot melt adhesive is lower than the melting points of the thermoplastic polyester resin and the thermoplastic resin. The method for producing a laminated sheet according to any one of claims 7 to 13 , wherein the laminated sheet is an exterior building material.

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