JP4908999B2 - Laminated molded body - Google Patents

Description

  The present invention relates to 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 resins are widely used as materials for building members because they are excellent in water resistance, flame retardancy, mechanical properties, and the like, and are relatively inexpensive. For example, rain gutters are generally formed by extrusion of a hard vinyl chloride resin.

However, the linear expansion coefficient of hard vinyl chloride resin molding is as large as 7.0 × 10 ^-5 (1 / ° C), so when installing a hard vinyl chloride resin gutter, It was necessary to connect with an absorbable joint or to make the end free. However, when the gutter length becomes longer, the joint becomes larger, the appearance is bad, and the joint part will be damaged if used for a long time. was there. In addition, the rain gutter itself has cracks and warpage due to repeated expansion and contraction, and has a drawback of low reliability when used for a long time.

For this reason, various studies have been made on rain gutters having a low linear expansion coefficient. For example, it consists of a vinyl chloride resin composition in which 20 to 35 parts by weight of mica, 20 to 40 parts by weight of calcium carbonate, and 5 to 15 parts by weight of processing aids are added to 100 parts by weight of vinyl chloride resin. A vinyl chloride resin rain gutter (see, for example, Patent Document 1) is proposed.
Japanese Patent No. 2905260

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

In addition, rain gutters impregnated with glass fiber as a reinforcing material or laminated with metal thin plates have been proposed. For example, a composite sheet composed of a thermoplastic resin and reinforcing fibers is shaped to the required cross-sectional shape, and the thermoplastic resin is extrusion-coated on the surface, and the composite sheet is reinforced at least on the shaped part. A composite molded product characterized in that short fibers are randomly oriented (see, for example, Patent Document 2), a metal thin plate as a core material, and a synthetic resin is coated on both surfaces of the core material to form a sheet material, In the rain gutter formed by pressing the bending jig distal end against the sheet material to be bent into a substantially U-shaped cross section, the bending jig distal end is located at the bending position of the synthetic resin on the inner surface side. A rain gutter (see, for example, Patent Document 3) characterized by providing a groove to be guided has been proposed.
Japanese Patent Laid-Open No. 11-19998 Japanese Patent Laid-Open No. 9-297883

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

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

Further, as a rain gutter having a low linear expansion coefficient without using a core material or glass fiber made of a thin metal plate, for example, an average linear expansion coefficient of 20 to 80 ° C. is 5 × 10 ⁻⁵ (1 / ° C.) or less. The low molecular weight compound that dissolves the polyolefin was adhered to the surface of the stretched polyolefin material, and then the polyolefin stretched material was adhered by pressing and heating, and the average linear expansion coefficient at 20 to 80 ° C. was 5 × 10 ⁻⁵ ( 1 / ° C) or less polyolefin molded body (see, for example, Patent Document 4), after extruding a thermoplastic resin, the extruded material is further stretched and stretched to orient the molecules in one direction. A synthetic resin rain gutter characterized in that the linear expansion coefficient of the thermoplastic synthetic resin is 6 × 10 ⁻⁵ / ° C. or less and the thickness is greater than 0.5 mm has been proposed (for example, see Patent Document 5). Yes.
JP-A-10-291250 Japanese Patent Laid-Open No. 2002-285685

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

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

The laminated molded article according to claim 1, wherein the thermoplastic polyester-based resin sheet in an amorphous state is a temperature between a glass transition temperature of the thermoplastic polyester-based resin of -20 ° C and a glass transition temperature of the thermoplastic polyester-based resin of + 20 ° C. The thermoplastic resin layers are γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition on both sides of the stretched thermoplastic polyester resin sheet obtained by uniaxial stretching at a temperature higher than the drawing stretching temperature It is characterized by being adhered by an object .

  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.

