JP4909096B2 - Method for producing laminated molded body - Google Patents

Description

  The present invention relates to a method for producing a laminated molded body that can be suitably used as an exterior building material using a stretched thermoplastic polyester resin sheet as a core material.

Vinyl chloride resin has excellent water resistance, flame retardancy, mechanical properties, etc. and is relatively inexpensive, so it is widely used as a material for construction materials such as rain gutters. Since the linear expansion coefficient of the body is as large as 7.0 x 10 ^-5 (1 / ° C), when installing a rain gutter made of hard vinyl chloride resin, connect it with a joint that can absorb the expansion and contraction of the gutter. It was necessary to make the end free, but when the length of the rain gutter was increased, the joint became larger, the appearance was poor, and the joint part could be damaged when used for a long time. 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 linear expansion coefficient. For example, a stretched polyolefin resin or polyester resin layer uniaxially stretched in the length direction of the molded body is embedded over the entire length of the molded body made of a thermoplastic synthetic resin such as vinyl chloride resin. A synthetic resin long molded body (see, for example, Patent Document 1) characterized by being integrated has been proposed.
Japanese Patent Laid-Open No. 2005-120613

  However, the adhesion between the vinyl chloride resin and the polyester resin is low, and the adhesion between the vinyl chloride resin layer and the stretched polyester resin layer is difficult. In order to firmly bond the two, it is preferable to interpose a hot melt adhesive or a reactive adhesive. However, a hot melt adhesive or a reactive adhesive is applied to or laminated on a vinyl chloride resin layer or a polyester resin layer. After that, it was difficult to bond the both uniformly and firmly by pressurization and / or heating.

  In view of the above drawbacks, the object of the present invention is that the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer are firmly bonded, have a low coefficient of linear expansion, are lightweight, and have impact resistance, durability, workability, and productivity. It is an object of the present invention to provide a method for producing a laminated molded body that can be suitably used as an exterior building material such as a rain gutter, draining water, and a trunk.

  The method for producing a laminated molded article according to claim 1, wherein the thermoplastic polyester resin sheet in an amorphous state is converted from a glass transition temperature of the thermoplastic polyester resin −20 ° C. to a glass transition temperature of the thermoplastic polyester resin +20. An adhesive layer and a thermoplastic resin layer are sequentially laminated by coextrusion on both sides of a drawing-drawn thermoplastic polyester resin sheet obtained by drawing-drawing at a temperature of ° C.

  Examples of the thermoplastic polyester resin used in the present invention include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyglycolic acid, poly (L-lactic acid), poly (3-hydroxybutyrate), poly ( 3-hydroxybutyrate / hydroxyvalerate), poly (ε-caprolactone), polyethylene succinate, polybutylene succinate, polybutylene succinate adipate, polybutylene succinate / lactic acid, polybutylene succinate / carbonate, polybutylene succinate Nate / terephthalate, polybutylene adipate / terephthalate, polytetramethylenadipate / terephthalate, polybutylene succinate / adipate / terephthalate, etc. Polyethylene terephthalate is preferable.

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

  The 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 there exists a tendency which becomes difficult, 0.1-5 mm is preferable, More preferably, it is 0.2-3 mm.

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

  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. If the preheating temperature is too low or too high, the resin sheet may not reach a predetermined temperature. Therefore, the glass transition temperature of the thermoplastic polyester resin −20 ° C. to the glass transition temperature of the thermoplastic polyester resin +10 A temperature of ° C is preferred.

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

  In addition, when the amorphous polyester resin sheet in an amorphous state is pulled out, the roll does not necessarily rotate. However, particularly when the thermoplastic polyester resin sheet is thick, heat accumulation of the roll due to shearing heat generation occurs. It is preferable to rotate the sheet in the drawing direction because the temperature of the resulting sheet is likely to increase.

  When the rotation speed of the roll is slow, the contact time between the roll and the thermoplastic polyester resin sheet becomes longer, frictional heat is generated, the roll temperature rises, and the effect of cooling the heated thermoplastic polyester resin is reduced. However, when the predetermined drawing and stretching temperature is exceeded and the rotational speed of the roll is increased, only the thermoplastic polyester resin on the surface of the thermoplastic polyester resin sheet flows and cannot be drawn and drawn uniformly. Further, the elastic modulus of the drawn and drawn thermoplastic polyester resin sheet is lowered.

  Therefore, the rotational speed of the roll is preferably substantially the same or lower than the feed speed when the thermoplastic polyester resin sheet is pulled out in the state where the roll is not rotating at the same drawing speed.

  Further, when the thickness of the thermoplastic polyester resin sheet is large (1.5 mm or more), heat generation due to shearing between the roll and the sheet becomes large, and therefore, the rotation speed of the roll is preferably 50 to 100% of the feed speed. . Moreover, when the thickness of the thermoplastic polyester resin sheet is thin, the cooling effect by the roll is great, so the rotation speed of the roll may be slow.

  The draw ratio of the above-described drawing stretching is not particularly limited, but if the stretching ratio is low, the tensile strength and the tensile elastic modulus tend to decrease, and if it is high, the sheet tends to break during stretching. Therefore, 2-9 times are preferable, More preferably, it is 2.5-7 times.

