JP2006281657A - Laminated molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated molded product low in the coefficient of linear expansion, having lightweight properties, excellent in impact resistance, durability, workability, productivity and the like and especially suitably used as a facing building material such as an eaves trough or the like. <P>SOLUTION: The laminated molded product is constituted by laminating a stretched thermoplastic polyester resin sheet and a stretched olefinic resin sheet. The stretched thermoplastic polyester resin sheet is preferably obtained by passing the an amorphous thermoplastic polyester resin sheet through the nip between a pair of rolls, which are held to (a temperature range from the glass transition temperature of a thermoplastic polyester resin)-20°C to (the glass transition temperature of the thermoplastic polyester resin)+20°C, to draw and stretch the same. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate molded body of a stretched thermoplastic polyester resin sheet and a stretched olefin resin sheet, and a laminate molded body that can be suitably used as an exterior building material using the laminate molded body as a core material.

  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 ^-3 (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, if the length of the gutter becomes longer, the joint becomes larger, the appearance is bad, and the joint part may be damaged if used for a long time. there were. 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.

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 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 thin metal 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 the glass fiber powder is scattered when cut during construction of rain gutters, so that workability is poor, there is a problem in environmental hygiene, 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 coefficient of linear expansion without using a core material or glass fiber made of a metal thin plate, for example, a polyolefin having an average linear expansion coefficient of 20 to 80 ° C. of 5 × 10 ⁻⁵ (/ ° C.) or less. After the low molecular weight compound that dissolves the polyolefin was adhered to the surface of the stretched material, 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 (/ ° C) The following is a polyolefin molded body (for example, see Patent Document 4), after extruding a thermoplastic resin, and further stretching and stretching the extruded resin to orient the molecules in one direction, A synthetic resin rain gutter (for example, see Patent Document 5) characterized in that the linear expansion coefficient of the plastic synthetic resin is 6 × 10 ⁻⁵ / ° C. or less and the thickness is greater than 0.5 mm has been proposed.
JP-A-10-291250 Japanese Patent Laid-Open No. 2002-285685

  However, the former rain gutter is a highly stretched sheet of polyolefin stretched material of 20 to 40 times, and has the disadvantage that it is easy to break along the stretching 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-mentioned drawbacks, the object of the present invention is a laminated molded body having a low coefficient of linear expansion, light weight, excellent impact resistance, durability, workability, productivity, etc., particularly as exterior building materials such as rain gutters. An object of the present invention is to provide a laminated molded body that can be suitably used.

  The laminated molded article according to claim 1 of the present invention is characterized in that a stretched thermoplastic polyester resin sheet and a stretched olefin resin sheet are laminated.

  The laminated molded article according to claim 2 is a laminated molded article according to claim 1, wherein the surface is a stretched thermoplastic polyester resin sheet.

  The laminated molded article according to claim 3, wherein the stretched thermoplastic polyester resin sheet is an amorphous thermoplastic polyester resin sheet, the glass transition temperature of the thermoplastic polyester resin is -20 ° C to the thermoplastic polyester resin. 3. The laminated molded article according to claim 1 or 2, which is a drawn stretch thermoplastic polyester resin sheet obtained by drawing through a pair of rolls having a glass transition temperature of the resin + 20 ° C and stretching. .

  The laminated molded article according to claim 4 is a uniaxially stretched thermoplastic polyester resin sheet obtained by uniaxially stretching a stretched thermoplastic polyester resin sheet at a temperature higher than the temperature of the roll after drawing and stretching. It is a laminated molded object of Claim 3.

  The laminated molded article according to claim 5 has a uniaxial stretching temperature ranging from a rising temperature of a crystallization peak of a thermoplastic polyester resin to a rising temperature of a melting peak in a differential operation calorimetric curve measured at a heating rate of 1 ° C./min. The laminated molded body according to claim 4, wherein the laminated molded body is provided.

  The laminated molded article according to claim 6 is the laminated molded article according to claim 4 or 5, wherein the uniaxially stretched thermoplastic polyester resin sheet is heat-set at a temperature higher than the uniaxially stretched temperature.

  In the laminated molded article according to claim 7, the heat setting temperature is the rising temperature of the melting peak of the thermoplastic polyester resin in the differential operation calorimetric curve measured at a uniaxial stretching temperature to a heating rate of 1 ° C / min. The laminated molded body according to claim 6, characterized in that it is a laminated molded body.

  The laminated molded body according to any one of claims 1 to 7, wherein the stretched thermoplastic polyester resin sheet has a stretch ratio of 3 to 8 times.

  The laminated molded body according to any one of claims 1 to 8, wherein the stretched thermoplastic polyester resin sheet has a negative linear expansion coefficient.

