WO2022186371A1 - Laminate - Google Patents

Laminate Download PDF

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Publication number
WO2022186371A1
WO2022186371A1 PCT/JP2022/009359 JP2022009359W WO2022186371A1 WO 2022186371 A1 WO2022186371 A1 WO 2022186371A1 JP 2022009359 W JP2022009359 W JP 2022009359W WO 2022186371 A1 WO2022186371 A1 WO 2022186371A1
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WO
WIPO (PCT)
Prior art keywords
layer
cloth
laminate
thermoplastic resin
adhesive layer
Prior art date
Application number
PCT/JP2022/009359
Other languages
French (fr)
Japanese (ja)
Inventor
健 伊藤
洋平 田辺
Original Assignee
ダイヤテックス株式会社
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Application filed by ダイヤテックス株式会社 filed Critical ダイヤテックス株式会社
Priority to JP2022572474A priority Critical patent/JP7369308B2/en
Publication of WO2022186371A1 publication Critical patent/WO2022186371A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/02—Layered products comprising a layer of synthetic resin in the form of fibres or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M17/00—Producing multi-layer textile fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M17/00—Producing multi-layer textile fabrics
    • D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives

Definitions

  • the present invention relates to a laminate used in suitcases and the like, and more particularly to a laminate capable of eliminating partial pressure unevenness due to tolerances in mold gaps and obtaining a molded product with excellent appearance.
  • Patent Document 1 a plurality of sets of woven fabrics with coating layers formed with coating layers (laminate sheets) on both sides of the woven fabric are prepared, and the woven fabrics with the coating layers are heated so that the woven fabrics are not adjacent to each other.
  • a technique for producing a plate-like sheet by thermocompression bonding at a temperature above the melting point of a plastic polymer and below the melting point of a woven fabric is disclosed.
  • the molded article thus obtained has excellent impact resistance and tensile strength, and has appropriate rigidity, and is suitable for cases such as suitcases.
  • An object of the present invention is to provide a laminate that does not cause poor appearance by preventing partial pressure unevenness due to the tolerance of mold gaps in press molding using male and female molds.
  • (Claim 1) On at least one surface of a cloth laminate obtained by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin, a cloth having a thickness of 0.02 mm or more and 1.0 mm or less made of the same component as the filaments and having a thickness of 0.02 mm or more and 1.0 mm or less.
  • a laminate comprising a laminate of thermoplastic resin coating layers.
  • (Claim 2) 2.
  • (Claim 3) 3.
  • the laminate according to claim 2 wherein the plurality of cloth-like bodies are laminated via an adhesive layer made of the same component.
  • (Claim 5) On at least one surface of a cloth laminate obtained by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin, a cloth having a thickness of 0.02 mm or more and 1.0 mm or less made of the same component as the filaments and having a thickness of 0.02 mm or more and 1.0 mm or less.
  • a laminate comprising a coating layer made of a thermoplastic resin and a top layer made of a thermoplastic resin having a thickness of 0.02 mm or more and 1.0 mm or less, which are laminated in this order.
  • (Claim 6) 6.
  • (Claim 7) 7.
  • (Claim 8) 6.
  • the adhesive layer uses at least one adhesive selected from acrylic adhesives, urethane adhesives, epoxy adhesives, vinyl acetate adhesives, styrene-butadiene rubber adhesives, and silicone adhesives.
  • the polar group-containing thermoplastic resin layer is a resin layer formed using modified polyolefin.
  • the modified polyolefin is a polyolefin acid-modified with an organic acid having a carboxyl group.
  • a cloth laminate formed by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin is provided on at least one surface of the cloth laminate with the same component as the filaments. It is characterized by laminating thermoplastic resin coating layers having a thickness of 0.02 mm or more and 1.0 mm or less.
  • FIG. 1 is a schematic cross-sectional view showing a first embodiment of the laminate of the present invention
  • FIG. 2 is a schematic cross-sectional view showing an example of improvement of FIG.
  • FIG. 1 shows an example in which a coating layer is laminated on one side of the laminate
  • FIG. 2 shows an example in which coating layers are laminated on both sides of the laminate.
  • a cloth laminate is formed by laminating a plurality of cloth-like bodies 2 made of filaments 1 made of a thermoplastic resin, and at least one of the cloth laminates is composed of the same components as those of the filaments 1.
  • the laminate of the present invention is obtained by laminating a thermoplastic resin coating layer 3 having a thickness of 0.02 mm or more and 1.0 mm or less and integrating them by thermocompression bonding.
  • the filamentous body 1 is mainly composed of a high-melting point resin component having a higher melting point than the thermocompression bonding temperature, but may contain a low-melting point resin component having a lower melting point than the thermocompression bonding temperature.
  • the structure of the striatum 1 can be exemplified by the aspect shown in FIG. FIG. 3( a ) is an example in which the filamentary body 1 is a single layer consisting of only the base layer 100 .
  • the resin constituting the filaments is composed of a high-melting point resin component, but can contain a low-melting point resin component within a range that does not impair the effects of the present invention.
  • 3(b) and 3(c) show a laminate structure in which a surface layer 101 made of a thermoplastic resin having a lower melting point than that of the base layer 100 is laminated on one or both sides of the base layer 100 of the filament 1. shows an example of FIG.
  • FIG. 3D shows an example in which a surface layer 101 made of a thermoplastic resin having a melting point lower than that of the base layer 100 has a core-sheath structure covering the periphery of the base layer 100 .
  • FIG. 3(e) is an example of a sea-island structure, and 102 is a portion of the low melting point resin component.
  • thermoplastic resin constituting the filamentous body for example, polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably used. Among them, polypropylene is particularly suitable.
  • means for forming a laminated film as a molding material include: (1) Means for preliminarily forming a film to be the base layer 100 and a film to be the surface layer 101 and forming a multilayer using a dry lamination method or a heat lamination method; (2) means for coating the surface of the film that serves as the base layer 100 with a thermoplastic resin that serves as the surface layer 101; (3) Means for extrusion laminating the surface layer 101 on a pre-formed film to serve as the base layer 100, or (4) Means for extruding a laminated film as a laminated film by a multi-layer coextrusion method.
