JP5064895B2 - Method for producing stretched thermoplastic polyester resin sheet - Google Patents

Description

The present invention relates to a method for producing oriented thermoplastic polyester resin sheet.

  Vinyl chloride resins are widely used as materials for building members because they are excellent in water resistance, flame retardancy, mechanical properties, etc., and are 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 an absorbable joint or to make the end free. However, when the gutter length becomes longer, the joint becomes larger, the appearance is bad, and the joint part will be damaged if used for a long time. was there. In addition, the rain gutter itself has cracks and warpage due to repeated expansion and contraction, and has a drawback of low reliability when used for a long time.

Therefore, 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 vinyl chloride resin rain gutter (see, for example, Patent Document 1) 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 2), 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 3) 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 is difficult to manufacture, and there is a problem in disposal.

  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 4), after extruding a thermoplastic resin, the extruded material 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 5). 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.

In order to remedy the above drawbacks, a sheet of thermoplastic polyester resin, for example, an amorphous thermoplastic polyester resin sheet, is used, the glass transition temperature of the thermoplastic polyester resin −20 ° C. to the thermoplastic polyester resin After drawing and stretching between a pair of rolls having a glass transition temperature of + 20 ° C., the linear expansion coefficient obtained by uniaxial stretching at a temperature higher than the temperature of the roll is −1.5 × 10 ⁻⁵ or more and less than 0. There is proposed a laminated molded body (see, for example, Patent Document 5) in which a thermoplastic resin layer is laminated on both surfaces of a thermoplastic polyester resin sheet having a tensile elastic modulus of 8 to 15 GPa. .
JP 2006-306002 A

  The above-mentioned thermoplastic polyester resin sheet and the laminate molded body in which the thermoplastic resin layers are laminated on both sides thereof have a low linear expansion coefficient, light weight, excellent impact resistance, durability, workability, productivity, etc. However, it was still easy to break during secondary processing, and bending was difficult.

In view of the above-mentioned drawbacks, the object of the present invention is a low coefficient of linear expansion, light weight, excellent impact resistance, durability, workability, productivity, etc., and excellent bending workability to prevent cracking during secondary processing. It is providing the manufacturing method of a thermoplastic polyester-type resin sheet .

The method for producing a stretched thermoplastic polyester resin sheet according to claim 1 has an elastic modulus in the stretching direction of 9 GPa or more measured in accordance with a tensile test method of JIS K 7113, and an elongation at break perpendicular to the stretching direction. Is a stretched thermoplastic polyester resin sheet having a glass transition temperature of −20 ° C. to the heat of the thermoplastic polyester resin. A differential measured by drawing at a glass transition temperature of the plastic polyester resin + 20 ° C., and measuring the temperature at a temperature rising rate of 10 ° C./min while fixing the length of the obtained drawn drawn thermoplastic polyester resin sheet in the drawing direction. The sample was heat-fixed at the rising temperature of the crystallization peak of the thermoplastic polyester resin on the scanning calorimetry curve to the rising temperature of the melting peak, Of the peak of the rising temperature or higher, characterized by annealing at a temperature below the heat setting temperature.

  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.

  In addition, if the intrinsic viscosity of the thermoplastic polyester resin is too low, it tends to cause drawdown at the time of producing the sheet, and if it is too high, the mechanical strength (particularly the elastic modulus) does not increase even when stretched. .6 to 1.0 is preferred.

  The elastic modulus of the stretched thermoplastic polyester resin sheet is an elastic modulus when a tensile test is performed in the stretching direction in accordance with the tensile test method of JIS K 7113, and is 9 GPa or more. When the elastic modulus in the stretching direction is less than 9 GPa, the mechanical strength is lowered and the linear expansion coefficient is lowered, so that it is limited to 9 GPa or more. The elongation at break of the stretched thermoplastic polyester resin sheet is based on the tensile test method of JIS K 7113, and is the elongation at break when a tensile test is performed in the direction perpendicular to the stretch direction. Therefore, it is limited to 3.5% or more.