  The laminated molded article according to claim 10, wherein two or more stretched thermoplastic polyester resin sheets or stretched olefin resin sheets are laminated so that the stretching directions are substantially the same. It is a laminated molded object of any one of 1-6.

  The laminated molded article according to claim 11, wherein the two or more stretched thermoplastic polyester resin sheets or stretched olefin resin sheets have a melting point lower than the melting point of the thermoplastic polyester resin, reactive adhesive The adhesive is bonded with one or more adhesives selected from the group consisting of an adhesive, an epoxy adhesive, a urethane adhesive, a polyester adhesive, and a rubber adhesive. It is a laminated molded object of description.

  The laminated molded article according to claim 12, wherein a woven fabric and / or a nonwoven fabric is laminated between two or more stretched thermoplastic polyester resin sheets or stretched olefin resin sheets. It is a laminated molded object of description.

  The laminated molded article according to claim 13 is a hot-melt adhesive having a melting point lower than the melting point of the thermoplastic polyester resin, reaction between two or more stretched thermoplastic polyester resin sheets or stretched olefin resin sheets. Woven and / or non-woven fabric impregnated with one or more adhesives selected from the group consisting of adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives The laminated molded body according to claim 10, wherein the laminated body is laminated and bonded.

  The laminated molded article according to claim 14, wherein the stretched olefin resin sheet is a polyethylene resin sheet having a total draw ratio of 10 to 40 times. Is the body.

  The multilayer molded body according to claim 15, wherein the total stretch ratio of 10 to 40 times comprises a rolling ratio of 5 to 10 times and a stretch ratio of 1.3 to 4 times. is there.

  The laminated molded body according to claim 16, wherein a thermoplastic resin layer is further laminated on both sides, and the laminated molded body according to any one of claims 1 to 15.

  The laminated molded article according to claim 17, wherein the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer have a melting point lower than the melting point of the thermoplastic polyester resin, a hot melt adhesive reactive adhesive, an epoxy adhesive The laminated molded article according to claim 16, wherein the laminated molded article is bonded with one type or two or more types of adhesives selected from the group consisting of urethane adhesives, polyester adhesives, and rubber adhesives. is there.

  The laminated molded article according to claim 18, wherein a woven fabric and / or a nonwoven fabric is laminated between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer. It is.

  The laminated molded article according to claim 19, wherein a hot-melt adhesive, a reactive adhesive, an epoxy having a melting point lower than the melting point of the thermoplastic polyester resin between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer A woven fabric and / or a non-woven fabric impregnated with one or two or more types of adhesives selected from the group consisting of adhesives, urethane adhesives, polyester adhesives, and rubber adhesives is laminated and bonded. The laminated molded body according to claim 16, wherein

  The laminated molded body according to claim 20 is the laminated molded body according to any one of claims 1 to 19, wherein the laminated molded body is an exterior building material.

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.
On the other hand, if the intrinsic viscosity is too low, drawdown is likely to occur 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.

  The thickness of the thermoplastic polyester resin sheet is not particularly limited, but if it is less than 0.1 mm, the sheet thickness after stretching becomes too thin, and the strength during handling may not be sufficiently large. Since it may become difficult, 0.1-5 mm is preferable, More preferably, it is 0.2-3 mm.

  The stretched thermoplastic polyester resin sheet used in the present invention comprises an amorphous thermoplastic polyester resin sheet, a glass transition temperature of the thermoplastic polyester resin of −20 ° C. to a glass transition of the thermoplastic polyester resin. A drawing-drawn thermoplastic polyester resin sheet obtained by drawing through a pair of rolls at a temperature of + 20 ° C. and drawing is preferred.

  When the temperature of the pair of rolls at the time of drawing and stretching is low, the thermoplastic polyester resin sheet is too hard to be pulled out, and when the temperature is high, the thermoplastic polyester resin sheet becomes soft and the tensile force pulls the sheet. Since the sheet is cut, the glass transition temperature of the thermoplastic polyester resin ranges from −20 ° C. to the glass transition temperature of the thermoplastic polyester resin + 20 ° C., preferably the glass transition of the thermoplastic polyester resin. The temperature is the temperature range of 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 need not be rotated, but may be slightly rotated in the pulling direction in order to make the temperature distribution uniform.

  The stretching ratio of the primary 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. 2-9 times is preferable, More preferably, it is 2.5-7 times.

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

  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 uniaxially stretched thermoplastic polyester resin sheet having 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. The temperature range from the rising temperature of the crystallization peak of the thermoplastic polyester resin to the rising temperature of the melting peak in the differential operation calorie curve measured at a rate of temperature increase of 1 ° C./min is preferred.