  • thermoplastic resin that will be the surface layer 101 is laminated, and this is slit into a tape shape to obtain the stretched filamentous body 1.
  • the filamentous body 1 can be obtained by slitting the laminated film in which the base layer 100 and the surface layer 101 are laminated, and then stretching it in a uniaxial direction.
  • the stretching method is not particularly limited, and it can be carried out by single-stage or multi-stage stretching using hot rolls, a hot plate, a hot air oven, hot water, hot oil, steam, infrared irradiation, or the like.
  • the thickness of the filaments can be arbitrarily selected according to the purpose, but in general, in the case of a laminated structure, a range of 50 to 10000 decitex (dt) is desirable. For core-sheath structures (cover structures) as shown, a range of 1 to 10000 decitex (dt) is desirable.
  • the drawn filaments are not particularly limited as long as they are drawn yarns of semi-crystalline thermoplastic polymers, and include multifilaments, monofilaments, flat monofilaments, flat yarns, slit yarns, and the like. Multifilaments, monofilaments and flat monofilaments have the disadvantage that the surface smoothness of molded articles is inferior, so flat yarns and slit yarns are preferably used.
  • the cloth-like body 10 used in the present invention is preferably a woven cloth (for example, plain weave, twill weave, satin weave, leno weave, modified weave, etc.) woven using the filamentary body 1. It may be a cross-bonded cloth (soft) in which the crossing points of the strips 1 are joined in a plane by arranging the strips 1 perpendicularly, or the strips 1 made of the thermoplastic resin described above may be used. Knitted fabrics are also acceptable.
  • the basis weight of the woven fabric is preferably 50-500 g/m 2 , more preferably 50-400 g/m 2 .
  • the weave density of the woven fabric is preferably 5 threads/inch or more for each of the warp and weft threads in order to maintain the strength of the molded product.
  • the upper limit of the weave density varies depending on the type of yarn, and is not particularly limited, but is preferably 5 to 30 yarns/inch.
  • the coating layer 3 is provided on one surface of a laminate obtained by laminating a plurality of cloth-like bodies 2 . Moreover, in FIG. 2, the coating layers 3 are provided on both surfaces of a laminate formed by laminating a plurality of cloth-like bodies 2 .
  • the coating layer 3 is preferably a film made of the same material as the cloth-like body 2.
  • a film of polyolefin such as polypropylene or polyethylene, polyester such as polyethylene terephthalate, or polyamide can be preferably used.
  • the coating layer 3 can be formed on both sides or one side of the cloth-like body 2 (woven fabric) by a known extrusion lamination method, heat lamination method, calendering method, coating method, dipping method, or the like.
  • the cloth laminated body having the coating layer laminated thereon is formed by thermocompression bonding so that the molten polymer obtained by melting the coating layer 3 is the same component as the low-melting resin component of the cloth-like body.
  • impregnating the body 2 it is possible to form a laminate in which the interlayer adhesion between the cloth-like body 2 and the coating layer 3 is strengthened.
  • the formed laminate is heated to the melting point of the coating layer or higher, it is set in a mold for a molded product having a predetermined shape, and when pressed by the mold, the coating layer flows and the gap between the molds As a result, the pressing force by the mold is made uniform through the coating layer 3, and partial unevenness in pressing due to the tolerance of the mold gap can be eliminated. Defects can be eliminated.
  • 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 drawback that it is difficult to manufacture.
  • the viscosity of the coating layer 3 preferably has a storage elastic modulus at 150° C. of 5.0 ⁇ 10 4 or more and 1.0 ⁇ 10 8 or less. More preferably, the storage elastic modulus is 1.0 ⁇ 10 5 or more and 5.0 ⁇ 10 7 or less, and still more preferably 1.0 ⁇ 10 5 or more and 3.0 ⁇ 10 7 or less.
  • the storage elastic modulus of the coating layer 3 can be measured, for example, using the following measuring device (dynamic viscoelasticity temperature dispersion measurement).
  • ⁇ Measuring device> Device name: EPLEXOR500N (manufactured by Netchigabo) Measurement mode: Tensile mode Frequency: 1Hz Environment: under N2 Temperature range: -20°C to 180°C Heating rate: 2°C/min
  • the resin component that constitutes the filamentary body 1 and the coating layer 3 is the same component, and the same component includes a polypropylene resin component in common.
  • FIGS. 4 and 5 are schematic sectional views showing another example of improvement of FIG. 1.
  • FIG. As shown in FIGS. 4 and 5, an adhesive layer 4 is interposed between the cloth-like bodies 2 adjacent to each other.
  • the adhesive layer 4 is arranged between the cloth-like bodies 2 and adheres the cloth-like bodies 2 to each other.
  • the existence of this adhesive layer 4 has the function of improving the rigidity of the obtained laminate.
  • the adhesive layer 4 is preferably a film made of a thermoplastic resin.
  • a thermoplastic resin a resin containing a high melting point resin component in a low melting point resin component can be used.
  • the adhesive layer can function as a rigidity improving layer.
  • melting point refers to a temperature measured as a melting peak temperature by DSC measurement (Differential scanning calorimetry).
  • the high melting point resin component has a higher melting peak temperature than the low melting point resin component.
  • the adhesive layer 4 can exhibit two melting peak temperatures derived from these resins.
  • Polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably used as the low-melting resin component used for the adhesive layer 4 .
  • polyolefin is preferred, and polypropylene is more preferred.
  • the high-melting point resin component used in the adhesive layer 4 should have a higher melting point than the low-melting point resin component, and preferably includes polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like. Among them, polypropylene is particularly suitable.
  • the low melting point resin component and the high melting point resin component used in the adhesive layer 4 are each selected from polypropylene, for example, random polypropylene can be used as the low melting point resin component and homopolypropylene can be used as the high melting point resin component. .
