JP4762000B2 - Laminated sheet - Google Patents

Description

  The present invention relates to a laminated sheet that can be suitably used as an exterior building material using 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 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, Although it was necessary to connect with an absorbable joint or to make the end free, when the entire length of the rain gutter to be constructed becomes longer, there are disadvantages that the number of joints and outlets increases and the appearance is poor. It was.

For this reason, various studies have been made on rain gutters having a low coefficient of linear expansion. 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 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.

  In view of the above drawbacks, the object of the present invention is that a stretched thermoplastic polyester resin sheet excellent in tensile strength, tensile elastic modulus and heat resistance and a thermoplastic resin layer are firmly bonded, have a low coefficient of linear expansion, and are lightweight. Then, it is providing the laminated sheet which can be used suitably as exterior building materials, such as a rain gutter, especially the laminated sheet which is excellent in impact resistance, durability, workability | operativity, productivity, etc.

  The laminated sheet of the present invention is drawn and drawn from an amorphous thermoplastic polyester resin sheet 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. After that, after subjecting the both sides of the stretched thermoplastic polyester resin sheet obtained by uniaxial stretching at a temperature higher than the drawing stretching temperature to fine concavo-convex processing, a thermoplastic resin layer is laminated.

  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, 0.5-5 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 5 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 amorphous thermoplastic polyester resin sheet is drawn and stretched. The method of drawing and stretching is not particularly limited, and may be drawn and drawn through a drawing die having a predetermined clearance, but drawing and drawing through a pair of rolls can freely control the thickness after drawing, and the drawing metal This is preferable because the specific part of the mold does not wear.

  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.

The preheating temperature is preferably a glass transition temperature of the thermoplastic polyester resin of −20 ° C. to a glass transition temperature of the thermoplastic polyester resin of + 10 ° C.
This is because the resin sheet may not reach a predetermined temperature if the preheating temperature is too low or too high.

  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 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 drawing and stretching.

  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 drawn thermoplastic polyester resin sheet at a temperature higher than the drawing and drawing temperature increases the degree of crystallinity 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.

  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. 1.05 to 3 times, and more preferably 1.1 to 2 times. Moreover, the total draw ratio of drawing drawing and uniaxial drawing is preferably 2.5 to 10 times for the same reason.

  In the present invention, the stretched thermoplastic polyester resin sheet that has been uniaxially stretched is preferably heat-set in order to further improve the heat resistance.

  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 And the temperature which is not 30 degreeC or more higher than a uniaxial stretching temperature 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, 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 resin sheet before heat setting, and is a lower ratio than the uniaxial stretch ratio. It is preferable to heat-fix like this.

  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 to heat-set by setting it to a magnification lower than the uniaxial stretching magnification at .95 to 1.1.

  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 longer, more preferably 30 seconds to 60 minutes, and further preferably 1 to 20 Minutes.

In the stretched thermoplastic polyester resin sheet of the present invention, the energy required for production is large and economical to produce a stretched thermoplastic polyester resin sheet having a linear expansion coefficient smaller than −1.5 × 10 ⁻⁵ / ° C. If the temperature is 0 / ° C. or higher, the linear expansion coefficient of the laminated sheet in which the thermoplastic resin layers are laminated on both sides of the stretched thermoplastic polyester resin sheet is increased, so that the linear expansion of the stretched thermoplastic polyester resin sheet is increased. The coefficient is preferably −1.5 × 10 ⁻⁵ / ° C. or more and less than 0 / ° C.

  When the tensile modulus of the thermoplastic polyester resin sheet is less than 7 GPa, the linear expansion coefficient of the laminate molded body in which the thermoplastic resin layers are laminated on both sides 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 7 to 15 GPa.

  In the present invention, the stretched thermoplastic polyester resin sheet has a thermoplastic resin layer laminated after fine concavo-convex processing on both sides thereof.

  The direction of the fine unevenness processing is not particularly limited, and the unevenness along the uniaxial stretching direction of the thermoplastic polyester resin sheet, the unevenness across the uniaxial stretching direction of the thermoplastic polyester resin sheet, and the unevenness drawing a curve are formed. Can do.

Further, if the fine unevenness is too small, a special polishing cloth or a tool such as a brush is required, which is not economical. If it is too large, it is difficult to obtain the effect of the unevenness processing, so the surface roughness Ra is 0.5 to 20 μm is preferable.
Here, the surface roughness Ra is a value measured with a surface roughness meter at a cutoff wavelength of 0.8 mm and a wavelength length of 4 mm.

  The fine concavo-convex processing method is not particularly limited as long as it is a processing method that can apply linear fine concavo-convex to the entire surface of the stretched thermoplastic polyester resin sheet. For example, sanding processing, brushing processing, etc. Can be mentioned.