  The drawn and drawn thermoplastic polyester resin sheet that has been drawn and drawn is preferably heat-set in order to further improve 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 However, when the temperature is higher than the melting peak rise temperature, the thermoplastic polyester resin dissolves and the stretching (orientation) disappears, the tensile modulus, tensile strength, etc. are lowered, and when the drawing stretching temperature is higher by 30 ° C. or more, Since the orientation of the crystallized crystal at the drawing 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 higher 30 degreeC or more than drawing drawing temperature is preferable.

  In addition, when heat-fixed, the drawn stretched thermoplastic polyester resin sheet is stretched if a load is applied, and shrinks in a free state. Therefore, the length of the drawn stretched thermoplastic polyester resin sheet in the stretching direction is substantially It is preferable to carry out in the state which did not change automatically, and it is preferable that the pressure is not applied to the drawing extending | stretching thermoplastic polyester-type resin sheet.

  That is, the length of the heat-set drawing stretched thermoplastic polyester resin sheet is 0.95 to 1.1 of the length of the draw-drawn thermoplastic polyester resin sheet before heat setting, which is lower than the drawing draw ratio. It is preferable to heat fix so that

  Therefore, when the stretch-drawn thermoplastic polyester resin sheet is continuously heat-fixed while moving in a heating chamber with a roll such as a pinch roll, the feed speed of the draw-stretched thermoplastic polyester resin sheet on the inlet side and the outlet side It is preferable that the ratio is set to 0.95 to 1.1 and set to be lower than the draw ratio and heat-set.

  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, and is generally 10 seconds to 10 minutes, although it varies depending on the thickness of the drawn stretched thermoplastic polyester resin sheet and the heat setting temperature.

  Further, the heat-drawn drawing stretch thermoplastic polyester resin sheet was measured for the rising temperature of the crystallization peak of the thermoplastic polyester resin on the differential scanning calorimetry curve measured at a glass transition temperature to a heating rate of 10 ° C./min. In the range, it is preferable to anneal in a state where substantially no tension is applied.

  By annealing, the drawn stretched thermoplastic polyester resin sheet has good mechanical properties such as elastic modulus, and the mechanical properties such as elastic modulus decrease even when heated to a temperature above the glass transition temperature. And the shrinkage rate can be kept low.

  Also, when the annealing is performed, the drawing stretched thermoplastic polyester resin sheet is stretched if a large tension is applied. Therefore, it is preferable that the drawing stretching thermoplastic polyester resin sheet is annealed in a state where substantially no tension is applied. .

  That is, it is preferable that annealing is performed so that the length of the drawn stretched thermoplastic polyester resin sheet after annealing is 1.0 or less of the length of the drawn stretched thermoplastic polyester resin sheet before annealing.

  Therefore, when the drawn stretched thermoplastic polyester resin sheet is continuously annealed while being moved in the heating chamber by a roll such as a pinch roll, the feed rate ratio of the drawn stretched thermoplastic polyester resin sheet on the inlet side and the outlet side is set to It is preferable that annealing is performed with setting to be 1.0 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 drawn stretched thermoplastic polyester resin sheet and the annealing temperature, but is generally preferably 10 seconds or more, more preferably 30 seconds to 60 minutes, and still more preferably 1 to 1. 20 minutes.

When the draw-stretched thermoplastic polyester resin sheet has a large linear expansion coefficient, it expands and contracts greatly due to a temperature difference. Therefore, it is preferably −1.5 × 10 ⁻⁵ or more and less than 0.

  Further, when the tensile modulus of the drawn thermoplastic polyester resin sheet is less than 7 GPa, the linear expansion coefficient of the laminated molded body in which the thermoplastic resin layers are laminated on both sides of the drawn stretched thermoplastic polyester resin sheet is increased to 15 GPa. If it exceeds the upper limit, the impact resistance of the laminated molded article is lowered, so that the tensile elastic modulus of the drawn stretched thermoplastic polyester resin sheet is preferably 7 to 15 GPa.

  In the present invention, the drawn and stretched thermoplastic polyester resin sheet is preferably further uniaxially stretched at a temperature higher than the drawing temperature.

  The polyester resin of the draw-drawn thermoplastic polyester resin sheet has high strength and elastic modulus because the molecular chains are highly oriented in a state where isotropic crystallization and orientation are suppressed due to heat, which is an impediment to stretching. However, since the degree of crystallinity is low, the orientation is easily relaxed and the elastic modulus is lowered when heated.

  However, this drawing stretch thermoplastic polyester resin sheet is uniaxially stretched at a temperature higher than the drawing temperature, so that the crystallinity is increased without relaxation and the orientation is not easily relaxed even when heated. A highly uniaxially stretched thermoplastic polyester resin sheet is obtained.

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

  The temperature at the time of the uniaxial stretching may be higher than the temperature of the pair of rolls at the time of primary stretching, but if it is too high, the drawn stretched thermoplastic polyester resin sheet tends to melt and be 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, the tensile strength, the tensile elastic modulus, etc. tend to decrease, and if it is high, the sheet tends to break during stretching. Therefore, 1.05 to 3 times is preferable, and 1.1 to 2 times is more preferable. Further, the total draw ratio of the drawing and uniaxial drawing (the product of the drawing and uniaxial drawing ratio) is preferably 2.5 to 10 times, more preferably 3 to 8 times for the same reason.