  • a relatively low melting point random polypropylene may be used as the low melting point resin component, and a relatively high melting point random polypropylene may be used as the high melting point resin component.
  • Random polypropylene includes propylene as a monomer component and ⁇ -olefins (e.g., ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc. other than propylene.
  • ⁇ -olefin e.g., ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc. other than propylene.
  • ⁇ -olefin is randomly copolymerized.
  • the ⁇ -olefin can be used, for example, in a proportion of preferably 20% by weight or less, more preferably 10% by weight or less, relative to all monomer components.
  • the proportion of ⁇ -olefin can be adjusted to provide the desired melting point.
  • the melting point of random polypropylene can be set, for example, by adjusting the proportion of ⁇ -olefin, as described above.
  • the random polypropylene used as the low-melting resin component can have a lower ⁇ -olefin ratio as the high-melting resin component.
  • the adhesive layer 4 it is possible to use a film formed by kneading pellets of a low-melting resin component and pellets of a high-melting resin component at a temperature above the melting point of both resin components, and by inflation molding or the like.
  • the content of the high melting point resin component is, for example, preferably in the range of 5 wt% to 50 wt%, more preferably in the range of 10 wt% to 30 wt%.
  • the weight ratio of the low melting point resin component and the high melting point resin component in the adhesive layer 4 is preferably in the range of 5:95 to 50:50, more preferably in the range of 10:90 to 30:70. .
  • the thickness of the adhesive layer 4 is not limited because it can be set appropriately according to the thickness of the cloth-like body and the thickness of the filamentary bodies constituting the cloth-like body, for example, but is in the range of 10 ⁇ m to 500 ⁇ m and more preferably in the range of 20 ⁇ m to 300 ⁇ m.
  • three cloth-like bodies 2 are laminated and have coating layers 3 on both sides.
  • it is an example of a laminate composed of coating layer 3/fabric body 2/fabric body 2/fabric body 2/coating layer 3.
  • FIG. 3 is an example of a laminate composed of coating layer 3/fabric body 2/fabric body 2/fabric body 2/coating layer 3.
  • FIG. 2 has a covering layer 3 as the bottom layer.
  • These laminates are obtained by laminating a coating layer 3 on at least one surface of the laminated cloth-like body 2, and when the laminate is thermocompression bonded, the temperature at which the polymer constituting the coating layer 3 softens or partially melts. to fuse the coating layers 3 of the laminate sheet to each other or to soften the coating layers 3 to enter between or fuse to the woven fabrics, and the surface of the filamentous body 1 used for the cloth-like body 2
  • the low-melting-point resin component forming the layer 101 is melted, and the plurality of cloth-like bodies 2 are thermally compressed to be integrated.
  • the high melting point resin component constituting the base layer 100 of the filamentous body 1 remains as the fiber component of the cloth-like body 2 .
  • This fiber component is preferred because it acts to increase the strength of the molded article.
  • the number of woven fabrics is preferably 2 to 20, more preferably 2 to 10, and the number can be appropriately selected according to the purpose and application of the molded product, and the overlapping direction is also arbitrary. is. From the viewpoint of imparting appropriate strength (hardness) and impact resistance to the molded product, it is preferable to use at least two woven fabrics.
  • a cloth-like body and an adjacent cloth-like body are laminated via an adhesive layer, and have a coating layer on the surface.
  • a laminate composed of coating layer 3/fabric body 2/adhesive layer 4/fabric body 2/adhesive layer 4/fabric body 2.
  • FIG. 5 is an example of a laminate consisting of coating layer 3/fabric body 2/adhesive layer 4/fabric body 2/adhesive layer 4/fabric body 2/coating layer 3.
  • FIG. 5 is an example of a laminate consisting of coating layer 3/fabric body 2/adhesive layer 4/fabric body 2/adhesive layer 4/fabric body 2/coating layer 3.
  • FIG. 5 has a coating layer 3 as the bottom layer.
  • the coating layer 3 when the coating layer 3 is laminated on at least one surface of the laminated cloth-like body 2 and thermocompression bonded, the polymer constituting the coating layer 3 is heated to a temperature at which it softens or partially melts, The covering layers 3 of the laminate sheet are fused together or the covering layers 3 are softened and penetrated between the woven fabrics or fused to the woven fabrics.
  • the woven fabric and the adhesive film are heated to a temperature 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, and the woven fabric and the adhesive film are pressure-bonded and integrated to form a laminate sheet. make.
  • a plurality of cloth-like bodies 2 are laminated with adhesive layers 4 made of the same component interposed therebetween.
  • the same component contained in the cloth-like body and the adhesive layer preferably includes a polypropylene resin component in common.
  • the filaments when the filaments contain a low-melting point resin component and a high-melting point resin component, the filaments used for the cloth-like body 2 during thermocompression bonding of the laminate are used in the same manner as in the embodiment of FIG.
  • the low-melting-point resin component constituting the surface layer 101 of 1 is melted, and furthermore, the adhesive film is melted as described above, and the plurality of cloth-like bodies 2 are thermocompressed and integrated.
  • the high melting point resin component constituting the base layer 100 of the remaining filamentous body 1 remains as a fiber component.
  • the number of woven fabrics is preferably 2 to 20, more preferably 2 to 10, and the number is appropriately selected according to the purpose and application of the molded product. and the direction of superimposition is arbitrary. From the viewpoint of imparting appropriate strength (hardness) and impact resistance to the molded product, it is preferable to use at least two woven fabrics.
  • thermocompression bonding method for forming the laminate is not particularly limited, and known extrusion lamination molding methods, heat lamination methods, calendar molding methods, press molding methods, etc. can be employed.
  • Methods for forming a molded article having a predetermined shape from the formed laminate include press molding, stamping molding, plug-assisted pressure forming, pressure forming, vacuum pressure forming, vacuum press molding, plug-assisted vacuum forming, and vacuum forming. etc.
  • thermocompression bonding temperature is desirably lower than the melting point of the polymer so as not to reduce the crystallization of the polymer constituting the stretched filament.