  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. However, if the stretching ratio is low, an excellent sheet such as tensile strength and tensile elastic modulus cannot be obtained. If the stretching ratio is high, the sheet tends to break during stretching. Therefore, 1.1-3 times are preferable, More preferably, it is 1.2-2 times. Moreover, 2.5 to 10 times are preferable for the same reason, and the total draw ratio of primary stretching and uniaxial stretching is 3 to 8 times more preferably.

  When the stretched thermoplastic polyester resin sheet has a large linear expansion coefficient, it expands and contracts greatly due to a temperature difference. Therefore, a smaller one is preferable, and a negative one is particularly preferable. Further, since the stretched thermoplastic polyester resin sheet is laminated as a core material of the laminated molded body, it is preferable that the strength is high and the elastic modulus is 9 GPa or more.

  The stretched thermoplastic polyester resin sheet that has been uniaxially stretched 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 is not improved, and the thermoplastic polyester system in the differential operation calorimetric curve measured at a heating rate of 1 ° C./min. If the temperature rises above the rise temperature of the melting peak of the resin, the thermoplastic polyester-based 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 1 ° C./min. The rising temperature of the melting peak of the thermoplastic polyester resin in the measured differential operation calorimetric curve is preferred.

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

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

  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. Hot melt adhesives such as polyesters and polyolefins having a melting point lower than that of the thermoplastic polyester resin constituting the resin sheet, reactive hot melt adhesives, epoxy adhesives, urethane adhesives, polyesters It is preferable that the adhesive is bonded with one or two or more adhesives selected from the group consisting of a rubber adhesive and a rubber adhesive.

  Further, a woven fabric and / or a nonwoven fabric may be laminated between the stretched thermoplastic polyester resin sheets. When the woven fabric and / or the nonwoven fabric are laminated, the adhesion of the stretched thermoplastic polyester resin sheet is improved, and the tensile strength, impact resistance, and the like of the obtained laminated molded body are improved.

  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, nylon Examples thereof include woven fabrics and non-woven fabrics made of fibers such as fibers, vinylon fibers, and acrylic fibers, and inorganic fibers such as glass fibers and carbon fibers.

The basis weight and thickness of the woven fabric and the 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.

  As a method of laminating the stretched thermoplastic polyester resin sheet and the woven fabric and / or the nonwoven fabric, any conventionally known method may be adopted. However, when heat-sealing, stretching of the stretched thermoplastic polyester resin sheet is alleviated. Therefore, polyester-based, polyolefin-based hot-melt adhesives and reactive hot-melt adhesives, epoxy-based adhesives having a melting point lower than that of the thermoplastic polyester resin constituting the stretched thermoplastic polyester-based resin sheet, Bonding is preferably performed with one or two or more adhesives selected from the group consisting of urethane adhesives, polyester adhesives, and rubber adhesives.

  In order to improve the impact resistance by simply laminating the stretched thermoplastic polyester resin sheet and the woven fabric and / or non-woven fabric to improve the impact resistance, a hot melt having a melting point lower than that of the thermoplastic polyester resin is used. Woven fabric impregnated with one or more adhesives selected from the group consisting of mold adhesives, reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives, and It is preferable to laminate and bond a nonwoven fabric between stretched thermoplastic polyester resin sheets.

  The stretched olefin resin sheet used in the present invention is preferably a stretched olefin resin sheet having a total stretch ratio of 10 to 40 times.

  As the olefin-based resin constituting the stretched olefin-based resin sheet, any olefin-based resin having a film forming ability can be used. For example, a high-density polyethylene resin, a medium-density polyethylene resin, a low-density polyethylene resin, a linear low-density Polyethylene resin, polypropylene resin, ethylene-propylene copolymer, ethylene-pentene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate copolymer, ethylene-vinyl chloride copolymer, Examples thereof include an ethylene-propylene-butene copolymer, and a high-density polyethylene resin is preferably used.

  A polymerizable unsaturated compound having an affinity for the olefin resin may be added to the olefin resin. By doing in this way, the heat resistance of the stretched olefin resin sheet obtained improves, and it becomes easy to laminate | stack with a stretched thermoplastic polyester resin sheet.

The stretched olefin-based resin sheet is preferably highly stretched 10 to 40 times and has high mechanical strength such as tensile strength and elastic modulus. However, when a high-density polyethylene resin is used as the olefin-based resin, its density When is reduced, the mechanical strength is not improved by stretching, so 0.94 g / cm ³ or more is preferable.

  Also, the weight average molecular weight of the high-density polyethylene resin is preferably 200,000 to 500,000 because the mechanical strength does not improve much even if stretched if it becomes too small, and film forming and stretching becomes difficult if it becomes too large. The melt index (MI) is preferably 0.1 to 20 and more preferably 0.2 to 10 because the film formability is excellent.

