Laminate and method for molding laminate product

Abstract

The present invention provides a laminate and a molding method of a laminate product, which can be demolded without waiting for cooling to 60°C or less and can proceed to the next molding cycle, and is excellent in molding cycle time, and the problem is solved by a laminate formed by laminating a plurality of cloth-like bodies composed of a linear body made of a thermoplastic resin, and a molding method of a laminate product, the laminate being formed by laminating a cladding layer of a thermoplastic resin on at least one face of the plurality of cloth-like bodies, the cladding layer being composed of the same component as the linear body and having a thickness of 0.02 mm or more and 1.0 mm or less, the cladding layer having a storage elastic modulus at 150°C of 3.00 x 10 6 Pa or more and 1.00 x 10 8 Pa or less, the molding method of a laminate product being characterized by performing die molding of the laminate with a punch press of a male and female die, then demolding in a range where the molded product temperature of the molded product obtained by the molding is 70°C or more and 120°C or less, and then cooling the molded product temperature to 60°C or less.

Description

TECHNICAL FIELD

[0001] The present application relates to a laminate and a molding method of a laminate molded product, and particularly to a laminate and a molding method of a laminate molded product, which are excellent in molding cycle time. BACKGROUND

[0002] In Patent Literature 1, there is disclosed a technology of preparing a plurality of coated woven fabrics in which a coating layer (laminate sheet) is formed on both sides of a woven fabric, and heat-pressing the coated woven fabrics in a non-adjacent manner at a temperature above the melting point of a thermoplastic polymer and lower than the melting point of the woven fabric, thereby producing a sheet-shaped product.

[0003] Thus, the coating layers of the adjacent laminate sheets are fused to each other, and therefore the strength of the molded product can be improved. The molded product thus obtained is excellent in impact resistance and tensile strength, and has a moderate rigidity, and is suitable as a case of a suitcase or the like.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: Japanese Patent Application Laid-Open No. 2014-218074 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, in the technology described in Patent Literature 1, if the fabric laminate is to be subjected to press molding at a temperature of 150°C to 170°C, and the mold is opened and the product is demolded at a temperature of 70°C to 120°C, there is a problem that the coating layer is lifted at the time of demolding.

[0009] In order to prevent the coating layer from being lifted at the time of demolding, it is necessary to cool to 60°C or lower and then demold.

[0010] However, if such cooling is necessary, the next molding cycle cannot be started until the temperature is cooled to 60°C or lower, and there is a disadvantage that the molding cycle takes too much time.

[0011] The present application has an object to provide a laminate and a molding method of a laminate molded product, which are excellent in molding cycle time, and in which demolding can be performed without waiting for cooling to 60°C or lower, and the next molding cycle can be started.

[0012] Further, other objects of the present application are clarified by the following description.

[0013] MEANS FOR SOLVING THE PROBLEMS

[0014] The above problems are solved by the following inventions.

[0015] (claim 1)

[0016] A laminate characterized by comprising

[0017] The laminate is formed by laminating a plurality of cloth-like bodies each of which is composed of a linear body made of a thermoplastic resin, and the laminate is formed by laminating a coating layer of a thermoplastic resin on at least one face of the plurality of cloth-like bodies, the coating layer being composed of the same component as the linear body and having a thickness of 0.02 mm or more and 1.0 mm or less,

[0018] The coating layer has a storage elastic modulus at 150°C of 3.00 x 10 6 Pa or more and 1.00 x 10 8 Pa or less.

[0019] (claim 2)

[0020] The laminate according to claim 1, characterized in that the cloth-like bodies are formed by being laminated via an adhesive layer composed of the same component.

[0021] (claim 3)

[0022] The laminate according to claim 1 or 2, characterized in that a top layer composed of a thermoplastic resin having a thickness of 0.02 mm or more and 0.1 mm or less is laminated on an upper surface of the one coating layer.

[0023] (claim 4)

[0024] The laminate according to claim 1 or 2, characterized in that a top layer composed of a thermoplastic resin having a thickness of 0.02 mm or more and 0.1 mm or less is formed by being laminated on an upper surface of the one coating layer via an adhesive layer.

[0025] (claim 5)

[0026] A molding method of a laminate molded product, characterized by

[0027] molding the laminate described in any one of claims 1 to 4 using a punch press having a male die and a female die,

[0028] then, releasing the mold in a range where a molded product temperature of the molded product obtained by the molding is 70°C or higher and 120°C or lower,

[0029] then, cooling the molded product temperature to 60°C or lower.

[0030] (claim 6)

[0031] The molding method of the laminate molded article according to claim 5, wherein the cooling is performed in a state where the molded article maintains a shape along the correction mold when the temperature of the molded article is cooled to 60°C or less.