  The uniaxially stretched thermoplastic polyester resin sheet is preferably heat-set and annealed in order to improve heat resistance in the same manner as the draw-stretched thermoplastic polyester resin sheet. The heat setting and annealing of the uniaxially stretched thermoplastic polyester resin sheet may be performed in the same manner as the heat setting and annealing of the drawing stretch thermoplastic polyester resin sheet, and only different points will be described below.

  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.

If the linear expansion coefficient of the uniaxially stretched thermoplastic polyester resin sheet is large, the linear expansion coefficient greatly expands / contracts due to a temperature difference. Therefore, it is preferably −1.5 × 10 ⁻⁵ or more and less than 0.

  If the tensile modulus of the uniaxial thermoplastic polyester resin sheet is also less than 7 GPa, the linear expansion coefficient of the laminated molded body in which the thermoplastic resin layers are laminated on both sides of the uniaxially stretched thermoplastic polyester resin sheet is increased to 15 GPa. If it exceeds the upper limit, the impact resistance of the laminated molded body is lowered, so that the tensile elastic modulus of the uniaxially stretched thermoplastic polyester resin sheet is preferably 7 to 15 GPa.

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

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

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

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

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

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

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

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

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

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

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

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

The basis weight 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.

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

  As the method of fusing with the ultrasonic welder, any conventionally known method may be employed. For example, the stretched thermoplastic polyester resin sheet, the hot melt adhesive, the woven fabric and / or the nonwoven fabric, and the thermoplastic resin. A method of passing a laminated body such as a layer between a horn and a knurl that are vibrated at a frequency of 15 to 40 kHz is mentioned.

  FIG. 1 is an explanatory view showing an example of a method in which two stretched thermoplastic polyester resin sheets are made by an ultrasonic welder with a thermoplastic polyester resin woven fabric which is a hot melt adhesive.

  In the figure, reference numerals 1 and 1 denote drawn or uniaxially stretched thermoplastic polyester resin sheets, and between the drawn or uniaxially stretched thermoplastic polyester resin sheets 1 and 1, a woven fabric hot melt adhesive sheet 2 made of thermoplastic polyester resin. Are stacked to form a stacked body 10.

  The laminate 10 is transported while being pressed by the horn 3 and the knurl 4 and is excited by the frictional heat generated by the ultrasonic vibration transmitted from the horn 3 by vibrating the horn 3 at a frequency of 15 to 40 kHz. The woven fabric 2 made of plastic polyester resin is heated and melted and fused.

  At this time, in order to fuse more efficiently, it is preferable that the gap between the horn 3 and the knurl 4 is set smaller than the thickness of the laminated body 10 and the laminated body 10 is fused while being pressed with the horn 3 and the knurl 4. In order to pressurize, it is preferable to connect an air cylinder, a hydraulic cylinder, etc. to the horn 3 and press the horn 3 against the knurl 4 through the laminate 10.

  In addition, since the protrusions are formed on the surface of the knurl 4, fusion can be performed more efficiently. By changing the arrangement and shape of the protrusions, the arrangement of the fusion parts and the pattern of the shape can be changed. can do.

  2-6 is explanatory drawing which shows the example of the arrangement | sequence pattern of a fusion | fusion part. In the figure, 10 is a laminate fused by an ultrasonic welder, A is the stretching direction of the stretched thermoplastic polyester resin sheet 1, and 5 is a fused site.

  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.

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

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

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

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

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

  In the present invention, an adhesive layer and a thermoplastic resin layer are sequentially laminated by coextrusion on both sides of a drawn stretched thermoplastic polyester resin sheet or a uniaxially stretched thermoplastic polyester resin sheet to produce a laminated molded body. However, in order to improve the adhesion between the drawn or uniaxially stretched thermoplastic polyester resin sheet and the adhesive layer and the thermoplastic resin layer, both surfaces of the drawn or uniaxially stretched thermoplastic polyester resin sheet are subjected to surface oxidation treatment or surface hydrolysis. It is preferable to apply the treatment and then laminate the adhesive layer and the thermoplastic resin layer sequentially by coextrusion to produce a laminated molded body.

  The surface oxidation treatment may be any treatment method conventionally used for oxidation treatment of thermoplastic resin sheets. For example, corona discharge treatment, flame treatment, plasma treatment, glow discharge treatment, ozone treatment, chromic acid, Examples include ultraviolet treatment, electron beam treatment, and radiation treatment, and corona discharge treatment and chromic acid treatment are preferred.

  The corona discharge treatment is performed by passing a stretched thermoplastic polyester resin sheet between an insulated electrode and a dielectric roll provided with a counter electrode, and applying high frequency and high voltage therebetween. The corona discharge treatment can be performed in an air atmosphere, a nitrogen gas atmosphere, an oxygen gas atmosphere, a nitrogen-oxygen mixed gas atmosphere, or the like.