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

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

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

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

  The temperature at the time of the uniaxial stretching may be higher than the temperature of the pair of rolls at the time of primary stretching, but if it is too high, the drawn and stretched thermoplastic polyester resin sheet tends to melt and be cut. Therefore, the temperature range from the rising temperature of the crystallization peak of the thermoplastic polyester resin to the rising temperature of the melting peak in the differential scanning calorimetry curve measured at a heating rate of 10 ° C./min is preferable.

  The rising temperature of the crystallization peak of polyethylene terephthalate is about 120 ° C., and the rising temperature of the melting peak is about 230 ° C. Accordingly, when the polyethylene terephthalate sheet is uniaxially stretched, it is preferably uniaxially stretched at about 120 ° C to about 230 ° C.

  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 drawing and the uniaxial drawing is preferably 2.5 to 10 times, more preferably 3 to 8 times for the same reason.

  The uniaxially stretched stretched thermoplastic polyester resin sheet is preferably heat-set at a temperature higher than the uniaxial stretch temperature in order to further improve the heat resistance.

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

  In addition, when heat-fixed, if the stretched thermoplastic polyester resin sheet is under load, it is stretched and shrinks in a free state, so the length of the stretched thermoplastic polyester resin sheet in the stretching direction changes substantially. It is preferable to carry out in such a state that it does not occur, and it is preferable that no pressure is applied to the stretched thermoplastic polyester resin sheet.

  That is, the length of the stretched thermoplastic polyester resin sheet that has been heat-set is 0.95 to 1.1 of the length of the stretched thermoplastic polyester resin sheet before heat setting, and is a lower ratio than the uniaxial stretch ratio. It is preferable to heat-fix like this.

  Therefore, when the stretched thermoplastic polyester resin sheet is heat-set continuously while moving in the heating chamber with a roll such as a pinch roll, the feed rate ratio of the stretched thermoplastic polyester resin sheet on the inlet side and the outlet side is set to 0. It is preferable to heat-set by setting it to a magnification lower than the uniaxial stretching magnification at .95 to 1.1.

  The heating method at the time of heat setting is not particularly limited, and examples thereof include a method of heating with hot air or a heater. The time for heat setting is not particularly limited, but is generally 10 seconds to 10 minutes, although it varies depending on the thickness of the stretched thermoplastic polyester resin sheet and the heat setting temperature.

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

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

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

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

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

  Further, when annealing the short sheet, it is preferable to open both ends so that no load is applied. The heating method at the time of annealing is not particularly limited, and examples thereof include a method of heating with hot air or a heater.

  The time for annealing is not particularly limited and varies depending on the thickness of the stretched thermoplastic polyester resin sheet and the annealing temperature, but is generally preferably 10 seconds or longer, more preferably 30 seconds to 60 minutes, and further preferably 1 to 20 Minutes.

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. Therefore, it is preferably −1.5 × 10 ⁻⁵ or more and less than 0.

  Moreover, when the tensile elastic modulus of the 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 stretched thermoplastic polyester resin sheet is increased, and when it exceeds 15 GPa. Since the impact resistance of the laminated molded body is lowered, the tensile elastic modulus of the stretched thermoplastic polyester resin sheet is preferably 7 to 15 GPa.

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

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

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

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

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

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

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

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

The basis weight, thickness, etc. of the thermoplastic polyester resin woven fabric and nonwoven fabric are not particularly limited, but 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 stretched thermoplastic polyester resin sheets, and a thermoplastic polyester resin woven fabric hot melt adhesive sheet 2 is laminated between the stretched thermoplastic polyester resin sheets 1 and 1 and laminated. A body 10 is formed.

  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 laminated molded article of the present invention, a thermoplastic resin layer is bonded to both surfaces of a stretched thermoplastic polyester resin sheet with a glycidyl (meth) acrylate-olefin copolymer composition.

  The thermoplastic resin layer is laminated on both sides of the stretched thermoplastic polyester resin sheet, and protects the stretched thermoplastic polyester resin sheet from being cracked or cracked along the stretch direction by impact, and the polyester resin. Is prevented from being subjected to hydrolysis or deterioration due to direct exposure to rainwater or sunlight, resulting in a decrease in durability.