[0032] (claim 7)

[0033] The molding method of the laminate molded article according to claim 5, wherein the cooling is performed in a state where a punch of a press machine to which the male mold of the male-female mold is attached is the male mold when the temperature of the molded article is cooled to 60°C or less.

[0034] Inventive Effects

[0035] According to the present application, it is possible to provide a laminate and a molding method of a laminate molded article, which can be demolded without waiting for cooling to 60°C or less and can enter the next molding cycle, and the molding cycle time is excellent. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 is a schematic cross-sectional view showing an example of the laminate of the present application.

[0037] Figure 2 is a schematic cross-sectional view showing another example of the laminate of the present application.

[0038] Figure 3 is a view showing one example of the structure of a line body.

[0039] Figure 4 is a schematic cross-sectional view showing still another example of the laminate of the present application.

[0040] Figure 5 is a schematic cross-sectional view showing still another example of the laminate of the present application.

[0041] Figure 6 is a schematic cross-sectional view showing still another example of the laminate of the present application.

[0042] Figure 7 is a schematic cross-sectional view showing still another example of the laminate of the present application.

[0043] Figure 8 is a schematic cross-sectional view showing still another example of the laminate of the present application.

[0044] Figure 9 is a view showing one example of the molding method of the laminate molded article of the present application.

[0045] Figure 10 is a view showing a demolding time photograph of an embodiment of the present application. DETAILED DESCRIPTION

[0046] The following describes preferred embodiments of the present application.

[0047] 1. Laminated body

[0048] Figure 1 is a schematic cross-sectional view showing an example of a laminated body obtained by laminating a coating layer 3 on one face of a plurality of cloth-like bodies 2 that are laminated, Figure 2 is a schematic cross-sectional view showing an example of a modification of the laminated body of Figure 1 .

[0049] In the present application, a plurality of cloth-like bodies 2 composed of thread-like bodies 1 made of a thermoplastic resin are laminated, a coating layer 3 is laminated on at least one face of the plurality of cloth-like bodies, and they are thermally pressure-bonded to be integrated, thereby obtaining the laminated body of the present application.

[0050] (Thread-like body)

[0051] The thread-like body 1 is composed of a high-melting-point resin component having a melting point higher than the thermal pressure-bonding temperature, and can contain a low-melting-point resin component having a melting point lower than the thermal pressure-bonding temperature.

[0052] As the structure of the thread-like body, for example, the scheme shown in Figure 3 can be exemplified. Figure 3 (a) is an example in which the thread-like body 1 is a single layer of a base layer 100. In the case of this example, the resin constituting the thread-like body is composed of a high-melting-point resin component, but a low-melting-point resin component can be contained within a range that does not impair the effects of the present application. Figure 3 (b), (c) show examples of a laminated structure in which the thread-like body 1 has a surface layer 101 composed of a thermoplastic resin having a melting point lower than the base layer 100 laminated on one or both faces of the base layer 100. Figure 3 (d) is an example of a core-sheath structure in which a surface layer 101 composed of a thermoplastic resin having a melting point lower than the base layer 100 covers the periphery of the base layer 100. Figure 3 (e) is an example of an island-in-sea structure, and 102 is a low-melting-point portion.

[0053] As the thermoplastic resin constituting the thread-like body, for example, polypropylene, polyolefins such as polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably cited. Among these, polypropylene is particularly suitable.

[0054] In the case where a laminated structure is adopted as the thread-like body 1, as a method of molding the laminated film that will become the molding material thereof, a dry lamination method or a heat lamination method can be appropriately selected and used from among the following methods and the like:

[0055] Method (1) of previously forming a film that will become the base layer 100 and a film that will become the surface layer 101, and performing multilayerization using a dry lamination method or a heat lamination method;

[0056] Method (2), coating a thermoplastic resin that becomes the surface layer 101 on the surface of a film that becomes the base layer 100;

[0057] Method (3), extruding and laminating the surface layer 101 on a film that is formed in advance and becomes the base layer 100; or

[0058] Method (4), extrusion molding as a laminated film by a multilayer co-extrusion method.

[0059] It is possible to obtain the stretched thread body 1 by, for example, stretching a film that becomes the base layer 100 in a uniaxial direction, then laminating a thermoplastic resin that becomes the surface layer 101, and cutting it into a tape shape.

[0060] Alternatively, it is also possible to obtain the thread body 1 by cutting a laminated film in which the base layer 100 and the surface layer 101 are laminated, and then stretching it in a uniaxial direction.

[0061] The stretching method is not particularly limited, and it is possible to use a hot roller, a hot plate, a hot air furnace, hot water, hot oil, steam, infrared radiation, or the like, and to perform stretching by one or more stages of stretching.