The above sanding process is a state in which an abrasive cloth or paper coated with ceramic, sand, metal particles, etc. on a cloth or paper with a binder is in contact with the stretched thermoplastic polyester resin sheet. By sliding or rotating, the resin on the surface of the stretched thermoplastic polyester resin sheet is scraped to provide an uneven portion.
The polishing cloth / paper is preferably in the form of a belt or in the form of a plurality of strips and one end fixed on the rotating shaft in the form of a water wheel, since it can be continuously processed into irregularities.

With the brushing process, the tip of a brush made of a hair material such as a metal wire, nylon fiber, polypropylene fiber, polyester fiber, aramid fiber, polyphenylene sulfide fiber is brought into contact with the stretched thermoplastic polyester resin sheet and slid. It is to scrape off the resin on the surface of the stretched thermoplastic polyester resin sheet by rotating it and to provide an uneven portion.
As the brush, a shape in which the hair is planted in a wheel shape or a cup shape is preferable because it can be continuously processed with unevenness.

  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.

  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. .

  When the thermoplastic resin is melted and applied to the stretched thermoplastic polyester resin sheet, the crystals of the stretched thermoplastic polyester resin sheet are relaxed if the melting point of the thermoplastic resin is higher than the melting point of the thermoplastic polyester resin. Since the linear expansion coefficient is high, the thermoplastic resin is preferably a resin having a lower melting point than the thermoplastic polyester 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 of 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 was finely textured. A method in which a thermoplastic resin melted by an extruder or a hot press is laminated on both sides and the recesses are filled with the thermoplastic resin by an extrusion pressure or a press pressure is preferable.

  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 adhesion lamination with a hot melt adhesive is not particularly limited, and any conventionally known method may be employed, for example, on both sides of a stretched thermoplastic polyester resin sheet subjected to fine uneven processing, There is a method in which a melted hot-melt adhesive is extrusion coated or roll-coated, the recesses are filled with the hot-melt adhesive, a hot-melt adhesive layer is laminated, and a thermoplastic resin layer is adhesively laminated thereon. Can be mentioned.

  In addition, a hot-melt adhesive layer and a thermoplastic resin layer are sequentially laminated on both sides of the stretched thermoplastic polyester resin sheet that have been processed with fine irregularities, and the hot-melt adhesive is melted by heating and pressurizing. A melt-type adhesive may be allowed to enter the recesses, and the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer may be bonded and laminated.

Examples of the heating and pressing method include a hot roll press and an ultrasonic welder.
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. 1 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, and hot melt adhesive sheets 2 and 2 are laminated on both sides of the stretched thermoplastic polyester resin sheet 1 on which fine irregularities are processed. The resin layers 3 and 3 are laminated to form a laminate 10.

  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, since the protrusions are formed on the surface of the knurling 5, it is possible to fuse more efficiently, and 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.

  In addition, a thermoplastic resin layer is laminated on both surfaces of a stretched thermoplastic polyester resin sheet that has been subjected to fine unevenness processing via an adhesive that is laminated so as to fill the recess.

  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 adhesives are listed.

  When laminating with an adhesive, apply adhesive on both sides of the stretched thermoplastic polyester-based resin sheet that have been subjected to fine irregularities so as to fill in the recesses, and then laminate and bond the thermoplastic resin layer on it. Good.

  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 stretched thermoplastic polyester resin sheet used in the present invention is excellent in tensile strength, tensile elastic 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 the laminated sheet of the present invention, since the thermoplastic resin is laminated after fine stretching processing on the stretched thermoplastic polyester resin sheet, the stretched thermoplastic polyester resin sheet and the thermoplastic resin are firmly bonded. It has a low coefficient of linear expansion, is lightweight, and has excellent impact resistance, durability, workability, productivity, and the like. 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
Polyethylene terephthalate (trade name “NEH-2070” manufactured by Unitika Ltd., intrinsic viscosity 0.88) obtained by melt-extrusion and quenching, polyethylene having a crystallinity of 1.3% and a thickness of 2.5 mm A terephthalate sheet is supplied to a stretching apparatus (manufactured by Kyowa Engineering Co., Ltd.), preheated to 80 ° C., and then heated to 74 ° C. and rotated in the stretching direction at 0.05 m / min (roll interval 0.6 mm) Pulling and stretching at a speed of 2 m / min, further heating the surface temperature of the polyethylene terephthalate sheet to 180 ° C. in a hot air heating tank, setting the outlet speed to 2.5 m / min, and uniaxially stretching the roll, A stretched polyethylene terephthalate sheet having a stretch ratio of about 5 times and a thickness of 0.5 mm was obtained.

  The polyethylene terephthalate 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 is about 140 ° C., and a rising temperature of the melting peak is It was about 234 ° C. The sheet feeding speed to the stretching apparatus was 0.4 mm / min.