  The stretch ratio of the stretched thermoplastic polyester resin sheet is not particularly limited, but if the stretch ratio is low, the tensile strength, the tensile elastic modulus, etc. tend to decrease. Since it tends to occur, it is preferably 2.5 to 10 times, more preferably 3 to 8 times.

A thermoplastic resin layer may be laminated on at least one surface of the stretched thermoplastic polyester resin sheet to form a laminated sheet .

  The thermoplastic resin layer is laminated on at least one surface of the stretched thermoplastic polyester resin sheet, and protects the stretched thermoplastic polyester resin sheet from cracking or cracking along the stretch direction due to impact, It is intended to prevent the resin from being directly exposed to rainwater or solar rays, resulting in hydrolysis or deterioration, resulting in a decrease in durability.

  Examples of the thermoplastic resin include vinyl chloride resin, chlorinated vinyl chloride resin, polyvinylidene fluoride resin, chlorinated polyethylene resin, ABS resin, AES resin, styrene resin, AS resin, methyl methacrylate resin, ethylene resin, and polypropylene resin. A vinyl chloride resin is preferable.

  The thickness of the thermoplastic resin layer 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 thickness becomes heavy and the stretched thermoplastic polyester resin sheet is low. Since the effect of an expansion coefficient is reduced, 0.1-3 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, and examples thereof include the following methods.
(1) A method in which a thermoplastic resin is extrusion coated on a stretched thermoplastic polyester resin sheet and laminated.
(2) A method in which a thermoplastic resin sheet is bonded to a stretched thermoplastic polyester resin sheet by hot pressing and laminated.

(3) A thermoplastic resin such as a polyester-based or polyolefin-based hot-melt adhesive having a melting point lower than the melting point of the thermoplastic polyester-based resin constituting the stretched thermoplastic polyester-based resin sheet. A method of adhering and laminating sheets.
(4) The thermoplastic resin sheet is laminated to the stretched thermoplastic polyester resin sheet with an adhesive such as a reactive adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, or a rubber adhesive. how to.

The method for producing the stretched thermoplastic polyester resin sheet is obtained by converting an amorphous thermoplastic polyester resin sheet into a glass transition temperature of the thermoplastic polyester resin of −20 ° C. to a glass transition temperature of the thermoplastic polyester resin of +20. The polyester film is drawn and drawn at a temperature of 10 ° C./min at a temperature rising rate of 10 ° C./min. It is characterized by heat setting at a rise temperature of the crystallization peak of the resin to a rise temperature of the melting peak, and then annealing at a temperature not lower than the rise temperature of the crystallization peak and lower than the heat setting temperature.

  The stretched thermoplastic polyester resin sheet is in an amorphous state. The stretched 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, it is less than 5%.

  The drawing and drawing method is not particularly limited, and the drawing and drawing may be performed through a drawing die having a predetermined clearance. However, the drawing and drawing through a pair of rolls can freely control the thickness after drawing and drawing. This is preferable because wear of a specific part of the drawing die does not occur.

  The temperature of the thermoplastic polyester resin sheet during drawing and drawing is not particularly limited, but it is preferably preheated to a temperature near the glass transition temperature. If the preheating temperature is too low or too high, the resin sheet may not reach a predetermined temperature. Therefore, the glass transition temperature of the thermoplastic polyester resin −20 ° C. to the glass transition temperature of the thermoplastic polyester resin +10 A temperature of ° C is preferred.

  If the temperature at the time of drawing and drawing is low, the thermoplastic polyester resin sheet is too hard, and even if it is to be drawn, it may be cut first. The thermoplastic polyester resin sheet becomes soft when the temperature is high, and the thermoplastic polyester resin sheet is cut by the tension that pulls out the sheet. Therefore, the glass transition temperature of the thermoplastic polyester resin − 20 ° C to the glass transition temperature of the thermoplastic polyester resin + 20 ° C, preferably the glass transition temperature of the thermoplastic polyester resin to the glass transition temperature of the thermoplastic polyester resin + 10 ° C. is there.

  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.

  Therefore, the rotational speed of the roll is preferably substantially the same or lower than the feed speed 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.