[0062] The thickness of the thread body can be arbitrarily selected according to the purpose, and in the case of a laminated structure, it is preferably in the range of 50 to 10,000 dt (decitex), and in the case of a core-sheath structure (coating structure) as shown in (d), it is preferably in the range of 1 to 10,000 dt (decitex). Figure 3

[0063] The stretched thread body is not particularly limited, and is only required to be a stretched yarn of a semi-crystalline thermoplastic polymer, and examples include a multifilament, a monofilament, a flat monofilament, a flat filament, a slit film flat yarn, and the like. Since the multifilament, the monofilament, and the flat monofilament have the disadvantage of poor surface smoothness of the molded product, it is preferable to use the flat filament or the slit film flat yarn.

[0064] (Woven fabric)

[0065] The woven fabric 2 used in the present application is preferably a woven fabric (for example, a plain weave, a twill weave, a satin weave, a tuck weave, or a derivative weave, or the like) woven with the thread body 1, and can be a cross-bound fabric (sof) formed by arranging a plurality of thread bodies 1 composed of a thermoplastic resin in an orthogonal manner to form a planar shape and connecting the intersections, or can be another knitted fabric formed of the thread body 1 composed of a thermoplastic resin described above.

[0066] The unit area weight of the woven fabric is preferably 30 to 500 g / m 2 , and more preferably 50 to 400 g / m 2 .

[0067] ​In order to maintain the strength of the molded product, the warp and weft of the woven fabric preferably have a weaving density of 5 or more per inch. The upper limit of the weaving density varies depending on the type of the yarn and is not particularly limited, and is preferably 5 to 30 per inch.

[0068] (coating layer)

[0069] In Figure 1 , the coating layer 3 is provided on one surface of the plurality of fabric-like bodies 2 that are stacked. In addition, in Figure 2 , the coating layer 3 is provided on both surfaces of the plurality of fabric-like bodies 2 that are stacked.

[0070] The coating layer of the present application has the following properties: the storage elastic modulus at 150°C is 3.00 x 10 6 Pa or more and 1.00 x 10 8 Pa or less.

[0071] The storage elastic modulus of the coating layer can be measured, for example, using a measuring device (EPLEXOR 500N (manufactured by NETZSCH GABO INSTRUMENTS CO., LTD.): dynamic viscoelastic temperature distribution measurement).

[0072] The coating layer 3 is preferably a film of the same material as the fabric-like body, and for example, a film of polyolefin such as polypropylene or polyethylene, polyester such as polyethylene terephthalate, polyamide, or the like can be preferably used, with polyolefin being preferred, and polypropylene being more preferred.

[0073] If the storage elastic modulus of the coating layer 3 is within the range of the present application, the following effect of excellent molding cycle time can be exerted: the mold can be released without waiting for cooling to 60°C or less, and the next molding cycle can be entered.

[0074] The coating layer 3 can be formed on both surfaces or one surface of the fabric-like body 2 (woven fabric) by a publicly known extrusion lamination method, thermal lamination method, calendering method, coating method, impregnation method, or the like.

[0075] The thickness of the coating layer 3 is 0.02 mm or more and 1.0 mm or less. If the thickness is less than 0.02 mm, there is a disadvantage that it is difficult to manufacture, and on the other hand, if the thickness is too large, the lightweight property is impaired.

[0076] In the present application, the resin component that constitutes the string-like body 1 and the coating layer 3 is preferably the same component, and the same component herein means that it collectively contains a polypropylene resin component.

[0077] (adhesive layer)

[0078] As Figure 4 and Figure 5As shown, it is preferable to perform the lamination between the cloth-like body 2 and the adjacent cloth-like body 2 via the adhesive layer 4 composed of the same component as the cloth-like body 2. It is preferable that the same component contained in the cloth-like body 2 and the adhesive layer 4 be a polypropylene resin component in common.

[0079] The adhesive layer 4 is disposed between the cloth-like bodies 2 and adheres between the cloth-like bodies 2. By the presence of the adhesive layer 4, there is a function of improving the rigidity of the resulting laminate.

[0080] The adhesive layer 4 is preferably a film composed of a thermoplastic resin. As the thermoplastic resin, a thermoplastic resin containing a high-melting-point resin component in a low-melting-point resin component can be used. If the high-melting-point resin component is contained in the low-melting-point resin component, the adhesive layer can function as a rigidity-improving layer.

[0081] In the present specification, the "melting point" refers to the temperature as the melting peak temperature measured by DSC measurement (Differential Scanning Calorimetry).

[0082] In other words, the high-melting-point resin component and the low-melting-point resin component are in a relationship in which the melting peak temperature of the high-melting-point resin component is higher than that of the low-melting-point resin component. The adhesive layer 4 can exhibit two melting peak temperatures derived from these resins.

[0083] As the low-melting-point resin component for the adhesive layer 4, polypropylene, polyolefins such as polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably exemplified. Among them, polyolefins are preferable, and polypropylene is more preferable.

[0084] As the high-melting-point resin component for the adhesive layer 4, as long as it is a resin having a higher melting point than the low-melting-point resin component, polypropylene, polyolefins such as polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably exemplified. Among them, polypropylene is particularly suitable.