  The chromic acid treatment is performed by immersing a drawn or uniaxially stretched thermoplastic polyester resin sheet in an acidic aqueous solution of dichromic acid or a salt thereof. For example, a drawn thermoplastic polyester resin sheet is immersed in a chromic acid mixture consisting of 120 g of sodium dichromate, 1 liter of water and 1.6 liter of concentrated sulfuric acid, and then washed with water and dried to remove the chromic acid. Alternatively, a uniaxially stretched thermoplastic polyester resin sheet can be obtained.

  The hydrolysis treatment is performed by immersing a drawn or uniaxially stretched thermoplastic polyester resin sheet in acidic or alkaline water. In this case, it is preferable to heat to accelerate the reaction. For example, a drawn or uniaxially stretched thermoplastic polyester resin sheet is immersed in a 20% by weight aqueous solution of sodium hydroxide at 80 ° C. for 1 minute or more, preferably 4 minutes or more, then washed with water and dried to perform drawing. Alternatively, a uniaxially stretched thermoplastic polyester resin sheet can be obtained.

  The thermoplastic resin is laminated on both sides of a drawn or uniaxially stretched thermoplastic polyester resin sheet to protect the stretched thermoplastic polyester resin sheet from cracking and cracking along the stretch direction due to impact, and polyester. This prevents the resin from being subjected to hydrolysis or deterioration by direct exposure to rainwater or sunlight, resulting in a decrease in durability.

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

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

  The above adhesive is for firmly bonding the drawn or uniaxially stretched thermoplastic polyester resin sheet and the thermoplastic resin layer, and has a melting point lower than the melting point of thermoplastic polyester resins such as polyurethane resins and polyester resins. The hot-melt type adhesive and reactive adhesive which have are used.

  Examples of the hot melt adhesive include urethane hot melt adhesives, polyester hot melt adhesives, rubber hot melt adhesives, olefin hot melt adhesives, and acrylic hot melt adhesives. Examples of reactive adhesives include silicone adhesives (for example, trade name “one-part silicone adhesive 8060” manufactured by Cemedine), modified silicone adhesives, and the like. Adhesive (for example, Cemedine Co., Ltd., trade name “one-component modified silicone adhesive PM-100”, Kaneka Chemical Co., Ltd., trade name “MS polymer”), urethane adhesive (for example, Auto Chemical Industries, Ltd.) Product name “one-component urethane adhesive autoadher 5000, manufactured by Sekisui Fuller, product name“ Sdyne 9635 ”), etc. .

  The above-mentioned adhesive is for strongly bonding the drawn or uniaxially stretched thermoplastic polyester resin sheet and the thermoplastic resin layer, and is drawn or uniaxially stretched thermoplastic polyester resin by sequentially co-extruding the adhesive and the thermoplastic resin. Since the sheet is extrusion coated, the adhesive layer is preferably thinner than the thermoplastic resin layer, and the melt viscosity of the adhesive is preferably lower than the melt viscosity of the thermoplastic resin.

  Since the adhesive and the thermoplastic resin are sequentially co-extruded and drawn or coated on the uniaxially stretched thermoplastic polyester resin sheet and laminated to produce a laminated molded body, the first supply port and the second supply port are Drawing or uniaxially stretched thermoplastic resin in the core material passage of an extrusion mold comprising a second mold that forms a core material passage between the first mold provided and the first mold It is preferable to supply a polyester-based resin sheet, draw out from the first supply port, or extrusion-coat the adhesive onto the uniaxially stretched thermoplastic polyester-based resin sheet, and extrusion-coat the thermoplastic resin from the second supply port.

  7 is a cross-sectional view showing an example of the extrusion mold, FIG. 8 is a partial enlarged cross-sectional view of a portion B in FIG. 7, and FIG. 9 is a partial enlarged cross-sectional view of a portion C in FIG.

  In the figure, reference numeral 6 denotes a first mold, 7 denotes a second mold, and a core material passage 8 is formed by the first mold 6 and the second mold 7. The first mold 6 and the second mold 7 have first supply ports 61 and 71 and second supply ports 62 and 72, respectively. The second supply port 62 and the second supply port 72 are formed to face each other.

  The core material passage 8 has a core from immediately after the first supply ports 61 and 71 to immediately before the second supply ports 62 and 72 through the clearance of the upstream core material passage 81 immediately before the first supply ports 61 and 71. The clearance of the material passage 82 is made larger, and the clearance of the core material passage 83 downstream of the second supply ports 62 and 72 is made larger than the clearance of the core material passage 82.

  The first supply ports 61 and 71 are connected to an extruder for supplying a melted adhesive, and are used for supplying an adhesive to a drawn or uniaxially stretched thermoplastic polyester resin sheet for extrusion coating. The two supply ports 62 and 72 are connected to an extruder for supplying a molten thermoplastic resin, and supply the thermoplastic resin to the drawn or uniaxially stretched thermoplastic polyester resin sheet on which the adhesive is laminated to perform extrusion coating. Is for.