  • the thermocompression bonding temperature is preferably about 115 to 125°C.
  • the thermocompression bonding temperature is preferably about 115 to 165.degree.
  • the laminate of the first aspect is set in a mold of a predetermined shape after being heated to the melting point or higher of the coating layer of the sheet-like laminate, and when pressed by the mold, the molten coating The resin of layer 3 flows and acts to close the mold gap tolerance.
  • the pressing force applied to the laminate by the mold is made uniform through the coating layer, and partial unevenness in pressing force due to the tolerance of the gap between molds can be eliminated, thereby eliminating poor appearance.
  • a cloth laminate formed by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin is provided on at least one surface of the cloth laminate with the same component as the filaments. It is characterized by laminating a thermoplastic resin coating layer having a thickness of 0.02 mm or more and 1.0 mm or less and a thermoplastic resin top layer having a thickness of 0.02 mm or more and 1.0 mm or less in this order.
  • the plurality of cloth-like bodies are laminated via an adhesive layer made of the same component, and the same component contained in the cloth-like body and the adhesive layer is polypropylene resin. It is to contain ingredients in common.
  • the coating layer and the top layer are preferably laminated in order via an adhesive layer.
  • the adhesive layer is preferably formed using at least one adhesive selected from adhesives, styrene-butadiene rubber-based adhesives, and silicone-based adhesives.
  • the coating layer and the top layer are laminated in order with the polar group-containing thermoplastic resin layer interposed therebetween.
  • the polar group-containing thermoplastic resin layer is preferably a resin layer formed using a modified polyolefin, and the modified polyolefin is a polyolefin acid-modified using an organic acid having a carboxyl group. Preferably.
  • FIG. A feature of this embodiment is that it has a top layer 5, as shown in FIGS.
  • top layer 5 is preferably made of the same material as the cloth-like body and the covering layer. Polypropylene and biaxially oriented polypropylene are preferred, and biaxially oriented polypropylene is more preferred.
  • the top layer 5 may be colored.
  • the top layer 5 itself may be colored with a pigment or paint, or a colored printed layer may be provided on the coating layer 3 side of the top layer 5 .
  • an adhesive layer 6 may be provided between the top layer 5 and the coating layer 3, as shown in FIG.
  • the adhesive is not particularly limited, but for example, an acrylic adhesive, a urethane adhesive, an epoxy adhesive, a vinyl acetate adhesive, a styrene/butadiene rubber adhesive, a silicone adhesive, or the like can be used. .
  • the method of providing the adhesive layer 6 is not particularly limited, but spraying, dip coating, brush coating, etc. can be exemplified.
  • top layer 5 provided on the upper surface of the adhesive layer 6 examples include unstretched polypropylene, biaxially stretched polypropylene film, unstretched polyethylene film, polyester film, polyamide film, acrylic film, and vinyl chloride film.
  • the material of the top layer can be changed.
  • an adhesive layer 4 may be provided between the cloth-like bodies 2 .
  • an adhesive film having the same structure as the adhesive layer 4 shown in FIGS. 4 and 5 can be used as the adhesive layer.
  • the feature of the embodiment shown in FIG. 8 is that the coating layer 3 and the top layer 5 are laminated in order with the polar group-containing thermoplastic resin layer 7 interposed therebetween.
  • the polar group-containing thermoplastic resin layer 7 of this embodiment is useful when it is desired to strengthen the bond with the top layer 5 .
  • the polar group-containing thermoplastic resin layer 7 is preferably composed of a modified polyolefin layer.
  • the modified polyolefin is preferably made of modified polyolefin obtained by modifying polyolefin.
  • the modified polyolefin layer 7 can also use at least one selected from acid-modified polypropylene and acid-modified modified polyethylene.
  • the polyolefin may be a homopolymer or a copolymer.
  • the monomer include ethylene, propylene, and the like, and these can be used singly or in combination of two or more. Any polymer may be used. In this aspect, these can be used alone or in combination of two or more. Among them, it is particularly preferable to use polypropylene and polyethylene as the polyolefin.
  • a method for modifying polyolefin includes a method of acid modification.
  • a technique for acid modification a method of graft-polymerizing an organic acid having a carboxyl group to a polyolefin, or the like can be used.
  • an acid-modified polyolefin in which an organic acid component is grafted onto polyolefin is obtained.
  • the polymerization method is not limited to graft polymerization, and any method can be appropriately selected and used.
  • organic acid is not particularly limited, it is preferably a saturated or unsaturated carboxylic acid or carboxylic anhydride having at least one carboxyl group.
  • organic acid for example, (1) maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, aconitic acid, crotonic acid, succinic acid, oxalic acid, malonic acid, malic acid, thiomarinic acid, tartaric acid, adipic acid, citric acid, pimelic acid, Carboxylic acids such as suberic acid, azelaic acid, acrylic acid, tetrahydrophthalic acid, isocrotonic acid, endocis-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid and sebacic acid; (2) Carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and succinic anhydride.
  • Carboxylic acids such as suberic acid, azelaic acid, acrylic acid, tetrahydrophthalic acid, isocrotonic acid, endocis-bicyclo(
  • the organic acids may be used singly or in combination of two or more.
  • modified polyolefin When the modified polyolefin is acid-modified, it can usually be modified to contain 0.01 to 10% by weight of the organic acid relative to the polyolefin.
  • the content of the organic acid is less than 0.01% by weight, it is not preferable because the interlayer adhesion is inferior when the modified polyolefin layer 7 is laminated between the cloth laminate and the copolymerized polyamide layer.
  • the amount exceeds 10% by weight if the polyolefin containing a molecularly crosslinked monomer as a main component is modified, the melt viscosity increases due to significant crosslinking of the polyolefin, and the polyolefin containing a molecularly cleaved monomer as a main component. When modified with respect to , the melt viscosity decreases due to significant main chain scission. As a result, when the modified polyolefin layer 7 is laminated between the cloth laminate and the copolymerized polyamide layer, the interlayer adhesion is poor.