[0085] In the case where the low-melting-point resin component and the high-melting-point resin component for the adhesive layer 4 are each selected from polypropylene, for example, a random polypropylene can be used as the low-melting-point resin component, and a homopolypropylene can be used as the high-melting-point resin component. In addition, as another option in the case where the low-melting-point resin component and the high-melting-point resin component for the adhesive layer 4 are each selected from polypropylene, a random polypropylene having a relatively low melting point can be used as the low-melting-point resin component, and a random polypropylene having a relatively high melting point can be used as the high-melting-point resin component.

[0086] The random polypropylene is a product obtained by random copolymerization of propylene as a monomer component and an α-olefin (for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, or the like other than propylene).

[0087] For example, the α-olefin can be preferably used in a proportion of 20% by weight or less, more preferably 10% by weight or less, relative to the total monomer component. The proportion of the α-olefin can be adjusted to exhibit a desired melting point.

[0088] As described above, the melting point of the random polypropylene can be set, for example, by adjusting the proportion of the α-olefin or the like. Specifically, for example, a random polypropylene having a proportion of the α-olefin smaller than that of the random polypropylene used as the low-melting-point resin component can be used as the high-melting-point resin component.

[0089] As the adhesive layer 4, a film formed by mixing pellets of the low-melting-point resin component and pellets of the high-melting-point resin component at a temperature above the melting points of the two resin components and by blow molding or the like can be used.

[0090] In the adhesive layer 4, the content of the high-melting-point resin component is preferably in the range of 5% by weight to 50% by weight, further preferably in the range of 10% by weight to 30% by weight, for example.

[0091] In addition, the weight ratio of the low-melting-point resin component to the high-melting-point resin component in the adhesive layer 4 is preferably in the range of 5:95 to 50:50, further preferably in the range of 10:90 to 30:70.

[0092] The thickness of the adhesive layer 4 can be appropriately set depending on the thickness of the cloth-like body, the thickness of the thread-like bodies constituting the cloth-like body, or the like, and is not limited, and is preferably in the range of 10 μm to 500 μm, further preferably in the range of 20 μm to 300 μm.

[0093] In the example of Figure 4 , three pieces of the cloth-like body 2 are laminated, and the surface has the coating layer 3. Specifically, this is an example of a laminate composed of the coating layer 3 / cloth-like body 2 / adhesive layer 4 / cloth-like body 2 / adhesive layer 4 / cloth-like body 2.

[0094] At the time of heat pressure bonding of the fabric laminate, the low-melting-point resin component constituting the surface layer of the thread-like body for the cloth-like body is melted, and the plurality of cloth-like bodies are integrated with each other by heat pressure bonding. At this time, the remaining thread-like body component composed of the high-melting-point resin component remains as the fiber component of the cloth-like body, thereby exhibiting an effect of enhancing the strength of the molded product, and is thus preferred.

[0095] Figure 5 The example of is an example of a laminate composed of the coating layer 3 / cloth-like body 2 / adhesive layer 4 / cloth-like body 2 / adhesive layer 4 / cloth-like body 2 / coating layer 3. The difference from the scheme of Figure 4 is that, in Figure 5 , the coating layer 3 is provided on the bottommost layer.

[0096] If the cloth-like body (woven fabric) and the adhesive film are alternately overlapped, the overlapping becomes easy.

[0097] The number of sheets of the woven fabric is preferably 2 to 20 sheets, further preferably 2 to 10 sheets, and the number of sheets can be appropriately selected depending on the purpose or use of the molded product, and the direction of the overlapping is also arbitrary. From the viewpoint of imparting moderate strength (hardness) and impact resistance to the molded product, it is preferable to use at least 2 or more sheets of the woven fabric.

[0098] The laminate of the present embodiment is heated to a temperature at which the polymer constituting the covering layer is softened or partially melted by heat pressure bonding, the covering layers of the laminated sheets are fused to each other or the covering layers are softened to intrude between the woven fabrics or to be fused to the woven fabrics to be integrated, and the cloth-like body and the adhesive film are overlapped and heated to a temperature above the melting point of the film and below the melting point of the woven fabric, that is, to a temperature at which the polymer constituting the adhesive film is softened or partially melted, the cloth-like body and the adhesive film are integrated, and thus the covering layers are firmly bonded to the cloth-like body, the cloth-like body, and the adjacent cloth-like body.

[0099] The heat pressure bonding method for forming the laminate is not particularly limited, and publicly known extrusion lamination molding, heat lamination, calender molding, mold molding, and the like can be used.