  The drawn and stretched thermoplastic polyester resin sheet may be further uniaxially stretched at a temperature higher than the drawing temperature. 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, the degree of crystallinity is low, so that when heated, the orientation is easily relaxed and the elastic modulus is lowered.

  However, uniaxial stretching of the drawn and drawn thermoplastic polyester resin sheet at a temperature higher than the drawing temperature increases the crystallinity without relaxing the orientation, and the orientation is easily relaxed even when heated. A stretched thermoplastic polyester resin sheet having excellent heat resistance that is not obtained 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.

  The temperature at the time of the uniaxial stretching may be higher than the temperature of the pair of rolls at the time of primary stretching, but if it is too high, the drawn and stretched thermoplastic polyester resin sheet tends to melt and be cut. Therefore, 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 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.

  As described above, the stretching ratio when stretching only by the above-described drawing stretching is preferably 2.5 to 10 times, more preferably 3 to 8 times. What is necessary is just to extend | stretch so that it may become a range. However, if the draw-drawing ratio is low, the tensile strength and the tensile modulus tend to decrease, and if it is high, the sheet tends to break during stretching, so 2 to 9 times is preferable, more preferably 2. The uniaxial stretching ratio is 5 to 7 times. When the stretching ratio is low, the tensile strength, the tensile elastic modulus and the like tend to decrease. When the stretching ratio is high, the sheet tends to break during stretching. 0.05 to 3 times is preferable, and 1.1 to 2 times is more preferable. In addition, the total draw ratio of drawing drawing and uniaxial drawing is represented by the product of drawing drawing magnification and uniaxial drawing rate.

  In order to improve the heat resistance of the drawn (uniaxial) stretched thermoplastic polyester resin sheet, the length of the obtained drawn (uniaxial) stretched thermoplastic polyester resin sheet was fixed, and the temperature was raised. Heat setting is performed at the rising temperature of the crystallization peak of the thermoplastic polyester resin to the rising temperature of the melting peak on the differential scanning calorimetry curve measured at a rate of 10 ° C./min.

  When the heat setting temperature is lower than the rising temperature of the crystallization peak of the thermoplastic polyester resin in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min, the crystallization of the thermoplastic polyester resin does not proceed, so the heat resistance However, when the temperature is higher than the rise temperature of the melting peak, the thermoplastic polyester-based resin dissolves and the stretching (orientation) disappears, the tensile elastic modulus, the tensile strength, etc. are lowered, and when the uniaxial stretching temperature is 30 ° C. or higher, Since the orientation of crystals crystallized at the uniaxial stretching temperature is relaxed, the rising temperature of the crystallization peak of the thermoplastic polyester resin in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min to the rising temperature of the melting peak However, the temperature is not higher by 30 ° C. than the uniaxial stretching temperature.

  Further, when heat-fixing, if the stretched thermoplastic polyester resin sheet is under load, it is stretched and shrinks in a free state. Therefore, the stretched thermoplastic polyester resin sheet is fixed in the length in the stretching direction. . 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 above-mentioned heat-set stretched thermoplastic polyester resin sheet has a temperature higher than the rising temperature of the crystallization peak of the thermoplastic polyester-based resin in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min, and lower than the heat setting temperature. Annealing at a temperature of By annealing, the stretched thermoplastic polyester resin sheet has good mechanical properties such as elastic modulus, and even when heated to a temperature above the glass transition temperature, the mechanical properties such as elastic modulus do not decrease. In addition, 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 longer, more preferably 30 seconds to 60 minutes, and further preferably 1 to 20 Minutes.

  Two or more of the stretched thermoplastic polyester resin sheets may be laminated, and when laminated, they are preferably laminated so that their stretching directions are substantially the same.

  As a method of laminating the stretched thermoplastic polyester resin sheets, any conventionally known method may be adopted. However, stretching of the stretched thermoplastic polyester resin sheet is eased by heat fusion. It is preferable to bond with a hot melt type adhesive such as polyester or polyolefin having a melting point lower than that of the thermoplastic polyester resin constituting the resin sheet.