Both sides of the obtained stretched polyethylene terephthalate sheet are sizing with a belt sander (made by Amitech) with No. 80 abrasive cloth belt (stretching polyethylene terephthalate sheet feed speed 7 m / min, abrasive cloth belt rotation speed 10 m / sec) Then, irregularities along the uniaxial stretching direction of the stretched polyethylene terephthalate sheet were formed.
When the uneven surface was measured with a surface roughness meter (trade name “Sarkoff 550A” manufactured by Tokyo Seimitsu Co., Ltd.) at a cutoff wavelength of 0.8 mm and a wavelength length of 4 mm, the surface roughness Ra value was 12.8 μm.

  Polyurethane-based hot-melt adhesive (product name “Sdyne 9615W” manufactured by Sekisui Fuller Co., Ltd.) is melted at 120 ° C. on both sides of the stretched polyethylene terephthalate sheet that has been subjected to unevenness processing. 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.

  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)
Both sides of the stretched polyethylene terephthalate sheet obtained in Example 1 were subjected to sizing treatment with a belt sander (Amitech Co., Ltd.) with a No. 120 abrasive cloth belt (stretching speed of the stretched polyethylene terephthalate sheet 3 m / min, rotational speed of the abrasive cloth belt) 5 m / sec) to form irregularities along the uniaxial stretching direction of the stretched polyethylene terephthalate sheet.
When the uneven surface was measured with a surface roughness meter (trade name “Sarkoff 550A”, manufactured by Tokyo Seimitsu Co., Ltd.) at a cutoff wavelength of 0.8 mm and a wavelength length of 4 mm, the surface roughness Ra value was 6.0 μm.

  Thickness 0.04mm hot melt formed by melting a polyester hot melt adhesive (trade name Byron GM-913, manufactured by Toyobo Co., Ltd., melting point 126 ° C.) on both sides of a stretched polyethylene terephthalate sheet subjected to unevenness processing. A mold adhesive sheet is laminated at 165 ° C., then a vinyl chloride resin (“TS1000R” manufactured by Tokuyama Sekisui Co., Ltd.) is melt extrusion coated at 200 ° C., and a vinyl chloride resin layer having a thickness of 0.4 mm is laminated on both sides. A laminated sheet was obtained.

(Comparative Example 1)
A polyester-based hot melt adhesive (trade name Byron GM-920, manufactured by Toyobo Co., Ltd., melting point 107 ° C.) was melt-coated on both sides of the stretched polyethylene terephthalate sheet obtained in Example 1, and the thickness was 0.03 mm. A melt-type adhesive sheet was laminated at 165 ° C., and then a vinyl chloride resin sheet having a thickness of 0.4 mm on both sides (obtained by extruding “TS1000R” manufactured by Tokuyama Sekisui Co., Ltd. at 195 ° C.) at 160 ° C., The laminate was pressed at a pressure of 1 MPa for 30 seconds to obtain a laminated sheet having vinyl chloride resin layers laminated on both sides.

  The physical properties of the obtained stretched polyethylene terephthalate sheet and laminated sheet were evaluated by the following evaluation methods, and the results are shown in Table 1.

(1) Linear expansion coefficient It measured based on JISK7197.
(2) Tensile modulus Measured according to the tensile test method of JIS K 7113.

(3) Peel strength In accordance with JIS K 6854, a test piece having a width of 25 mm was prepared, the end of the thermoplastic resin layer was peeled off, and a T-type peel test was performed at a peel rate of 100 mm / min.

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 (6)

  After drawing and stretching an amorphous thermoplastic polyester resin sheet 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., the drawing stretching temperature A laminated sheet characterized in that a thermoplastic resin layer is laminated after fine concavo-convex processing on both surfaces of a stretched thermoplastic polyester resin sheet obtained by uniaxial stretching at a higher temperature. The laminated sheet according to claim 1 , wherein the unevenness processing is sanding processing or brushing processing. The laminated sheet according to claim 1 or 2 , wherein the thermoplastic resin layer is laminated by melt-coating a thermoplastic resin on a stretched thermoplastic polyester resin sheet. The laminated sheet according to any one of claims 1 to 3 , wherein the thermoplastic resin layer is bonded and laminated to the stretched thermoplastic polyester resin sheet with a hot melt adhesive having a lower melting point than the stretched thermoplastic polyester resin. . The thermoplastic resin layer is stretched by one or more adhesives selected from the group consisting of reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives. The laminated sheet according to any one of claims 1 to 4 , wherein the laminated sheet is bonded and laminated to a polyester resin sheet. The laminated sheet according to any one of claims 1 to 5 , wherein the laminated sheet is an exterior building material.