[0100] It is preferable to produce the laminate sheet by heat pressure bonding before molding the molded product into a predetermined shape. In this case, in order not to reduce the crystallization of the polymer constituting the tensile cord body, it is desirable to set the heat pressure bonding temperature to a temperature lower than the melting point of the polymer. For example, in the case where the polymer constituting the covering layer is polyethylene, the heat pressure bonding temperature is preferably around 115 to 125°C. In addition, in the case where the polymer constituting the covering layer is polypropylene, the heat pressure bonding temperature is preferably around 115 to 165°C.

[0101] According to Figure 6 , Figure 7 and Figure 8 , a modified example of the laminate shown in Figure 1 , Figure 2 , Figure 4 and Figure 5 will be described.

[0102] The modified example can be exemplified by the following scheme: a top layer composed of a thermoplastic resin having a thickness of 0.02 mm or more and 0.1 mm or less is laminated on the upper surface of the one covering layer.

[0103] As the top layer 5, a layer of the same material as the cloth-like body and the covering layer is preferable, and for example, unstretched polypropylene film, biaxially stretched polypropylene film, unstretched polyethylene film, polyester film, polyamide film can be exemplified, of which unstretched polypropylene, biaxially stretched polypropylene is preferable, and biaxially stretched polypropylene is more preferable.

[0104] In the present embodiment, the top layer 5 can be colored. As a coloring method for the top layer 5, the top layer 5 itself can be colored with a pigment, paint, or a printed layer colored on the back layer 3 side of the top layer 5 can be provided.

[0105] In this modification, as shown in Figure 7 the top layer 5 composed of a thermoplastic resin of 0.02 mm or more and 0.1 mm or less is preferably layered on the upper surface of one back layer 3 via an adhesive layer 6.

[0106] The adhesive layer 6 is preferably an adhesive layer formed using at least one adhesive selected from the group consisting of an acrylic adhesive, a urethane adhesive, an epoxy adhesive, a vinyl acetate adhesive, a styrene butadiene rubber adhesive, and a silicone adhesive.

[0107] The method of providing the adhesive layer 6 is not particularly limited, and examples include spraying, dip coating, brush coating, and the like.

[0108] In addition, as shown in Figure 8 the back layer 3 and the top layer 5 are preferably sequentially layered via a thermoplastic resin layer 7 containing a polar group. Figure 8 The scheme shown in the above is characterized in that the back layer 3 and the top layer 5 are sequentially layered via the thermoplastic resin layer 7 containing a polar group.

[0109] The thermoplastic resin layer 7 containing a polar group is useful when stronger interlayer adhesion with the top layer 5 is desired. Furthermore, compared to the case where the adhesive layer 6 is formed after the layered body precursor is formed at one time and the top layer 5 is layered, the case where the thermoplastic resin layer 7 containing a polar group is used is useful in that it is possible to concentrate on the formation of the layered body without forming the layered body precursor.

[0110] The thermoplastic resin layer 7 containing a polar group is preferably a resin layer formed using a modified polyolefin, and the modified polyolefin is preferably a modified polyolefin obtained by acid-modifying a polyolefin with an organic acid having a carboxyl group.

[0111] In addition, in the case where the thermoplastic resin layer 7 containing a polar group is a resin layer formed using a modified polyolefin (hereinafter, referred to as a modified polyolefin layer 7 as necessary), at least one selected from the group consisting of an acid-modified modified polypropylene and an acid-modified modified polyethylene can be used.

[0112] As the polyolefin, a homopolymer or a copolymer can be used. As monomers thereof, ethylene, propylene, and the like can be used, and they can be used alone or in combination of two or more. The copolymer can be any one of a random copolymer, an alternating copolymer, a block copolymer, and a graft copolymer. In the present scheme, they can be used alone or in combination of two or more. Among them, polypropylene and polyethylene are particularly preferable as the polyolefin.

[0113] As a method of modifying the polyolefin, a method of performing acid modification is exemplified. As the method of performing acid modification, a method of graft-polymerizing an organic acid having a carboxyl group on the polyolefin or the like can be used.

[0114] By this graft polymerization, an acid-modified polyolefin in which an organic acid component is grafted on the polyolefin is obtained. The polymerization method is not limited to the graft polymerization, and any method can be appropriately selected and used.

[0115] The kind of the organic acid is not particularly limited, and a saturated or unsaturated carboxylic acid or carboxylic anhydride having at least one or more carboxyl groups is preferable.

[0116] As the organic acid, for example, the following are exemplified:

[0117] (1) carboxylic acids such as maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, aconitic acid, crotonic acid, succinic acid, oxalic acid, malonic acid, malic acid, thiophosphoric acid, tartaric acid, adipic acid, citric acid, pimelic acid, suberic acid, azelaic acid, acrylic acid, tetrahydrophthalic acid, isocrotonic acid, endo-cis- bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid, and sebacic acid;

[0118] (2) carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, and succinic anhydride.

[0119] The organic acid can be used alone or in combination of two or more kinds.