  Examples of the thermoplastic resin constituting the thermoplastic resin layer 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, etc. are mentioned, 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 γ-glycidyl methacrylate-methyl acrylate-olefin copolymer is a copolymer of γ-glycidyl methacrylate, methyl acrylate, and olefins, and may be a random copolymer or a block copolymer. It may be a coalescence. Although content of ( gamma) -glycidyl methacrylate in a copolymer is not specifically limited, Preferably it is 3 to 20 weight%. The content of methyl acrylate is not particularly limited, but is preferably 3 to 40% by weight.

  Examples of the olefins include ethylene, propylene, butene-1, isobutylene, pentene-1, hexene-1, heptene-1, octene-1, dodecene-1, 4-methyl-pentene-1, and the like. Ethylene and propylene are preferred. The content of olefins in the copolymer is not particularly limited, but is preferably 50 to 97% by weight.

The γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition may be the γ-glycidyl methacrylate-methyl acrylate-olefin copolymer alone or in a mixture with other thermoplastic resins. There may be. Examples of other thermoplastic resins include vinyl chloride resin, chlorinated polyethylene resin, ABS resin, AES resin, AS resin, acrylic resin, ethylene resin, polypropylene resin, urethane resin, and polyester resin.

When laminating a vinyl chloride resin as a thermoplastic resin layer on a stretched thermoplastic polyester resin sheet, a urethane resin is preferred, and the amount of urethane resin added is 100 parts by weight of a γ-glycidyl methacrylate-methyl acrylate-olefin copolymer. The amount is preferably 20 to 400 parts by weight.

As a bonding method, any conventionally known method may be employed. For example, a γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition sheet and a thermoplastic resin sheet are provided on both sides of a stretched thermoplastic polyester resin sheet. , A method of softening and melting the γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition sheet by a hot press or the above-described ultrasonic welder, and bonding by pressing, a stretched thermoplastic polyester resin sheet A method of laminating a γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition layer on both sides of the sheet, and extrusion-coating a thermoplastic resin thereon, γ-glycidyl methacrylate on both sides of the stretched thermoplastic polyester resin sheet -Methyl acrylate-Olephy A method in which co-extrusion coating of a copolymer composition and a thermoplastic resin.

In this case, in order to enhance the adhesion between the stretched thermoplastic polyester resin sheet and the γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition, the surface of the stretched thermoplastic polyester resin sheet is subjected to surface oxidation treatment or surface hydrolysis. It is preferable to perform a decomposition treatment.

  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 treatment UV treatment, electron beam treatment, radiation treatment and the like, and corona discharge treatment and chromic acid treatment are preferred.

  The corona discharge treatment can be performed by passing a stretched thermoplastic polyester resin sheet between the insulated electrode and the installed counter electrode dielectric roll, 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 carried out by immersing the stretched thermoplastic polyester resin sheet in an acidic aqueous solution of dichromic acid or a salt thereof. For example, after immersing a stretched thermoplastic polyester resin sheet in a dichromic acid 30 g / liter sulfuric acid (90 Wt% or more aqueous solution) solution, washing with water and drying, the chromic acid treatment and the stretched thermoplastic polyester resin sheet Obtainable.

  The hydrolysis treatment is carried out by immersing the stretched thermoplastic polyester resin sheet in acidic or alkaline water. Heating is preferred to promote the reaction. For example, the 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, and then subjected to decomposition treatment of stretched thermoplastic polyester resin. A sheet can be obtained.

  Further, the above-mentioned non-woven fabric or work cloth may be impregnated with the acid-modified olefin resin composition and bonded.

  The laminated molded body of the present invention can be molded into a predetermined shape by a molding method such as profile molding or 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 sheet, 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 configuration of the laminated molded body of the present invention is as described above, and a thermoplastic resin layer is bonded to both surfaces of a specific stretched thermoplastic polyester resin sheet by a γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition. Therefore, the stretched thermoplastic polyester resin sheet and the thermoplastic resin layer are firmly bonded, have a low coefficient of linear expansion, are lightweight, have excellent impact resistance, durability, etc. It can be suitably used as a building material.