  • the modified polyolefin layer 7 may contain other resins such as unmodified polyolefin to the extent that the effects of the present invention are not impaired.
  • the form of the modified polyolefin layer 7 is not particularly limited.
  • it can be in the form of a film or a sheet, or in a molten state for use in extrusion lamination or the like. From the viewpoint of versatility, a film-like or sheet-like one is preferable.
  • additives can be added to the filaments, the adhesive layer, the modified polyolefin layer, the copolyamide layer, and the thermoplastic polyurethane resin layer used in the cloth laminate, depending on the purpose. .
  • antioxidants such as organic phosphorus and thioether, light stabilizers such as hindered amines, UV absorbers such as benzophenones, benzotriazoles and benzoates, antistatic agents, bisamides, waxes, Dispersants such as organometallic salts, lubricants such as amides and organometallic salts, bromine-containing organic agents, phosphoric acid agents, melamine cyanurate agents, antimony trioxide flame retardants, low-density polyethylene, linear low-density Examples include stretching aids such as density polyethylene, organic pigments, inorganic pigments, inorganic fillers, organic fillers, inorganic antibacterial agents such as metal ion-based agents, and organic antibacterial agents.
  • FIG. 6 (Laminate of the second aspect)
  • the cloth-like body 2 has a covering layer 3 on at least one surface, and a top layer 5 is provided on the covering layer 3.
  • FIG. 2 It is a laminated body having a top layer 5 in addition to the laminated body of the first embodiment shown in FIG.
  • the top layer is laminated on the coating layer 3, and when the laminate is thermocompression bonded, the polymer constituting the coating layer 3 is heated to a temperature at which it softens or partially melts, and the coating layer 3 of the laminate sheet is heated. can be fused to each other or by softening the cover layer 3 to penetrate between or fused to the woven fabric and fused to the top layer 5 to form a laminate.
  • three cloth-like bodies 2 are laminated, and a coating layer 3 is provided on at least one surface of the cloth-like body 2, and an adhesive layer 6 is disposed on the coating layer 3. It has a top layer 5 .
  • a laminate composed of top layer 5 /adhesive layer 6 /coating layer 3 /fabric body 2 /fabric body 2 /fabric body 2 .
  • This laminated body further includes an adhesive layer 6 and a top layer 5 in addition to the laminated body of the first embodiment shown in FIG.
  • an adhesive is applied to the produced laminate to form an adhesive layer 6, and the top layer 5 is adhered via the adhesive of the adhesive layer 6, thereby obtaining a laminate of this embodiment. can be made.
  • a coating layer 3 is provided on at least one surface of the cloth-like body 2, and a polar group-containing thermoplastic resin layer is formed on the coating layer 3. It has a top layer 5 via 7 .
  • a polar group-containing thermoplastic resin layer 7 is laminated on the coating layer 3
  • a top layer 5 is laminated on the polar group-containing thermoplastic resin layer 7, and the laminate is thermocompression bonded to form the coating layer 3.
  • the layers are bonded to each other to produce the laminate of the present embodiment.
  • the top layer 5 when it is set in a mold of a predetermined shape and pressed by the mold, the top layer 5 becomes the outermost layer.
  • the coating layer 3 between the top layer 5 and the cloth-like body 2 is melted, melted from a portion with a large pressing force to a portion with a small pressing force, and the components of the coating layer move, resulting in , the pressing force for pressing the top layer 5 of the laminate is made uniform by the covering layer 3, and the occurrence of poor appearance can be prevented.
  • the laminate of the first aspect and the laminate of the second aspect of the present invention in press molding using male and female molds, partial pressing unevenness due to the tolerance of the mold gap is prevented, and the appearance is poor. Since it is possible to produce a laminate that does not generate , it is possible to produce moldings with excellent appearance, such as suitcases, attache cases, camera cases, musical instrument cases, and the like.
  • Adhesive Layer As the adhesive layer, a 0.06 mm polypropylene film containing a low melting point polypropylene having a melting point of 125° C. and a high melting point polypropylene having a melting point of 161° C. was used.
  • Laminate layer structure The three cloth-like bodies obtained and the two adhesive layers obtained were alternately arranged in a cloth-like body/adhesive layer/cloth-like body/adhesive layer/cloth-like body. A coating layer and a top layer were sequentially provided on the upper surface of the cloth-like body.
  • the coating layer was a 0.17 mm polypropylene film
  • the top layer was a 0.04 mm biaxially oriented polypropylene film.
  • the layer structure was made to be top layer/coating layer/fabric body/adhesive layer/fabric body/adhesive layer/fabric body.
  • the surface of the laminate was heated with an infrared heater until it reached 160 ° C., then press-molded with a mold heated to 80 ° C., closed for 2 minutes, and then demolded.
  • the pressing force by the mold was made uniform through the coating layer, and partial unevenness in pressing force due to the tolerance of the gap between the molds could be eliminated, thereby obtaining a molding with an excellent surface appearance.
  • Example 2 In Example 1, the infrared heater was replaced with a constant temperature furnace, and the surface of the laminate was heated to 170 ° C., press-molded with a mold heated to 100 ° C., and closed for 1.5 minutes. tested in the same way.
  • Example 2 similarly to Example 1, the pressing force by the mold is made uniform through the coating layer, and partial unevenness in pressing due to the tolerance of the mold gap can be eliminated, and the appearance of the surface can be improved. A molded product with excellent ductility was obtained.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention addresses the problem of providing a laminate which prevents partial pressing unevenness due to the tolerance of the die gap and does not cause a defect in appearance in press molding by male and female dies. The problem is solved by a laminate obtained by laminating, on at least one surface of a cloth laminate 2 obtained by laminating a plurality of cloth-like bodies 2 made of striatal bodies of thermoplastic resin, a coating layer 3 of a thermoplastic resin having a thickness of 0.02-1.0 mm made of the same component as the striatal bodies. The same component contained in the striatal bodies and the coating layer 3 preferably contains, in common, a polypropylene resin component. The plurality of cloth-like bodies are more preferably laminated via an adhesive layer 4 composed of the same component.