  When the total draw ratio of the stretched olefin-based resin sheet is small, the tensile strength, the tensile elastic modulus and the like are not improved, and when it is large, it is easy to split laterally.

  Any conventionally known method may be adopted as a method for stretching the olefin resin sheet, but since it is highly stretched 10 to 40 times, the olefin resin sheet is rolled and then stretched or stretched several times. A method of repeated multistage stretching is preferred.

  That is, after rolling so that the rolling ratio is 5 to 10 times, the olefin resin sheet is stretched so that the stretching ratio is 1.3 to 4 times and the total stretching ratio is 10 to 40 times. preferable. The total draw ratio refers to the product of the rolling ratio and the draw ratio.

  The rolling is a method in which an olefin-based resin sheet is supplied to a pair of rolls rotating in opposite directions and pressed to reduce the thickness of the sheet and extend, and the rolled sheet differs from the stretched sheet in that it is an olefin-based sheet. Since the resin is dense without being oriented, it is highly stretchable.

  The rolling temperature cannot be uniformly rolled when the temperature is low, and is melt-cut when it is high. Therefore, the roll temperature during rolling is in the range of “melting point −40 ° C.” to “melting point” of the olefin resin of the olefin resin sheet to be rolled. The melting point is more preferably “melting point−30 ° C.” to “melting point−5 ° C.” of the olefin resin.

  The melting point refers to the maximum point of the endothermic peak that accompanies the melting of the crystal, which is recognized when thermal analysis is performed with a differential scanning calorimeter (DSC).

  Further, if the rolling ratio is small, the subsequent stretching is burdened, and increasing the rolling ratio makes rolling difficult, so 5 to 10 times is preferable. The rolling magnification is a value obtained by grading the cross-sectional area of the sheet before rolling by the cross-sectional area of the sheet after rolling.

  The stretching may be any conventionally known method, and examples thereof include a method of stretching while heating with a heater or hot air by a roll stretching method or a zone stretching method.

  The stretching temperature cannot be uniformly stretched when it is low, and the sheet melts and cuts when it is high. Therefore, the range of “melting point−60 ° C.” to “melting point” of the olefin resin of the olefin resin sheet to be stretched is preferable, more preferably. The melting point of the olefin resin is “melting point−50 ° C.” to “melting point−5 ° C.”.

  Further, since the total draw ratio is 10 to 40 times, the draw ratio may be determined in consideration of the rolling ratio so that the total draw ratio is within this range. If the elastic modulus is not improved and the stretch ratio is large, the sheet is laterally cracked or makes noise when bent, so 1.3 to 4 times is preferable, more preferably 1.5 to 3.0. Is double.

  When the stretched olefin resin sheet becomes thin, the mechanical strength decreases. When the stretched olefin resin sheet becomes thick, the stretched olefin resin sheet is easily cracked in the stretching direction. Therefore, the thickness is generally 0.05 to 1 mm, preferably 0.1 to 0.5 mm. is there.

  The stretched olefin resin sheet may be appropriately laminated depending on the use and the thickness of the stretched olefin resin sheet.

  As the method for laminating the stretched olefin resin sheet, any conventionally known laminating method may be employed. For example, a stretched olefin resin sheet is laminated and an adhesive such as rubber, acrylic, urethane, or silicon is used. Adhesion with adhesive and adhesive, ethylene-vinyl acetate copolymer, adhesion with hot melt adhesive such as linear low density polyethylene resin, low melting point such as linear low density polyethylene resin between stretched olefin resin sheets Examples include a method of laminating resins and heat-sealing.

  When bonding with a hot melt adhesive, the hot melt adhesive may be melted and bonded while being applied, or a hot melt adhesive sheet may be laminated and bonded while being heated and pressed. When the heating temperature is increased, the stretched olefin resin sheet contracts. Therefore, the temperature at which the stretched olefin resin sheet does not substantially heat shrink, that is, the “melting point of the thermoplastic resin constituting the stretched olefin resin sheet. Adhesion is preferably performed at -10 ° C or lower. The same applies to a method in which a low melting point resin is laminated between stretched olefin resin sheets and heat-sealed.

  Furthermore, the woven fabric and / or the nonwoven fabric described above may be laminated between the stretched olefin resin sheets, or a hot melt adhesive having a melting point lower than the melting point of the olefin resin, a reactive adhesive, an epoxy adhesive, Laminate and / or nonwoven fabric impregnated with one or more adhesives selected from the group consisting of urethane adhesives, polyester adhesives and rubber adhesives is laminated between stretched olefin resin sheets And may be bonded.