  The method of adhering with the hot melt adhesive is not particularly limited. For example, at least one of the methods in which the molten hot melt adhesive is applied to at least one stretched thermoplastic polyester resin sheet and the two are laminated and fused at the same time. A molten hot-melt adhesive is applied to the stretched thermoplastic polyester resin sheet and cooled to form a hot-melt adhesive layer and then laminated, or a sheet between two or more stretched thermoplastic polyester-based resin sheets And a method of heating a laminated body obtained by laminating a hot-melt adhesive in the form of a melt to melt and melt the hot-melt adhesive.

  A thermoplastic polyester resin having a melting point lower than the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet as the hot melt adhesive because it is a fusion of the stretched thermoplastic polyester resin sheets. A woven fabric and / or a non-woven fabric is preferably used. When fused with a woven fabric and / or a nonwoven fabric made of thermoplastic polyester resin, the adhesive strength is high, and the tensile strength, impact resistance and the like are improved.

  As the fibers constituting the thermoplastic polyester resin woven fabric and / or nonwoven fabric, the above-mentioned thermoplastic polyester resin fibers and the above-mentioned thermoplastic polyester resins and natural fibers such as cotton and suf, polyethylene fibers, Examples thereof include synthetic fibers such as polypropylene fibers, polyester fibers, polyimide fibers, polyvinyl alcohol fibers, and acrylic fibers, and mixed fibers with fibers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers.

  As the nonwoven fabric, any conventionally known nonwoven fabric can be used. For example, dry-type nonwoven fabrics such as range bond nonwoven fabrics, thermal bond nonwoven fabrics, needle punch nonwoven fabrics, spunlace nonwoven fabrics, airlaid nonwoven fabrics, spunbond nonwoven fabrics, and melt blown nonwoven fabrics. Examples include a directly-spun type nonwoven fabric, a wet nonwoven fabric, and the like. Needle punch nonwoven fabrics and spunlace nonwoven fabrics that are rich in bulk properties, flexibility, and the like and are difficult to delaminate are preferable.

  The needle punched nonwoven fabric is a nonwoven fabric in which a needle (needle) that moves up and down at high speed is repeatedly pierced on a web formed by arranging short fibers randomly, and the fibers are entangled by protrusions called barbs carved in the needle.

  The spunlace nonwoven fabric uses a high pressure pump to eject a 30 to 500 bar high pressure water stream from the nozzle to the web, and the high pressure water stream uses the force to punch the web and the rebounding force of the punched high pressure water stream to three-dimensionalize the fiber. It is a nonwoven fabric intertwined.

  The basis weight, thickness, etc. of the thermoplastic polyester resin woven fabric and nonwoven fabric are not particularly limited, but in general, the basis weight is preferably 10 to 500 g / m @ 2, and the thickness is preferably 0.03 to 4 mm. .

  In addition, in order to more easily laminate stretched thermoplastic polyester resin sheets and fuse them firmly to improve impact resistance, the melting point is lower than the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet. A method of laminating and fusing a woven fabric and / or a nonwoven fabric impregnated with a polyester-based, polyolefin-based or other hot-melt type adhesive between stretched thermoplastic polyester-based resin sheets is also preferable.

  The woven fabric and / or nonwoven fabric is not particularly limited, and any conventionally known woven fabric and nonwoven fabric can be used. For example, natural fibers such as cotton and suf, polyethylene fibers, polypropylene fibers, polyester fibers, polyimides Examples thereof include woven fabrics and non-woven fabrics composed of fibers such as fibers, polyvinyl alcohol fibers, acrylic fibers and other synthetic fibers, glass fibers, carbon fibers, metal fibers, ceramic fibers, and other inorganic fibers.

  As the nonwoven fabric, any conventionally known nonwoven fabric can be used. For example, dry-type nonwoven fabric such as range bond nonwoven fabric, thermal bond nonwoven fabric, needle punch nonwoven fabric, spunlace nonwoven fabric, airlaid nonwoven fabric, spunbond nonwoven fabric, and melt blown nonwoven fabric. Examples include a directly-spun type nonwoven fabric, a wet nonwoven fabric, and the like. Needle punch nonwoven fabrics and spunlace nonwoven fabrics that are rich in bulk properties, flexibility, and the like and are difficult to delaminate are preferable.