Description

積層体laminate
　本発明は、スーツケースなど用いられる積層体に関し、詳しくは、金型隙間の公差による部分的な押圧ムラを解消し、外観に優れる成形品を得ることができる積層体に関する。 The present invention relates to a laminate used in suitcases and the like, and more particularly to a laminate capable of eliminating partial pressure unevenness due to tolerances in mold gaps and obtaining a molded product with excellent appearance.
　特許文献1には、織布の両面に被覆層（ラミネートシート）を形成した被覆層付きの織布を複数セット用意し、その被覆層付きの織布を、織布が隣接しないように、熱可塑性ポリマーの融点以上かつ織布の融点未満の温度で熱圧着して板状シートを製造する技術が開示されている。 In Patent Document 1, a plurality of sets of woven fabrics with coating layers formed with coating layers (laminate sheets) on both sides of the woven fabric are prepared, and the woven fabrics with the coating layers are heated so that the woven fabrics are not adjacent to each other. A technique for producing a plate-like sheet by thermocompression bonding at a temperature above the melting point of a plastic polymer and below the melting point of a woven fabric is disclosed.
　これにより隣接するラミネートシートの被覆層を互いに融着させるので、成形品の強度を向上させることができる。こうして得られた成形品は、耐衝撃性及び引張強度に優れ適度な剛性を有する、スーツケースなどのケースとして好適なものとなる。 As a result, the coating layers of the adjacent laminate sheets are fused together, so the strength of the molded product can be improved. The molded article thus obtained has excellent impact resistance and tensile strength, and has appropriate rigidity, and is suitable for cases such as suitcases.
特開２０１４－２１８０７４号公報JP 2014-218074 A
　従来、クロス積層体を用いて、雄雌の金型によるプレス成形してスーツケースなどの成形品を製造する際に、金型隙間の公差による部分的な押圧ムラにより、外観不良が発生する問題があった。 Conventionally, when a cloth laminate is used to press-mold male and female molds to produce a molded product such as a suitcase, there is a problem of appearance defects due to partial pressure unevenness due to the tolerance of the mold gap. was there.
　特許文献１のような、被覆層付きの織布のセットを複数枚重ねて熱融着する手法では、金型隙間の公差による部分的な押圧ムラによる外観不良が発生するのを防止できなかった。 In the method of stacking and heat-sealing a plurality of sets of woven fabrics with a coating layer, as in Patent Document 1, it was not possible to prevent the occurrence of poor appearance due to partial uneven pressing due to the tolerance of the mold gap. .
　本発明の課題は、雄雌の金型によるプレス成形において、金型隙間の公差による部分的な押圧ムラを防止して、外観不良の発生しない積層体を提供することにある。 An object of the present invention is to provide a laminate that does not cause poor appearance by preventing partial pressure unevenness due to the tolerance of mold gaps in press molding using male and female molds.
　さらに本発明の他の課題は、以下の記載によって明らかとなる。 Further, other problems of the present invention will become clear from the following description.
　上記課題は以下の各発明によって解決される。 The above problems are solved by the following inventions.
（請求項１）
　熱可塑性樹脂製の線条体からなる複数の布状体を積層してなるクロス積層体の少なくとも一方の面に、前記線条体と同一成分からなる厚さ０．０２ｍｍ以上 １．０ｍｍ以下の熱可塑性樹脂の被覆層が積層してなることを特徴とする積層体。
（請求項２）
　前記線条体と前記被覆層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことを特徴とする請求項１記載の積層体。
（請求項３）
　前記複数の布状体同士が、同一成分からなる接着層を介して積層してなることを特徴とする請求項２記載の積層体。
（請求項４）
　前記布状体と接着層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことを特徴とする請求項３記載の積層体。
（請求項５）
　熱可塑性樹脂製の線条体からなる複数の布状体を積層してなるクロス積層体の少なくとも一方の面に、前記線条体と同一成分からなる厚さ０．０２ｍｍ以上 １．０ｍｍ以下の熱可塑性樹脂の被覆層と、０．０２ｍｍ以上１．０ｍｍ以下の熱可塑性樹脂からなるトップ層が順に積層してなることを特徴とする積層体。
（請求項６）
　前記複数の布状体同士が、同一成分からなる接着層を介して積層してなることを特徴とする請求項５記載の積層体。
（請求項７）
　前記布状体と接着層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことを特徴とする請求項６記載の積層体。
（請求項８）
　前記被覆層と、前記トップ層が、接着剤層を介して順に積層してなることを特徴とする請求項５記載の積層体。
（請求項９）
　前記接着剤層は、アクリル系接着剤、ウレタン系接着剤、エポキシ系接着剤、酢酸ビニル系接着剤、スチレン・ブタジエンゴム系接着剤、シリコーン系接着剤から選ばれる少なくとも１種の接着剤を用いて形成された接着剤層であることを特徴とする請求項８記載の積層体。
（請求項１０）
　前記被覆層と、前記トップ層が、極性基含有熱可塑性樹脂層を介して順に積層してなることを特徴とする請求項５記載の積層体。
（請求項１１）
　前記極性基含有熱可塑性樹脂層が、変性ポリオレフィンを用いて形成されて樹脂層であることを特徴とする請求項１０記載の積層体。
（請求項１２）
　前記変性ポリオレフィンは、ポリオレフィンに、カルボキシル基を有する有機酸を用いて酸変性されたものであることを特徴とする請求項１１記載の積層体。　　 (Claim 1)
On at least one surface of a cloth laminate obtained by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin, a cloth having a thickness of 0.02 mm or more and 1.0 mm or less made of the same component as the filaments and having a thickness of 0.02 mm or more and 1.0 mm or less. A laminate comprising a laminate of thermoplastic resin coating layers.
(Claim 2)
2. The laminate according to claim 1, wherein the same component contained in said filaments and said coating layer includes a polypropylene resin component in common.