[0120] In the acid modification of the modified polyolefin, the modified polyolefin can be generally modified so as to contain 0.01 to 10% by weight of the organic acid with respect to the polyolefin.

[0121] In the case where the content of the organic acid is less than 0.01% by weight, in the case where the modified polyolefin layer 7 is laminated between the cloth-like body 2 and the copolymer polyamide layer, the interlayer adhesion is poor, and thus is not preferable. In the case where it exceeds 10% by weight, in the case where the polyolefin is modified with a molecular crosslinking type monomer as a main component, the crosslinking of the polyolefin is significant, and thus the melt viscosity increases, and in the case where the polyolefin is modified with a molecular cleavage type monomer as a main component, the main chain cleavage becomes significant, and thus the melt viscosity decreases. As a result, in the case where the modified polyolefin layer 7 is laminated between the cloth-like body and the copolymer polyamide layer, the interlayer adhesion is poor.

[0122] In addition to the above-described modified polyolefin, other resins such as an unmodified polyolefin can be contained in the resin layer formed of the modified polyolefin, within a range not impairing the effects of the present application.

[0123] The form of the resin layer formed from the modified polyolefin is not particularly limited, and for example, can be a form of a film or a sheet, or a molten state formed in order to provide extrusion lamination or the like. From the viewpoint of versatility, a form of a film or a sheet is preferred.

[0124] 2. A molding method of a laminate molded article.

[0125] Next, the molding method of the laminate molded article of the present application will be described. Figure 9 The molding method of the laminate molded article of the present application will be described.

[0126] Figure 9 (A) shows a punching process.

[0127] As the puncher 8, a puncher of a male-female die composed of a female die 81 and a male die 82 is used.

[0128] In the illustrated example, the laminate 83 is installed between the female die 81 and the male die 82, and the puncher 8 is used to perform die molding at a molded article temperature of 150 to 170°C.

[0129] After a predetermined time elapses, the die molding is completed, and the mold is opened as shown in Figure 9 (B), and the molded article is demolded while the molded article temperature is in a range of 70°C or higher and 120°C or lower.

[0130] At this demolding, if the storage elastic modulus of the clad layer is lower than the range of the present application, the clad layer floats up at the demolding. Therefore, in the past, it was necessary to wait until the temperature is cooled to 60°C or lower and then demold. That is, the demolding cannot be performed until the temperature is cooled to 60°C or lower, and thus the subsequent punching work cannot be performed, and there is a problem that the molding cycle is greatly lost.

[0131] However, in the present application, since the storage elastic modulus of the clad layer is in the range of the present application, the clad layer does not float up at the demolding.

[0132] Therefore, in the present application, as shown in Figure 9 (C), the molded article temperature can be cooled to 60°C or lower.

[0133] In the present application, at the time of cooling the molded article temperature to 60°C or lower, the cooling can be performed in a state where the shape is maintained along the correction die 84.

[0134] In addition, as another aspect, at the time of cooling the molded article temperature to 60°C or lower, the cooling can be performed in a state where the male die 82 of the puncher of the male-female die is installed.

[0135] Since floating of the coating layer does not occur at the time of demolding, there is no obstacle at the time of demolding and cooling of the molded product to 60°C or less, and thus the molding cycle can be smoothly advanced. Figure 9 The laminated molded product can be completed as shown in (D).

[0136] In addition, even in the case where a top layer is formed on the coating layer, at the time of demolding of the molded product composed of the laminated body including the top layer, the top layer is firmly bonded to the coating layer, and floating of the top layer does not occur, and thus there is no obstacle at the time of demolding and cooling of the molded product to 60°C or less, and thus the molding cycle can be smoothly advanced.

[0137] Example

[0138] Hereinafter, examples of the present application will be described, but the present application is not limited by these examples.

[0139] (Example 1)

[0140] Fabrication of the stack

[0141] (1) Production of cloth-like body

[0142] Manufacture of two kinds of three-layer polypropylene films

[0143] Two kinds of three-layer polypropylene films in which low-melting polypropylene was used as a surface layer and high-melting polypropylene was used as an inner layer were manufactured by a blow molding method using high-melting polypropylene (MFR = 0.4 g / 10 minutes, weight average molecular weight Mw = 630,000, melting point 164°C) and low-melting polypropylene (propylene-ethylene random copolymer, MFR = 7.0 g / 10 minutes, weight average molecular weight Mw = 220,000, melting point 125°C).

[0144] Manufacture of flat filaments

[0145] The obtained film was cut using a razor. Then, after stretching 7 times on a hot plate at a temperature of 110 to 120°C, 10% relaxation heat treatment was performed in a hot air circulating oven at a temperature of 145°C, and thus flat filaments having a filament width of 4.5 mm and a fineness of 1700 denier (dt) were obtained.