  The basis weight, thickness, etc. of the woven fabric and nonwoven fabric are not particularly limited, but generally the basis weight is preferably 10 to 500 g / m @ 2, and the thickness is preferably 0.03 to 4 mm.

  In the method of melting and fusing the hot melt adhesive, it is preferable to melt and fuse the hot melt adhesive with an ultrasonic welder.

  As the 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, the woven fabric and / or the nonwoven fabric, and the thermoplastic resin. A method of passing a laminated body such as a layer between a horn and a knurl that are vibrated at a frequency of 15 to 40 kHz is mentioned.

  As a method of laminating different stretched thermoplastic polyester resin sheets, a woven fabric and / or a non-woven fabric having a melting point higher than that of the thermoplastic polyester resin is laminated between two or more stretched thermoplastic polyester resin sheets. The stretched thermoplastic polyester resin sheet is softened and melted and pressed to cause the woven fabric and / or the nonwoven fabric to bite into the stretched thermoplastic polyester resin sheet and be fused. Any conventionally known method may be adopted as a method for softening and melting the stretched thermoplastic polyester resin sheet, but it is preferably heated by an ultrasonic welder.

  Examples of the woven fabric and / or nonwoven fabric include the woven fabric and / or nonwoven fabric described above, and the woven fabric and / or nonwoven fabric having a melting point higher than the melting point of the thermoplastic polyester resin constituting the thermoplastic polyester resin sheet. can give.

  Further, as a method of laminating different stretched thermoplastic polyester resin sheets, one kind selected from the group consisting of reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, and rubber adhesives Or the method of adhering with 2 or more types of adhesives is mention | raise | lifted.

  Alternatively, the woven fabric and / or the nonwoven fabric impregnated with the adhesive may be laminated between stretched thermoplastic polyester resin sheets and bonded by the adhesive. When a woven fabric and / or a nonwoven fabric impregnated with an adhesive is laminated and bonded, the adhesion of the stretched thermoplastic polyester resin sheet is improved, and the resulting laminate has tensile strength, impact resistance, etc. improves.

  As the nonwoven fabric, any conventionally known nonwoven fabric can be used. For example, dry-type nonwoven fabric such as range bond nonwoven fabric, thermal bond nonwoven fabric, needle punch nonwoven fabric, spunlace nonwoven fabric, airlaid nonwoven fabric, spunbond nonwoven fabric, and melt blown nonwoven fabric. Examples include a directly-spun type nonwoven fabric, a wet nonwoven fabric, and the like. Needle punch nonwoven fabrics and spunlace nonwoven fabrics that are rich in bulk properties, flexibility, and the like and are difficult to delaminate are preferable.

The stretched thermoplastic polyester resin sheet obtained by the method for producing a stretched thermoplastic polyester resin sheet of the present invention can be molded into a predetermined shape by a molding method such as atypical molding or bending, and a molded body having a predetermined shape And is suitably used as an interior and exterior building material, particularly as a rain gutter. Moreover, in order to improve the weather resistance and designability of a molded object, you may laminate | stack a different resin layer on the surface of a thermoplastic resin sheet, or may apply a coating material.

The structure of the manufacturing method of the extending | stretching thermoplastic polyester-type resin sheet of this invention is as above-mentioned, an extending | stretching thermoplastic polyester-type resin sheet can be manufactured easily, and the obtained extending | stretching thermoplastic polyester-type resin sheet is a wire. Low expansion coefficient, light weight, excellent impact resistance, durability, workability, productivity, etc., and difficult to break during secondary processing, excellent bending workability, can be used suitably as interior and exterior building materials, etc. .