  The laminated molded body of the present invention may be formed by laminating a stretched thermoplastic polyester resin sheet and a stretched olefin resin sheet, and the order of lamination and the number of layers may be appropriately determined, but the surface is a stretched thermoplastic polyester. A resin sheet is preferable.

  Further, the method for laminating the stretched thermoplastic polyester resin sheet and the stretched olefin resin sheet is not particularly limited, and is the same as the method for laminating the stretched thermoplastic polyester resin sheets and the stretched olefin resin sheets described above. In this method, the stretched thermoplastic polyester resin sheet and the stretched olefin resin sheet may be laminated at a temperature that does not shrink.

The laminated molded body may have a thermoplastic resin layer laminated on both sides thereof.
The thermoplastic resin is laminated on both surfaces of the laminate molded body, and the stretched olefin resin sheet and the stretched thermoplastic polyester resin sheet are protected from cracking and cracking along the stretching direction by impact, and the olefinic resin is protected. The resin and the polyester resin are prevented from being subjected to hydrolysis or deterioration due to direct exposure to rainwater or sunlight, resulting in a decrease in durability.

  Also, when the thermoplastic resin is melted and laminated on the stretched thermoplastic polyester resin sheet or stretched olefin resin sheet, if the melting point of the thermoplastic resin is higher than the melting point of the thermoplastic polyester resin or olefin resin, the stretch Since the crystal of the thermoplastic polyester resin sheet or the stretched olefin resin sheet is relaxed and the linear expansion coefficient is increased, the thermoplastic resin is preferably a resin having a lower melting point than the stretched thermoplastic polyester resin or olefin resin to be laminated.

  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. . Moreover, paints such as fluorine paint, acrylic silicon paint, and urethane paint may be used.

  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 both sides of the stretched thermoplastic polyester resin sheet or stretched olefin resin sheet is not particularly limited, and any conventionally known laminating method may be employed. For example, the following method may be used. Can be mentioned.

(1) A method of laminating a thermoplastic resin by extrusion coating on the surface of the stretched thermoplastic polyester resin sheet or stretched olefin resin sheet to be laminated.
(2) A method in which a thermoplastic resin sheet is bonded and laminated on the surface of a stretched thermoplastic polyester resin sheet or stretched olefin resin sheet to be laminated by hot pressing.

(3) The thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet or the olefin resin constituting the stretched olefin resin sheet on both sides of the stretched thermoplastic polyester resin sheet or stretched olefin resin sheet to be laminated Adhesives such as polyester and polyolefin hot melt adhesives and reactive hot melt adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, rubber adhesives and the like having a melting point lower than the melting point A method of adhering and laminating thermoplastic resin sheets.

In order to increase the adhesive force in the above methods (1) and (2), the following method is employed.
(A) The surface of the stretched thermoplastic polyester resin sheet or stretched olefin resin sheet to be laminated is scraped to form irregularities on the surface, and the thermoplastic resin is extrusion-coated, or the thermoplastic resin sheet is pressed and the anchor effect is applied. Lamination method.
(B) A method in which a large number of through holes are formed in the product molded body and the thermoplastic resin is extrusion-coated, or a thermoplastic resin sheet is pressed and the thermoplastic resin sheets on both sides are fused and laminated through the through holes.

(C) The olefin resin constituting the thermoplastic polyester resin or the stretched olefin resin sheet constituting the stretched thermoplastic polyester resin sheet on the surface of the stretched thermoplastic polyester resin sheet or the stretched olefin resin sheet to be laminated. After the thermoplastic resin sheet is bonded with a hot melt type adhesive or reactive hot melt type adhesive such as polyester or polyolefin having a melting point lower than the melting point of the thermoplastic resin, the thermoplastic resin is extrusion coated or the thermoplastic resin sheet Method of pressing and laminating.

  Among these laminating methods, a method of laminating with an adhesive such as a hot melt adhesive is preferably used.

  Further, a woven fabric and / or a non-woven fabric may be laminated between the stretched thermoplastic polyester resin sheet or stretched olefin resin sheet and the thermoplastic resin layer. When the woven fabric and / or the nonwoven fabric are laminated, the adhesion between the stretched thermoplastic polyester resin sheet or stretched olefin resin sheet and the thermoplastic resin layer is improved, and the resulting molded laminate has tensile strength and impact resistance. Etc. are improved.

  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, nylon Examples thereof include woven fabrics and non-woven fabrics made of fibers such as fibers, vinylon fibers, and acrylic fibers, and inorganic fibers such as glass fibers and carbon fibers.

The basis weight and thickness of the woven fabric and the 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.