  When the drawn or uniaxially stretched thermoplastic polyester resin sheet is supplied to the core material passage 8 of the extrusion mold, the drawn or uniaxially stretched thermoplastic polyester resin sheet collides with the inlet or side wall of the core material passage 8. When contacted, the physical properties and appearance of the laminated molded body in which the drawn or uniaxially stretched thermoplastic polyester resin sheet is scratched are deteriorated, so that the clearance is gradually increased from the opening of the extrusion mold to the entrance of the core material passage 81. The tapered portion 9 is formed so as to be small.

  FIG. 10 is a partial cross-sectional view showing an example of a method for producing a laminate according to the present invention. In the figure, reference numeral 1 denotes a drawn or uniaxially stretched thermoplastic polyester resin sheet, and a drawn or uniaxially stretched thermoplastic polyester resin sheet 1 in the core material passage 81 immediately before the first supply ports 61 and 71 of the extrusion mold. The distance from the inner wall surface of the core material passage 81 is T1, the distance of the core material passage 81 on the upstream side of the first supply port whose distance is T1 is L1, and the core material passage 82 just before the second supply ports 62 and 72 is used. The distance between the drawing material or the uniaxially stretched thermoplastic polyester resin sheet 1 and the inner wall surface of the core material passage 82 is T2, and the distance of the core material passage 82 upstream of the second supply ports 62 and 72 whose distance is T2 is L2. In this case, it is preferable that L1 / T1> L2 / T2.

  When the drawn or uniaxially stretched thermoplastic polyester resin sheet 1 becomes thin and the distance between the drawn or uniaxially stretched thermoplastic polyester resin sheet 1 and the inner wall surface of the core material passage 81 becomes larger, the supplied adhesive becomes the core material passage 31. There is a risk of leakage. In particular, since the thermoplastic resin supplied from the second supply port is pressurized and sealed, and is pressurized by the pressure of the extruder that supplies the adhesive from the first supply port, the distance T1 is If it is large or the distance of the core material passage 81 is short, the adhesive may leak from the core material passage 81. Furthermore, it is remarkable when the melt viscosity of the adhesive is lower than the melt viscosity of the thermoplastic resin. Therefore, the relationship between the distance of the core material passage 81 and the clearance is preferably L1 / T1> L2 / T2.

  In addition, when an adhesive and a thermoplastic resin are laminated on the extrusion-molding die by drawing or uniaxially stretched thermoplastic polyester resin sheet by coextrusion, the drawn or uniaxially stretched thermoplastic polyester resin sheet is used as a core passage. 8 and is preferably stacked while being taken from the downstream side of the core material passage 8. As shown in FIG. 11, the middle of the core material passage 82 is expanded to form the resin reservoir 11. The adhesive can be drawn more uniformly or laminated on a uniaxially stretched thermoplastic polyester resin sheet. When the resin reservoir 11 is formed, the distance of the core material passage 82 on the upstream side of the second supply ports 62 and 72 whose distance is T2 is the second distance L2 from the downstream side of the resin reservoir 11. This is the distance to the supply ports 62 and 72.

  Moreover, as shown in FIG. 12, the core material passage 82 may be formed with a stepped portion 12 and the clearance may be gradually reduced, or the clearance may be gradually reduced in a tapered shape. In this case, the distance L2 of the core material passage 82 upstream of the second supply ports 62 and 72 whose distance is T2 is the distance from the portion where the distance is T2 to the second supply ports 62 and 72. The distance to just before.

  The laminated molded body produced by the present invention can be molded into a predetermined shape by a molding method such as odd-shaped molding and bending, and a laminated molded body having a predetermined shape is obtained. Moreover, in order to improve the weather resistance and designability of the laminated molded body, different resin layers may be laminated on the surface of the thermoplastic resin layer, or a paint may be applied.

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

  The structure of the method for producing the laminated molded body of the present invention is as described above, and the drawn or uniaxially stretched thermoplastic polyester resin sheet and the thermoplastic resin layer are firmly bonded, the coefficient of linear expansion is low, the weight is light, and the impact resistance It is possible to easily produce a laminated molded body having excellent properties, durability, workability, productivity and the like.

  In addition, when an adhesive and a thermoplastic resin are laminated by coextrusion on a single extrusion mold or drawn or uniaxially stretched thermoplastic polyester resin sheet, the adhesive and the thermoplastic resin are laminated by coextrusion using different molds. Compared to the above, the drawn or uniaxially stretched thermoplastic polyester resin sheet is less likely to be damaged by contact with the extrusion mold, and the adhesive layer laminated on the drawn or uniaxially stretched thermoplastic polyester resin sheet has Since it is not scraped off by the mold, the appearance is good, and a laminated molded body in which the drawn or uniaxially stretched thermoplastic polyester resin sheet and the thermoplastic resin layer are firmly bonded can be produced.

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

Example 1
Polyethylene terephthalate (trade name “NEH-2070” manufactured by Unitika Ltd., intrinsic viscosity 0.88) was melt-extruded and then rapidly cooled to obtain a polyethylene terephthalate sheet (crystallinity 1.3%) having a thickness of 2.5 mm. It was. The obtained polyethylene terephthalate sheet is supplied to a stretching apparatus (manufactured by Kyowa Engineering Co., Ltd.), preheated to 80 ° C., heated to 74 ° C., and rotated in the stretching direction at a speed of 0.05 m / min. The film was drawn and stretched at a speed of 2 m / min between rolls (0.5 mm between rolls) to obtain a drawn stretched polyethylene terephthalate sheet having a stretch ratio of about 5 times and a thickness of 0.5 mm.