[0146] Manufacture of cloth-like body

[0147] The obtained flat filaments were woven into a twill weave having 15 warps / 25.4 mm and 15 wefts / 25.4 mm using a shuttle loom, and thus a cloth-like body was obtained.

[0148] (2) Adhesive layer

[0149] As the adhesive layer, a 0.6 mm polypropylene film was used which contained a high-melting-point polypropylene having a melting point of 161°C in a low-melting-point polypropylene having a melting point of 125°C.

[0150] (3) Cover layer

[0151] The cover layer was produced by mixing 55% by weight of polypropylene (PP A) (propylene-ethylene random copolymer, MFR = 2.0 g / 10 minutes, density = 0.90 g / ml) and 45% by weight of polypropylene (PP C) (homopolypropylene, MFR = 0.5 g / 10 minutes, density = 0.90 g / ml) and melt-fabricating it into a film, thereby producing a polypropylene film having a thickness of 110 μm.

[0152] The same film as the produced polypropylene film was prepared, and test pieces were produced, and the storage elastic modulus at 150°C was measured using the measuring device (dynamic viscoelastic temperature distribution measurement) shown below. The results are shown in Table 1.

[0153] <Measuring device>

[0154] Device name: EPLEXOR 500N (manufactured by NETZSCH GABO INSTRUMENTS CO., LTD.)

[0155] Measurement mode: Tensile mode

[0156] Frequency: 1 Hz

[0157] Environment: Under N2

[0158] Temperature range: -20°C to 180°C

[0159] Temperature increasing rate: 2°C / minute

[0160] (4) Production of the laminate

[0161] The three pieces of the cloth-like body and the two pieces of the adhesive layer were alternately layered so as to become cloth-like body / adhesive layer / cloth-like body / adhesive layer / cloth-like body, and the obtained cover layer was provided on the upper surface of the cloth-like body.

[0162] The layer structure was cover layer / cloth-like body / adhesive layer / cloth-like body / adhesive layer / cloth-like body.

[0163] The product having this layer structure was heated and pressed for 2 minutes at a pressing temperature of 145°C and a pressure of 1 MPa using an oil press, and then cooled and pressed for 2 minutes at a pressing temperature of 20°C and a pressure of 5 MPa using the oil press, thereby obtaining the integrated sheet-like laminate of Example 1.

[0164] (Example 2)

[0165] In Example 1, the same operation as in Example 1 was performed except that the polypropylene film (PP C) of the cladding layer was replaced with polypropylene (PP D) (ethylene-propylene block copolymer, MFR = 2.1 g / 10 minutes, density = 0.90 g / ml), to obtain the laminate of Example 2.

[0166] (Comparative Example 1)

[0167] In Example 1, the content of polypropylene (PP A) was replaced with 70 wt%, the polypropylene (PP C) of the cladding layer used in Example 1 was replaced with polypropylene (PP B) (homopolypropylene, MFR = 2.0 g / 10 minutes, density = 0.90 g / ml) and the content was replaced with 30 wt%, and the same operation as in Example 1 was performed except for this, to obtain the laminate of Comparative Example 1.

[0168] (Comparative Example 2)

[0169] In Example 1, the same operation as in Example 1 was performed except that polypropylene (PP C) was replaced with polypropylene (PP B) and the content was set to 45 wt%, to obtain the laminate of Comparative Example 2.

[0170] <Manufacture Test of Molded Article>

[0171] While holding the outer periphery of the laminate of Example 1, Example 2, Comparative Example 1 and Comparative Example 2 obtained by the above operation, heating was performed with an infrared heater until the surface of the laminate was 160°C, and then mold pressing was performed with a metal mold heated to 80°C, the mold was closed for 2 minutes, and then the mold was opened and the molded article was demolded, to obtain a molded article.

[0172] [Temperature at the time of demolding]

[0173] The temperature of the molded article at the time of demolding was measured, as shown in Table 1.

[0174] [Evaluation of appearance after demolding]

[0175] The molded article at the time of demolding was evaluated according to the following criteria. The results are shown in Table 1.

[0176] O: No occurrence of cladding layer floating, and a molded article with excellent surface appearance could be obtained

[0177] X: Occurrence of cladding layer floating, and a molded article with appearance deformation was obtained

[0178] Table 1

[0179]

[0180] [Evaluation]

[0181] The post-mold photographs of the molded products of the examples and comparative examples shown in Table 1 are shown in Figure 10

[0182] In Figure 10 Figure 10 (A) is a post-mold photograph of a molded product obtained by molding the laminate of Comparative Example 1, Figure 10 (B) is a post-mold photograph of a molded product obtained by molding the laminate of Comparative Example 2, Figure 10 (C) is a post-mold photograph of a molded product obtained by molding the laminate of Example 1, Figure 10 (D) is a post-mold photograph of a molded product obtained by molding the laminate of Example 2.