(Claim 3)
3. The laminate according to claim 2, wherein the plurality of cloth-like bodies are laminated via an adhesive layer made of the same component.
(Claim 4)
4. The laminate according to claim 3, wherein the same component contained in the cloth-like body and the adhesive layer includes a polypropylene resin component in common.
(Claim 5)
On at least one surface of a cloth laminate obtained by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin, a cloth having a thickness of 0.02 mm or more and 1.0 mm or less made of the same component as the filaments and having a thickness of 0.02 mm or more and 1.0 mm or less. A laminate comprising a coating layer made of a thermoplastic resin and a top layer made of a thermoplastic resin having a thickness of 0.02 mm or more and 1.0 mm or less, which are laminated in this order.
(Claim 6)
6. The laminate according to claim 5, wherein the plurality of cloth-like bodies are laminated via an adhesive layer made of the same component.
(Claim 7)
7. The laminate according to claim 6, wherein the same component contained in the cloth-like body and the adhesive layer includes a polypropylene resin component in common.
(Claim 8)
6. The laminate according to claim 5, wherein said coating layer and said top layer are laminated in order via an adhesive layer.
(Claim 9)
The adhesive layer uses at least one adhesive selected from acrylic adhesives, urethane adhesives, epoxy adhesives, vinyl acetate adhesives, styrene-butadiene rubber adhesives, and silicone adhesives. 9. The laminate according to claim 8, wherein the adhesive layer is formed by
(Claim 10)
6. The laminate according to claim 5, wherein the coating layer and the top layer are laminated in order via a polar group-containing thermoplastic resin layer.
(Claim 11)
11. The laminate according to claim 10, wherein the polar group-containing thermoplastic resin layer is a resin layer formed using modified polyolefin.
(Claim 12)
12. The laminate according to claim 11, wherein the modified polyolefin is a polyolefin acid-modified with an organic acid having a carboxyl group.
　本発明によれば、雄雌の金型によるプレス成形において、被覆層が金型隙間に流れ込むことでの押圧ムラが解消し外観に優れる成形品を得ることができる。 According to the present invention, in press molding using male and female molds, it is possible to eliminate uneven pressing caused by the coating layer flowing into the mold gap, and to obtain a molded product with excellent appearance.
　更に、本発明によれば、トップ層が存在する場合には、表面の傷付き防止性能に加え、光沢感、マット調感など意匠性への効果も期待できる。 Furthermore, according to the present invention, when the top layer is present, in addition to the scratch-preventing performance of the surface, effects on design properties such as glossiness and matte tone can be expected.
本発明の積層体の第１態様を示す概略断面図BRIEF DESCRIPTION OF THE DRAWINGS The schematic sectional drawing which shows the 1st aspect of the laminated body of this invention. 図１に示す態様の改良の一例を示す概略断面図Schematic cross-sectional view showing an example of improvement of the embodiment shown in FIG. 本発明に用いられる線条体を示す概略断面図Schematic cross-sectional view showing a filamentary body used in the present invention 図１に示す態様の改良の他の例を示す概略断面図Schematic cross-sectional view showing another example of improvement of the embodiment shown in FIG. 図１に示す態様の改良の他の例を示す概略断面図Schematic cross-sectional view showing another example of improvement of the embodiment shown in FIG. 本発明の積層体の第２態様を示す概略断面図Schematic cross-sectional view showing a second embodiment of the laminate of the present invention 図６に示す態様の改良の例を示す概略断面図Schematic cross-sectional view showing an example of improvement of the embodiment shown in FIG. 図６に示す態様の改良の他の例を示す概略断面図Schematic cross-sectional view showing another example of improvement of the embodiment shown in FIG.
　以下、本発明について好ましい実施の形態について説明する。 Preferred embodiments of the present invention will be described below.
〔第１態様〕
　本発明の積層体の第１態様は、熱可塑性樹脂製の線条体からなる複数の布状体を積層してなるクロス積層体の少なくとも一方の面に、前記線条体と同一成分からなる厚さ０．０２ｍｍ以上 １．０ｍｍ以下の熱可塑性樹脂の被覆層が積層してなることを特徴とする。 [First aspect]
In a first aspect of the laminate of the present invention, a cloth laminate formed by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin is provided on at least one surface of the cloth laminate with the same component as the filaments. It is characterized by laminating thermoplastic resin coating layers having a thickness of 0.02 mm or more and 1.0 mm or less.
　図１は、本発明の積層体の第１態様を示す概略断面図であり、図２は、図１の改良の一例を示す概略断面図である。図１は積層物の一方の面に被覆層を積層した例を示し、図２は、積層物の両方の面に被覆層を積層した例を示す。 FIG. 1 is a schematic cross-sectional view showing a first embodiment of the laminate of the present invention, and FIG. 2 is a schematic cross-sectional view showing an example of improvement of FIG. FIG. 1 shows an example in which a coating layer is laminated on one side of the laminate, and FIG. 2 shows an example in which coating layers are laminated on both sides of the laminate.
　本発明において、熱可塑性樹脂製の線条体１からなる複数の布状体２を積層してなるクロス積層体が形成され、該クロス積層体の少なくとも一方に、線条体１と同一成分からなる厚さ０．０２ｍｍ以上 １．０ｍｍ以下の熱可塑性樹脂の被覆層３が積層され、これらを熱圧着して一体化されることによって本発明の積層体が得られる。 In the present invention, a cloth laminate is formed by laminating a plurality of cloth-like bodies 2 made of filaments 1 made of a thermoplastic resin, and at least one of the cloth laminates is composed of the same components as those of the filaments 1. The laminate of the present invention is obtained by laminating a thermoplastic resin coating layer 3 having a thickness of 0.02 mm or more and 1.0 mm or less and integrating them by thermocompression bonding.