  As a method of laminating the stretched thermoplastic polyester resin sheet and the woven fabric and / or the nonwoven fabric and the woven fabric and / or the nonwoven fabric and the thermoplastic resin layer, any conventionally known method may be adopted. Since the stretching of the thermoplastic polyester resin sheet or the stretched olefin resin sheet is relaxed, the melting point of the thermoplastic polyester resin constituting the stretched thermoplastic polyester resin sheet or the olefin resin constituting the stretched olefin resin sheet Selected from the group consisting of hot melt adhesives such as polyesters and polyolefins having a low melting point, reactive hot melt adhesives, epoxy adhesives, urethane adhesives, polyester adhesives, and rubber adhesives It is preferable to adhere with one or more kinds of adhesives.

  In addition, stretched thermoplastic polyester resin sheet or stretched olefin resin sheet and woven fabric and / or nonwoven fabric, and woven fabric and / or nonwoven fabric and thermoplastic resin layer are more easily laminated and firmly bonded to improve impact resistance. Hot melt adhesives having a melting point lower than that of thermoplastic polyester resin or stretched olefin resin sheet, reactive adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber systems A woven fabric and / or a non-woven fabric impregnated with one or two or more types of adhesives selected from the group consisting of adhesives, between a stretched thermoplastic polyester resin sheet or stretched olefin resin sheet and a thermoplastic resin layer. It is preferable to laminate and bond.

  The laminated molded body can be molded into a predetermined shape by a molding method such as odd-shaped molding or bending, and a laminated molded body having a predetermined shape is obtained.

  Further, in order to improve the weather resistance and designability of the laminated molded body, a different resin layer may be laminated on the surface of the thermoplastic resin layer, or a paint may be applied.

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

  The structure of the laminated molded body according to claim 1 of the present invention is as described above. Since the stretched thermoplastic polyester resin sheet and the stretched olefin resin sheet are laminated, the linear expansion coefficient is low, the weight is low, and the tensile The strength, impact resistance, heat resistance, durability, workability, productivity, etc. are excellent, and the mechanical strength does not decrease even when used at a high temperature for a long time. Therefore, it can be suitably used as an exterior building material such as a rain gutter.

  The structure of the laminated molded body according to claim 2 is as described above, and a stretched thermoplastic polyester resin sheet and a stretched olefin resin sheet are laminated, and both surfaces thereof are stretched polyester resin sheets. , Low in weight, excellent in tensile strength, impact resistance, heat resistance, durability, workability, productivity and the like, and mechanical strength does not decrease even when used at high temperatures for a long time. Moreover, the adhesiveness with a thermoplastic resin is excellent, a thermoplastic resin can be laminated | stacked easily, Therefore, it can use suitably as exterior building materials, such as a rain gutter.

  The configuration of the laminated molded body according to claim 16 is as described above, and the thermoplastic resin layers are laminated on both sides of the laminated molded body comprising the stretched thermoplastic polyester resin sheet and the stretched olefin resin sheet. Low linear expansion coefficient, light weight, excellent tensile strength, impact resistance, heat resistance, weather resistance, durability, workability, productivity, etc. There is nothing to do. Therefore, it can be suitably used as an exterior building material such as a rain gutter.

  A stretched sheet of a thick thermoplastic polyester resin sheet is accelerated by crystallization due to uneven cooling during stretching, causing sink marks, resulting in uneven thickness and reduced quality. By laminating the resin sheets, the thickness accuracy is improved, and the laminated molded body has a uniform quality with no defects.

  In addition, the woven fabric and / or the nonwoven fabric are laminated between the stretched thermoplastic polyester resin sheet and / or between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer, so that the tensile strength and impact resistance of the laminated molded body are obtained. Etc. improve more.

  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
A polyethylene terephthalate sheet having a thickness of 1 mm (manufactured by Teijin Chemicals Ltd., trade name “A-PET sheet FR”: intrinsic viscosity 0.7) is supplied to a stretching apparatus (manufactured by Kyowa Engineering Co., Ltd.) and preheated to 75 ° C. A pair of rolls heated to ℃ (roll interval 0.2 mm) was pulled out at a speed of 2 m / min, and the polyethylene terephthalate sheet surface temperature was heated to 180 ℃ in a hot air heating tank, and the outlet speed was 2.5 m / min. Set to min and roll-stretched to obtain a stretched polyethylene terephthalate sheet having a stretch ratio of about 5 times and a thickness of 0.2 mm.

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

A high-density polyethylene resin (manufactured by Nippon Polychem Co., Ltd.) having a weight average molecular weight (Mw) of 3.3 × 10 ⁵ and a melting point of 135 ° C. is supplied to the same-direction biaxial kneading extruder (manufactured by Plastic Engineering Laboratory), and the resin temperature is 200 After melt-kneading at 0 ° C., the melt-kneaded product was formed into a sheet having a thickness of 4.8 mm using a calendar molding machine controlled at a roll temperature of 110 ° C. to obtain a polyethylene resin sheet.