  The polyethylene terephthalate sheet has a glass transition temperature of 76.7 ° C., a rising temperature of the crystallization peak in a differential scanning calorimetry curve measured at a heating rate of 10 ° C./min is about 140 ° C., and a rising temperature of the melting peak. Was about 234 ° C.

  The obtained drawn stretched polyethylene terephthalate sheet is supplied to the extrusion mold shown in FIGS. 7 to 10, the adhesive is supplied from the first supply ports 61 and 71, and the heat is supplied from the second supply ports 62 and 72. A plastic resin was supplied at 200 ° C. and taken from the downstream side at a speed of 1 m / min to obtain a laminate in which an adhesive and a thermoplastic resin were laminated.

  The adhesive was a polyester-based hot melt adhesive (manufactured by Toyobo Co., Ltd., trade name “Byron GM913”, melting point 126 ° C.), and the thickness of the obtained laminate was 0.07 mm. The thermoplastic resin was a vinyl chloride resin (manufactured by Tokuyama Sekisui Co., Ltd., product number “TS1000R”), and the thickness of the obtained laminate was 0.4 mm.

  The extrusion mold L1 was 20 mm, L2 was 6 mm, T1 was 0.125 mm, and T2 was 0.150 mm. Therefore, (L1 / T1) = (20 / 0.125) = 160, (L2 / T2) = (6 / 0.150) = 40, and L1 / T1> L2 / T2.

It was 1.4 * 10 < ^-5 > (1 / degreeC) when the linear expansion coefficient of the obtained laminated molded object was measured based on JISK7197. The tensile modulus measured according to JIS K 7113 was 4.9 GPa, and the T-peeling strength measured according to JIS K 6854 was 59 N / 25 mm width.

(Example 2)
Polyethylene terephthalate (trade name “NEH-2070” manufactured by Unitika Ltd., intrinsic viscosity 0.88) was melt-extruded and then rapidly cooled to obtain a polyethylene terephthalate sheet (crystallinity 1.3%) having a thickness of 2.5 mm. It was. The obtained polyethylene terephthalate sheet is supplied to a stretching apparatus (manufactured by Kyowa Engineering Co., Ltd.), preheated to 80 ° C., heated to 74 ° C., and rotated in the stretching direction at a speed of 0.05 m / min. (Roll interval 0.5 mm) is drawn and stretched at a speed of 2 m / min, and further, the surface temperature of the polyethylene terephthalate sheet is heated to 180 ° C. in a hot air heating tank, and the outlet speed is set to 2.5 m / min. The film was stretched to obtain a uniaxially stretched polyethylene terephthalate sheet having a stretch ratio of about 5 times and a thickness of 0.5 mm.

  The polyethylene terephthalate sheet has a glass transition temperature of 76.7 ° C., a rising temperature of the crystallization peak in a differential scanning calorimetry curve measured at a heating rate of 10 ° C./min is about 140 ° C., and a rising temperature of the melting peak. Was about 234 ° C.

Using the obtained uniaxially stretched polyethylene terephthalate sheet, an adhesive and a thermoplastic resin were laminated in the same manner as in Example 1 to obtain a laminated molded body. It was 1.3 * 10 < ^-5 > (1 / degreeC) when the linear expansion coefficient of the obtained laminated molded object was measured based on JISK7197. In addition, the tensile modulus measured according to JIS K 7113 was 5.1 GPa, and the T-peeling strength measured according to JIS K 6854 was 57 N / 25 mm width.

Example 3
Both surfaces of the uniaxially stretched polyethylene terephthalate sheet obtained in Example 2 were subjected to corona discharge treatment under the following conditions to obtain a surface oxidized uniaxially stretched polyethylene terephthalate sheet. Discharge amount: 133 W · min / m ²
Sheet processing speed: 7 m / min Sheet / electrode distance: 2 mm

Using the obtained surface oxidation-treated uniaxially stretched polyethylene terephthalate sheet, an adhesive and a thermoplastic resin were laminated in the same manner as in Example 1 to obtain a laminated molded body. It was 1.3 * 10 < ^-5 > (1 / degreeC) when the linear expansion coefficient of the obtained laminated molded object was measured based on JISK7197. The tensile modulus measured according to JIS K 7113 was 5.1 GPa, and the T-peeling strength measured according to JIS K 6854 was 80 N / 25 mm width.