The laminated sheet in which a thermoplastic resin layer is laminated on the thermoplastic polyester resin sheet has a thermoplastic polyester layer as a core material, the thermoplastic resin layer is firmly bonded, and has a low coefficient of linear expansion. It is lightweight, has excellent weather resistance, impact resistance, durability, workability, productivity and the like, is difficult to break during secondary processing, has excellent bending workability, and can be suitably used as an interior or exterior building material.

  Next, although an example of the present invention is given and explained in detail, the present invention is not limited to the following example.

Example 1
Polyethylene terephthalate (trade name “NEH-2070” manufactured by Unitika Ltd., intrinsic viscosity 0.88) melt-extruded polyethylene terephthalate sheet (crystallinity 1.3%) with a thickness of 2.5 mm is stretched (Kyowa Engineering Co., Ltd.) After preheating to 80 ° C., a pair of rolls heated to 74 ° C. (roll interval: 0.5 mm) is drawn at a rate of 2 m / min, thickness is 0.5 mm, and draw ratio is about 5 A double-stretched polyethylene 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 a differential scanning calorimetry curve measured at a heating rate of 10 ° C./min is about 140 ° C., and a rising temperature of the melting peak. Was about 234 ° C.

  Both ends of the obtained stretched polyethylene terephthalate sheet were held, supplied to a hot air heating tank set at 200 ° C., and heat fixed for 2 minutes to obtain a heat-stretched stretched polyethylene terephthalate sheet.

  The stretched polyethylene terephthalate sheet heat-fixed was supplied to a hot air heating tank set at 140 ° C. with substantially no tension, and annealed for 5 minutes to obtain an annealed stretched polyethylene terephthalate sheet. The length of the stretched polyethylene terephthalate sheet annealed was 0.98 times the length of the stretched polyethylene terephthalate sheet before annealing.

  The obtained stretched polyethylene terephthalate sheet and the annealed stretched polyethylene terephthalate sheet had tensile elastic moduli of 11.0 GPa and 9.2 GPa measured according to the tensile test method of JIS K 7113. Moreover, the elongation at break measured according to the tensile test method of JIS K 7113 of the annealed stretched polyethylene terephthalate sheet was 3.7%.

  The obtained annealed stretched polyethylene terephthalate sheet was heated to 140 ° C. to produce a U-shaped molded body with each side bent at a right angle, but no cracks occurred in the stretched polyethylene terephthalate sheet.

  Further, hot-melt adhesive (trade name “Byron GM920” manufactured by Toyobo Co., Ltd.) and vinyl chloride resin (trade name “TS1000R” manufactured by Tokuyama Sekisui Co., Ltd.) are applied to both surfaces of the obtained molded product on the surface. In this way, melt extrusion coating was performed at 200 ° C., and an adhesive layer having a thickness of 0.01 mm and a vinyl chloride resin layer having a thickness of 0.05 mm were laminated on both surfaces to obtain a laminated molded body.

When the linear expansion coefficient was measured in accordance with JIS K 7197 using the obtained laminated molded product, it was 0.1 × 10 ⁻⁵ (/ ° C.), which was in accordance with the tensile test method of JIS K 7113. The tensile modulus was measured and found to be 3.9 GPa.

Claims (2)

Production of a stretched thermoplastic polyester resin sheet having an elastic modulus in the stretching direction of 9 GPa or more and an elongation at break in the direction perpendicular to the stretching direction of 3.5% or more , measured according to the tensile test method of JIS K 7113 A thermoplastic polyester resin sheet in an amorphous state is drawn and stretched at a temperature between the glass transition temperature of the thermoplastic polyester resin of −20 ° C. to the glass transition temperature of the thermoplastic polyester resin of + 20 ° C., Rise temperature of the crystallization peak of the thermoplastic polyester resin in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min with the length of the drawn stretched thermoplastic polyester resin sheet fixed in the drawing direction Heat fixing at the rising temperature of the melting peak and then annealing at a temperature higher than the rising temperature of the crystallization peak and lower than the heat fixing temperature. Oriented thermoplastic method for producing a polyester-based resin sheet characterized by. The method for producing a stretched thermoplastic polyester resin sheet according to claim 1, wherein the stretch ratio is 3 to 8 times.