  The obtained polyethylene resin sheet was rolled at a rolling ratio of 8.0 times using a rolling molding machine (manufactured by Sekisui Koki Co., Ltd.) heated to 120 ° C. to obtain a rolled sheet having a thickness of 0.6 mm.

  The obtained rolled sheet is subjected to 3.0-fold multi-stage stretching with a hot-air heating type multi-stage stretching apparatus (manufactured by Kyowa Engineering) heated to 110 ° C., with a total draw ratio of 24.0 times and a thickness of 0.2 mm. A stretched polyethylene resin sheet was obtained.

  A polyester hot melt adhesive (trade name “Byron GM-920”, melting point 107 ° C., manufactured by Toyobo Co., Ltd., melting point 107 ° C.) is melt-extruded and coated to a thickness of 0.05 mm on both sides of the obtained stretched polyethylene sheet. An agent laminated stretched polyethylene sheet was obtained.

  Between the obtained two stretched polyethylene terephthalate sheets, one adhesive laminated stretched polyethylene sheet is sandwiched with the stretching direction aligned, and is passed between 150 ° C. hot roll presses to have a thickness of 0.61 mm A three-layer laminate was obtained.

  The obtained three-layer laminate was supplied to an 80 ° C. gear oven and subjected to a heat resistance test for 7 days. The tensile modulus was measured according to JIS K 7113, and it was 13 GPa.

(Comparative Example 1)
On both sides of the stretched polyethylene terephthalate sheet obtained in Example 1, a polyester hot melt adhesive (trade name “Byron GM-920”, melting point 107 ° C., manufactured by Toyobo Co., Ltd.) was melted to a thickness of 0.05 mm. By extrusion coating, an adhesive laminated stretched polyethylene terephthalate sheet was obtained.

  Between the two stretched polyethylene terephthalate sheets obtained in Example 1, the obtained adhesive-laminated stretched polyethylene terephthalate sheet was sandwiched by matching the stretching direction, and passed between 150 ° C. hot roll presses, 0 A three layer laminate of 61 mm was obtained.

  Thickness that vinyl chloride resin (product number “TS1000R” manufactured by Tokuyama Sekisui Co., Ltd., product number “TS1000R”) is extrusion coated at 190 ° C. on both sides of the obtained three-layer laminate, and vinyl chloride resin is laminated on both sides of the three-layer laminate. A 0.61 mm laminated molded body was obtained.

  The obtained three-layer laminate was supplied to an 80 ° C. gear oven and subjected to a heat resistance test for 7 days. The tensile elastic modulus was measured according to JIS K 7113, and was 10 GPa.

(Example 2)
A vinyl chloride resin (manufactured by Tokuyama Sekisui Co., Ltd., product number “TS1000R”) was extrusion coated at 190 ° C. on both sides of the three-layer laminate obtained in Example 1, and chlorinated on both sides of the three-layer laminate. A five-layer laminated molded body having a thickness of 1.61 mm on which vinyl resin was laminated was obtained.
It was 0.3 * 10 < ^-5 > / degreeC as a result of measuring the linear expansion coefficient of the obtained 5 layer lamination molded object based on JISK7197.

(Comparative Example 2)
A vinyl chloride resin (manufactured by Tokuyama Sekisui Co., Ltd., product number “TS1000R”) was extrusion coated at 190 ° C. on both surfaces of the three-layer laminate obtained in Comparative Example 1, and chlorinated on both surfaces of the three-layer laminate. A five-layer laminated molded body having a thickness of 1.61 mm on which vinyl resin was laminated was obtained.
It was 1.5 * 10 < ^-5 > / degreeC as a result of measuring the linear expansion coefficient of the obtained 5 layer lamination molded object based on JISK7197.

(Comparative Example 3)
A linear low-density polyethylene resin sheet (manufactured by Sekisui Film Co., Ltd.) having a melting point of 120 ° C. and a thickness of 0.05 mm was thermally fused on both sides of the stretched polyethylene resin sheet obtained in Example 1 with a 160 ° C. heating roll ( Sheet temperature was 125 ° C.) to obtain an adhesive laminated stretched polyethylene resin sheet having a thickness of 0.21 mm.

  Between the two stretched polyethylene resin sheets obtained in Example 1, the obtained adhesive-laminated stretched polyethylene resin sheet was sandwiched by matching the stretching direction, and passed between 160 ° C. hot roll presses. A layer stack was obtained.

  Polyvinyl chloride resin (product number “TS1000R” manufactured by Tokuyama Sekisui Co., Ltd.) was extrusion-coated at 190 ° C. on both sides of the obtained three-layer laminate, but laminate molding in which vinyl chloride resin was laminated on both sides of the three-layer laminate. No body was obtained.