[0183] Upon observation of the post-mold photographs of Table 1 and Figure 10 , it was confirmed that in the case where the storage elastic modulus at 150°C of the cladding layer having a thickness of 110 μm was less than 3.00 x 10 6 Pa, if the temperature at the time of demolding was 120°C, the cladding layer floated up, and a molded product having a distorted appearance was obtained (see Figure 10 (A), Figure 10 (B)).

[0184] On the other hand, in the case where the storage elastic modulus at 150°C of the cladding layer having a thickness of 110 μm was 3.00 x 10 6 Pa or more and 1.00 x 10 8 Pa or less, even if the temperature at the time of demolding was 120°C, the cladding layer did not float up, and a molded product having an excellent surface appearance was obtained (see Figure 10 (C), Figure 10 (D)).

[0185] Therefore, it was confirmed that even if the temperature at the time of demolding was high, a molded product having an excellent surface appearance was obtained, and as a result, the molding cycle time could be shortened.

[0186] Example 3, Example 4, Comparative Example 3, and Comparative Example 4

[0187] In the production test of the molded products produced from the laminates of Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the molding conditions were changed as follows (the points of change are shown below), and the same operations were performed except for this, to perform the experiments of Example 3, Example 4, Comparative Example 3, and Comparative Example 4.

[0188] (Example 3)

[0189] ​​Using the laminate used in Example 1, the laminate was heated to 170°C using a constant temperature oven while holding the outer periphery of the laminate, and then was subjected to press molding using a metal mold heated to 100°C, and after 1.5 minutes of closing the mold, the mold was opened and the molded product was removed, thereby obtaining a molded product.

[0190] (Example 4)

[0191] Using the laminate used in Example 2, the test was performed in the same manner as in Example 3.

[0192] (Comparative Example 3)

[0193] Using the laminate used in Comparative Example 1, the test was performed in the same manner as in Example 3.

[0194] (Comparative Example 4)

[0195] Using the laminate used in Comparative Example 2, the test was performed in the same manner as in Example 3.

[0196] (Evaluation)

[0197] In the case of Comparative Examples 3 and 4, as in the case of Comparative Examples 1 and 2, the clad layer floated up, and a molded product having a distorted appearance was obtained.

[0198] On the other hand, in the case of Examples 3 and 4, as in the case of Examples 1 and 2, the clad layer did not float up, and a molded product having an excellent surface appearance was obtained.

[0199] Therefore, it was confirmed that even if the temperature at the time of demolding is high, a molded product having an excellent surface appearance can be obtained, and as a result, the molding cycle time can be shortened.

[0200] Explanation of Reference Numerals:

[0201] 1: Threaded body

[0202] 100: Base layer

[0203] 101: Surface layer

[0204] 102: Low-melting point portion

[0205] 2: Cloth-like body

[0206] 3: Clad layer

[0207] 4: Adhesive layer

[0208] 5: Top layer

[0209] 6: Adhesive layer

[0210] 7: Thermoplastic resin layer containing a polar group

[0211] 8: Press machine

[0212] 81: male mold

[0213] 82: female mold

[0214] 83: laminate

[0215] 84: correction mold

Claims

1. A laminate characterized by, a plurality of cloth-like bodies formed of a linear body made of a thermoplastic resin are laminated, the laminate is formed by laminating a cladding layer of a thermoplastic resin on at least one outermost layer of the plurality of the cloth-like bodies laminated, the cladding layer is composed of the same component as the linear body and has a thickness of 0.02 mm or more and 1.0 mm or less, The storage elastic modulus of the clad layer at 150°C is 3.00 x 10 6 Pa or more and 1.00 x 10 8 Pa or less.

2. The laminate according to claim 1, characterized by, the cloth-like bodies are laminated via an adhesive layer composed of a thermoplastic resin of the same component as the linear body that constitutes the cloth-like bodies.

3. The laminate according to claim 1 or 2, characterized by, a top layer composed of a thermoplastic resin of 0.02 mm or more and 0.1 mm or less is formed by laminating on the upper surface of the one cladding layer.

4. The laminate according to claim 1 or 2, characterized by, a top layer composed of a thermoplastic resin of 0.02 mm or more and 0.1 mm or less is formed by laminating on the upper surface of the one cladding layer via an adhesive layer.

5. A molding method of a laminate molded product, characterized by, molding the laminate according to any one of claims 1 to 4 with a punch press of a male and female mold, then, demolding in a range where the molded product temperature of the molded product obtained by the molding is 70°C or higher and 120°C or lower, then, cooling the molded product temperature to 60°C or lower.

6. The molding method of a laminate molded product according to claim 5, characterized by, cooling while maintaining the shape along the correction mold when cooling the molded product temperature to 60°C or lower.

7. The molding method of a laminate molded product according to claim 5, characterized by, cooling while being held by the male mold of the punch press of the male and female mold when cooling the molded product temperature to 60°C or lower.

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