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

Example 1
Polyethylene terephthalate (trade name “NEH-2070” manufactured by Unitika Ltd., intrinsic viscosity 0.88) melt-extruded polyethylene terephthalate sheet (crystallinity 4.5%) with a thickness of 2.5 mm is stretched (Kyowa Engineering Co., Ltd.) ), Preheated to 80 ° C., then drawn between a pair of rolls heated to 74 ° C. (roll interval 0.5 mm) at a rate of 2 m / min, and further in a hot air heating tank, a polyethylene terephthalate sheet The surface temperature was heated to 180 ° C., the outlet speed was set to 2.5 m / min, and roll-stretched to obtain a stretched polyethylene terephthalate sheet having a thickness of 0.5 mm and a stretch ratio of about 5 times.

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

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

A γ-glycidyl methacrylate-methyl acrylate-ethylene copolymer (weight ratio 6:27:67) having a thickness of 0.05 mm on both surfaces of the obtained surface oxidation-treated sheet (trade name “Bond First 7M” manufactured by Sumitomo Chemical Co., Ltd.) )) And a 0.5 mm-thick vinyl chloride resin sheet (product number “TS1000R” manufactured by Tokuyama Sekisui Co., Ltd.), and heat-pressed with a hot press machine at 195 ° C. and 3 MPa for 20 seconds to obtain a laminated molded body. Obtained. 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 46 N / 25 mm width.

(Example 2)
γ-glycidyl methacrylate-methyl acrylate-ethylene copolymer (weight ratio 6:27:67) (manufactured by Sumitomo Chemical Co., Ltd., trade name “Bond First 7M”) and urethane resin (manufactured by Kuraray Co., Ltd., trade name “ Clamillon U3190 ") 100 parts by weight of a glycidyl methacrylate-olefin copolymer composition obtained by melting and kneading at 215 ° C using a lab plast mill (manufactured by Toyo Seiki Co., Ltd.) was formed into a sheet having a thickness of 0.05 mm. Example 1 was repeated except that γ-glycidyl methacrylate-methyl acrylate-ethylene copolymer was used.
The obtained laminated molded article had a linear expansion coefficient of 1.3 × 10 ⁻⁵ (1 / ° C.), a tensile elastic modulus of 5.1 GPa, and a T-type peeling strength of 66 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.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Stretched thermoplastic polyester-based resin sheet 2 Thermoplastic polyester-based resin woven fabric hot melt adhesive sheet 3 Horn 4 Knurl 5 Fusion site 10 Laminate

Claims (6)

After drawing and stretching an amorphous thermoplastic polyester resin sheet at a temperature between the glass transition temperature of the thermoplastic polyester resin of −20 ° C. to the glass transition temperature of the thermoplastic polyester resin of + 20 ° C., the drawing stretching temperature A thermoplastic resin layer is adhered to both surfaces of a stretched thermoplastic polyester resin sheet obtained by uniaxial stretching at a higher temperature by a γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition. Laminated molded body. Molded laminate according to claim 1, wherein the thermoplastic resin is characterized in that the vinyl chloride resin. The γ-glycidyl methacrylate-methyl acrylate-olefin copolymer composition comprises 100 parts by weight of a γ-glycidyl methacrylate-methyl acrylate-olefin copolymer and 20 to 400 parts by weight of a urethane resin. 2. Laminated molded product according to 2.   The laminated molded body according to any one of claims 1 to 3, wherein the surface of the stretched thermoplastic polyester resin sheet is subjected to surface oxidation treatment or surface hydrolysis treatment.   The layered molded article according to claim 4, wherein the surface oxidation treatment is corona discharge treatment or chromic acid treatment.   The laminated molded body according to any one of claims 1 to 5, wherein the laminated molded body is an exterior building material.

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