Claims (20)

  A laminated molded body comprising a stretched thermoplastic polyester resin sheet and a stretched olefin resin sheet laminated.   2. The laminated molded body according to claim 1, wherein the surface is a stretched thermoplastic polyester resin sheet.   The stretched thermoplastic polyester resin sheet is a non-crystalline thermoplastic polyester resin sheet having a glass transition temperature of −20 ° C. to a glass transition temperature of the thermoplastic polyester resin + 20 ° C. The laminated molded body according to claim 1 or 2, which is a drawn-drawn thermoplastic polyester resin sheet obtained by drawing and drawing through a pair of rolls.   The laminated thermoplastic polyester resin sheet according to claim 3, wherein the stretched thermoplastic polyester resin sheet is a uniaxially stretched thermoplastic polyester resin sheet obtained by uniaxial stretching at a temperature higher than the temperature of the roll after drawing and stretching. Molded body.   The uniaxial stretching temperature is from a rising temperature of a crystallization peak of a thermoplastic polyester resin to a rising temperature of a melting peak in a differential operation calorie curve measured at a heating rate of 1 ° C / min. Laminated molded body.   The laminated molded article according to claim 4 or 5, wherein the uniaxially stretched thermoplastic polyester resin sheet is heat-set at a temperature higher than the uniaxial stretch temperature.   The lamination molding according to claim 6, wherein the heat setting temperature is a rising temperature of a melting peak of the thermoplastic polyester resin in a differential operation calorie curve measured at a uniaxial stretching temperature to a temperature rising rate of 1 ° C / min. body.   The laminated molded article according to any one of claims 1 to 7, wherein a stretch ratio of the stretched thermoplastic polyester resin sheet is 3 to 8 times.   The laminated molded article according to any one of claims 1 to 8, wherein the stretched thermoplastic polyester resin sheet has a negative coefficient of linear expansion.   The stretched thermoplastic polyester resin sheet and the stretched olefin resin sheet or two or more stretched thermoplastic polyester resin sheets are laminated so that the stretching directions are substantially the same. The laminated molded body according to any one of -6.   Stretched thermoplastic polyester resin sheet and stretched olefin resin sheet or two or more stretched thermoplastic polyester resin sheets having a melting point lower than the melting point of the thermoplastic polyester resin, a hot melt adhesive, a reactive adhesive 11. The adhesive according to claim 10, wherein the adhesive is bonded with one or more adhesives selected from the group consisting of epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives. Laminated molded body.   11. A woven fabric and / or a non-woven fabric is laminated between a stretched thermoplastic polyester resin sheet and a stretched olefin resin sheet or two or more stretched thermoplastic polyester resin sheets. Laminated molded body.   A hot melt adhesive having a melting point lower than the melting point of the thermoplastic polyester resin, reactive between the stretched thermoplastic polyester resin sheet and the stretched olefin resin sheet or two or more stretched thermoplastic polyester resin sheets A woven fabric and / or a nonwoven fabric impregnated with one or more adhesives selected from the group consisting of adhesives, epoxy adhesives, urethane adhesives, polyester adhesives and rubber adhesives. The laminated molded body according to claim 10, wherein the laminated molded body is laminated and bonded.     The laminated molded body according to any one of claims 1 to 13, wherein the stretched olefin resin sheet is a polyethylene resin sheet having a total stretch ratio of 10 to 40 times.   The laminate formed article according to claim 14, wherein the total draw ratio is 10 to 40 times, and the roll ratio is 5 to 10 times and the draw ratio is 1.3 to 4 times.   Furthermore, the thermoplastic resin layer is laminated | stacked on both surfaces, The laminated molded object of any one of Claims 1-15 characterized by the above-mentioned.   Hot-melt adhesive reactive adhesive, epoxy adhesive, urethane adhesive, polyester adhesive in which the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer have a melting point lower than that of the thermoplastic polyester resin The laminate molded body according to claim 16, wherein the laminate molded body is bonded with one or two or more types of adhesives selected from the group consisting of rubber adhesives.   The laminated molded body according to claim 16, wherein a woven fabric and / or a nonwoven fabric is laminated between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer.   Hot-melt adhesive, reactive adhesive, epoxy adhesive, urethane adhesive, polyester having a melting point lower than that of the thermoplastic polyester resin between the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer 17. A woven fabric and / or a nonwoven fabric impregnated with one or two or more types of adhesives selected from the group consisting of a base adhesive and a rubber adhesive is laminated and bonded. The laminated molded article described.   The laminated molded body according to any one of claims 1 to 19, wherein the laminated molded body is an exterior building material.