It is explanatory drawing which shows an example of the method of fuse | melting two extending | stretching thermoplastic polyester-type resin sheets by the ultrasonic welder with the thermoplastic polyester-type resin woven fabric which is a hot-melt-type adhesive agent. It is explanatory drawing which shows an example of the arrangement pattern of the fusion | melting site | part of a laminated body. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated body differs. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated body differs. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated body differs. It is explanatory drawing which shows the example from which the sequence pattern of the fusion | melting site | part of a laminated body differs. It is sectional drawing which shows an example of the metal mold | die for extrusion molding. It is a partial expanded sectional view of the A section in FIG. It is a partial expanded sectional view of the B section in FIG. It is a fragmentary sectional view showing an example of a manufacturing method of a lamination fabrication object of the present invention. It is sectional drawing which shows an example of the die for extrusion molding in which the resin reservoir part was formed in the core material channel | path. It is sectional drawing which shows an example of the metal mold | die for extrusion molding by which the clearance of the core material channel | path is made small in steps.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Pulled or uniaxially stretched thermoplastic polyester resin sheet 2 Thermoplastic polyester resin woven fabric hot melt adhesive sheet 3 Horn 4 Knurl 5 Fusion site 6 First mold 7 Second mold 8 Core material passage 9 Tapered portion 10 Laminate 11 Resin reservoir 12 Staircase

Claims (42)

  Drawing stretching obtained by 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. An adhesive layer and a thermoplastic resin layer are sequentially laminated on both surfaces of a thermoplastic polyester resin sheet by coextrusion.   The method for producing a laminated molded article according to claim 1, wherein the amorphous polyester resin sheet has a crystallinity of less than 10% as measured by a differential scanning calorimeter.   The method for producing a laminated molded article according to claim 1 or 2, wherein the drawing and drawing are performed through a pair of rolls set at the temperature.   After preheating the amorphous polyester resin sheet in an amorphous state at 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., a gap between the pair of rolls is obtained. The method for producing a laminated molded article according to claim 3, wherein the laminated molded article is passed.   4. The roll according to claim 3, wherein the roll is rotated in the drawing direction at a speed substantially equal to or less than a feed speed when the sheet is pulled out in a state where the roll is not rotated at the same drawing speed. Or the manufacturing method of the laminated molded object of 4.   The method for producing a laminated molded article according to any one of claims 1 to 5, wherein the draw ratio of the drawn stretched thermoplastic polyester resin sheet is 2 to 9 times.   Drawing stretch thermoplastic polyester resin sheet is the rising temperature of the crystallization peak to the melting peak of the thermoplastic polyester resin on the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min. The method for producing a laminated molded body according to any one of claims 1 to 6, wherein the heat-fixing is performed at a temperature not higher than 30 ° C by a temperature.   8. The method for producing a laminated molded article according to claim 7, wherein the heat setting is performed in a state in which the length of the drawn and drawn thermoplastic polyester resin sheet does not substantially change.   The length of the heat-fixed drawing-drawn thermoplastic polyester resin sheet is 0.95 to 1.1 of the length of the drawing-drawn thermoplastic polyester resin sheet before heat setting. Or the manufacturing method of the laminated molded object of 8.   The method for producing a laminated molded article according to any one of claims 7 to 9, wherein the heat setting time is 10 seconds to 10 minutes.   The heat-set drawing-drawn thermoplastic polyester resin sheet is annealed at a temperature below the glass transition temperature to less than the melting point in a state where no tension is substantially applied. The manufacturing method of the laminated molded object of description.   The annealing temperature is in a range of a rising temperature of a crystallization peak of a thermoplastic polyester resin in a differential scanning calorimetry curve measured at a glass transition temperature to a heating rate of 10 ° C / min. The manufacturing method of the laminated molded object of description.   The method for producing a laminated molded product according to claim 11 or 12, wherein the annealing time is 10 seconds or more.   14. A surface oxidation treatment or a surface hydrolysis treatment is performed on both surfaces of a drawing-drawn thermoplastic polyester resin sheet, and then an adhesive layer and a thermoplastic resin layer are sequentially laminated by coextrusion. The manufacturing method of the laminated molded object of any one of these.   The method for producing a laminated molded article according to claim 14, wherein the surface oxidation treatment is a corona discharge treatment or a chromic acid treatment.   The method for producing a laminated molded article according to any one of claims 1 to 15, wherein the adhesive is a hot-melt adhesive having a melting point lower than that of the thermoplastic polyester resin.   The method for producing a laminated molded body according to any one of claims 1 to 16, wherein the thermoplastic resin is a vinyl chloride resin.   Extrusion mold comprising a first mold provided with a first supply port and a second supply port, and a second mold forming a core passage between the first mold and the first mold The drawn stretched thermoplastic polyester resin sheet is supplied to the core material passage, the adhesive is extruded onto the drawn stretched thermoplastic polyester resin sheet from the first supply port, and the thermoplastic resin is applied from the second supply port. The method for producing a laminated molded body according to any one of claims 1 to 17, wherein extrusion coating is performed.   The upstream side of the first supply port where the distance between the draw-stretched thermoplastic polyester resin sheet and the inner wall surface of the core material passage in the core material passage just before the first supply port of the extrusion mold is T1, and the distance is T1 The distance of the core material passage is L1, the distance between the drawn and stretched thermoplastic polyester resin sheet and the inner wall surface of the core material passage in the core material passage immediately before the second supply port is T2, and the distance is T2. 19. The method for producing a laminated molded article according to claim 18, wherein L1 / T1> L2 / T2 is established, where L2 is a distance of the core material passage on the upstream side of the mouth.   The method for producing a laminated molded body according to claim 18 or 19, wherein a resin reservoir is formed in a core material passage between the first supply port and the second supply port of the mold for extrusion molding.   The laminate molding according to claim 19 or 20, wherein the clearance of the core material passage between the first supply port and the second supply port of the mold for extrusion molding is narrowed gradually or stepwise. Body manufacturing method.   The laminated molded body according to any one of claims 19 to 21, wherein a tapered portion is formed so that the clearance gradually decreases from the opening of the extrusion molding die to the entrance of the core passage. Production method.   The drawn stretched thermoplastic polyester resin sheet is further uniaxially stretched at a temperature higher than the drawing stretch temperature, and the adhesive layer and the thermoplastic resin layer are sequentially co-located on both sides of the obtained uniaxially stretched thermoplastic polyester resin sheet. It laminates by extrusion, The manufacturing method of the laminated molded object of any one of Claims 1-6 characterized by the above-mentioned.   The uniaxial stretching temperature is from a rising temperature of a crystallization peak of a thermoplastic polyester resin to a rising temperature of a melting peak in a differential scanning calorimetry curve measured at a heating rate of 10 ° C / min. A method for producing a laminated molded article.   The method for producing a laminated molded article according to claim 23 or 24, wherein the total stretching ratio (drawing stretching ratio x uniaxial stretching ratio) of the uniaxially stretched thermoplastic polyester resin sheet is 3 to 8 times.   The uniaxially stretched thermoplastic polyester resin sheet is the rising temperature of the crystallization peak of the thermoplastic polyester resin to the rising temperature of the melting peak on the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min. The method for producing a laminated molded article according to any one of claims 23 to 25, wherein heat setting is performed at a temperature not higher by 30 ° C than the temperature.   27. The method for producing a laminated molded body according to claim 26, wherein the heat setting is performed in a state where the length of the uniaxially stretched thermoplastic polyester resin sheet does not substantially change.   27. The length of the heat-fixed uniaxially stretched thermoplastic polyester resin sheet is 0.95 to 1.1 of the length of the uniaxially stretched thermoplastic polyester resin sheet before heat setting. Or the manufacturing method of the laminated molded object of 27.   The method for producing a laminated molded article according to any one of claims 26 to 28, wherein the heat setting time is 10 seconds to 10 minutes.   30. The heat-fixed uniaxially stretched thermoplastic polyester resin sheet is annealed at a temperature between the glass transition temperature and the melting point and substantially free of tension. The manufacturing method of the laminated molded object of description.   The annealing temperature is in the range of the rising temperature of the crystallization peak of the thermoplastic polyester resin in the differential scanning calorimetry curve measured at a glass transition temperature to a heating rate of 10 ° C / min. The manufacturing method of the laminated molded object of description.   32. The method for producing a laminated molded article according to claim 30, wherein the annealing time is 10 seconds or longer.   The surface of the uniaxially stretched thermoplastic polyester resin sheet is subjected to surface oxidation treatment or surface hydrolysis treatment, and then an adhesive layer and a thermoplastic resin layer are sequentially laminated by coextrusion. The manufacturing method of the laminated molded object of any one of these.   The method for producing a laminated molded article according to claim 33, wherein the surface oxidation treatment is corona discharge treatment or chromic acid treatment.   The method for producing a laminated molded article according to any one of claims 23 to 34, wherein the adhesive is a hot-melt adhesive having a melting point lower than that of the thermoplastic polyester resin.   36. The method for producing a laminated molded body according to any one of claims 23 to 35, wherein the thermoplastic resin is a vinyl chloride resin.   Extrusion mold comprising a first mold provided with a first supply port and a second supply port, and a second mold forming a core passage between the first mold and the first mold A uniaxially stretched thermoplastic polyester resin sheet is supplied to the core material passage, and an adhesive is extrusion coated on the uniaxially stretched thermoplastic polyester resin sheet from the first supply port, and the thermoplastic resin is applied from the second supply port. 37. The method for producing a laminated molded body according to any one of claims 23 to 36, wherein extrusion coating is performed.   The upstream side of the first supply port where the distance between the uniaxially stretched thermoplastic polyester resin sheet and the inner wall surface of the core material passage in the core material passage immediately before the first supply port of the extrusion mold is T1, and the distance is T1 The distance of the core material passage is L1, the distance between the uniaxially stretched thermoplastic polyester resin sheet and the inner wall surface of the core material passage in the core material passage just before the second supply port is T2, and the distance is T2. 38. The method for producing a laminated molded body according to claim 37, wherein L1 / T1> L2 / T2 is established, where L2 is a distance between the core material passages upstream of the mouth.   The method for producing a laminated molded body according to claim 37 or 38, wherein a resin reservoir is formed in a core material passage between the first supply port and the second supply port of the mold for extrusion molding.   40. Laminate molding according to claim 38 or 39, wherein the clearance of the core material passage between the first supply port and the second supply port of the mold for extrusion molding is narrowed gradually or stepwise. Body manufacturing method.   41. The laminated molded body according to any one of claims 37 to 40, wherein a taper portion is formed so that a clearance gradually decreases from an opening of the extrusion molding die to an entrance of the core material passage. Production method.   The method for producing a laminated molded body according to any one of claims 1 to 41, wherein the laminated molded body is an exterior building material.

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