（線条体）
　線条体１は、熱圧着の温度よりも融点の高い高融点樹脂成分を主体として構成されるが、熱圧着の温度よりも融点の低い低融点樹脂成分を含むことができる。 (striatum)
The filamentous body 1 is mainly composed of a high-melting point resin component having a higher melting point than the thermocompression bonding temperature, but may contain a low-melting point resin component having a lower melting point than the thermocompression bonding temperature.
　線条体１の構造は、図３に示すような態様が例示できる。図３（ａ）は、線条体１が基層１００のみの単層とした例である。この例の場合、線条体を構成する樹脂は、高融点樹脂成分で構成されるが、本発明の効果を損なわない範囲で、低融点樹脂成分を含むことができる。図３（ｂ）、（ｃ）は、線条体１が基層１００の片面又は両面に、基層１００よりも融点の低い低融点樹脂成分の熱可塑性樹脂からなる表面層１０１が積層された積層構造の例を示している。図３（ｄ）は、基層１００よりも融点の低い熱可塑性樹脂からなる表面層１０１が、基層１００の周囲を覆う芯鞘構造とした例である。図３（ｅ）は、海島構造の例であり、１０２は低融点樹脂成分の部位である。 The structure of the striatum 1 can be exemplified by the aspect shown in FIG. FIG. 3( a ) is an example in which the filamentary body 1 is a single layer consisting of only the base layer 100 . In the case of this example, the resin constituting the filaments is composed of a high-melting point resin component, but can contain a low-melting point resin component within a range that does not impair the effects of the present invention. 3(b) and 3(c) show a laminate structure in which a surface layer 101 made of a thermoplastic resin having a lower melting point than that of the base layer 100 is laminated on one or both sides of the base layer 100 of the filament 1. shows an example of FIG. 3D shows an example in which a surface layer 101 made of a thermoplastic resin having a melting point lower than that of the base layer 100 has a core-sheath structure covering the periphery of the base layer 100 . FIG. 3(e) is an example of a sea-island structure, and 102 is a portion of the low melting point resin component.
　線条体１を構成する熱可塑性樹脂としては、例えば、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリエチレンテレフタレート等のポリエステルなどを好ましく挙げることができる。中でも、ポリプロピレンが特に好適である。 As the thermoplastic resin constituting the filamentous body 1, for example, polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably used. Among them, polypropylene is particularly suitable.
　線条体１として積層構造のものが使用される場合、その成形材料となる積層フィルムを成形する手段としては、
　（１）予め基層１００となるフィルムと表面層１０１となるフィルムを形成してドライラミネート法や熱ラミネート法を用いて複層化する手段、
　（２）基層１００となるフィルムの表面に表面層１０１となる熱可塑性樹脂をコーティングする手段、
　（３）予め形成した基層１００となるフィルムに表面層１０１を押出ラミネートする手段、あるいは
　（４）多層共押出法によって積層フィルムとして押出成形する手段等から適宜選択して用いることができる。 When a laminated structure is used as the linear body 1, means for forming a laminated film as a molding material include:
(1) Means for preliminarily forming a film to be the base layer 100 and a film to be the surface layer 101 and forming a multilayer using a dry lamination method or a heat lamination method;
(2) means for coating the surface of the film that serves as the base layer 100 with a thermoplastic resin that serves as the surface layer 101;
(3) Means for extrusion laminating the surface layer 101 on a pre-formed film to serve as the base layer 100, or (4) Means for extruding a laminated film as a laminated film by a multi-layer coextrusion method.
　基層１００となるフィルムを、例えば一軸方向に延伸した後、表面層１０１となる熱可塑性樹脂を積層し、これをテープ状にスリットして延伸された線条体１を得ることができる。 After the film that will be the base layer 100 is uniaxially stretched, for example, a thermoplastic resin that will be the surface layer 101 is laminated, and this is slit into a tape shape to obtain the stretched filamentous body 1.
　あるいは、基層１００と表面層１０１とが積層された積層フィルムをスリットした後、一軸方向に延伸することによって線条体１を得ることもできる。 Alternatively, the filamentous body 1 can be obtained by slitting the laminated film in which the base layer 100 and the surface layer 101 are laminated, and then stretching it in a uniaxial direction.
　延伸方法は特に限定されるものではなく、熱ロール、熱板、熱風炉、温水、熱油、蒸気、赤外線照射等を用い、一段もしくは多段延伸によって行うことができる。 The stretching method is not particularly limited, and it can be carried out by single-stage or multi-stage stretching using hot rolls, a hot plate, a hot air oven, hot water, hot oil, steam, infrared irradiation, or the like.
　線条体の太さは、目的に応じて任意に選定することができるが、一般的には、積層構造の場合は、５０～１００００デシテックス（ｄｔ）の範囲が望ましく、図３（ｄ）で示されるような芯鞘構造（被覆構造）の場合は、１～１００００デシテックス（ｄｔ）の範囲が望ましい。 The thickness of the filaments can be arbitrarily selected according to the purpose, but in general, in the case of a laminated structure, a range of 50 to 10000 decitex (dt) is desirable. For core-sheath structures (cover structures) as shown, a range of 1 to 10000 decitex (dt) is desirable.
　延伸された線条体は、半結晶性熱可塑性ポリマーの延伸糸であれば特に限定されるものではなく、マルチフィラメント、モノフィラメント、扁平モノフィラメント、フラットヤーン、スリットヤーンなどが挙げられる。マルチフィラメント、モノフィラメント及び扁平モノフィラメントは、成形品の表面平滑性が劣る欠点があるため、フラットヤーン、スリットヤーンが好適に用いられる。 The drawn filaments are not particularly limited as long as they are drawn yarns of semi-crystalline thermoplastic polymers, and include multifilaments, monofilaments, flat monofilaments, flat yarns, slit yarns, and the like. Multifilaments, monofilaments and flat monofilaments have the disadvantage that the surface smoothness of molded articles is inferior, so flat yarns and slit yarns are preferably used.
　（布状体）　
　本発明に用いられる布状体１０は、線条体１を用いて織成した織布（例えば平織、綾織、朱子織、絡み織や変化組織など）が好ましいが、多数の熱可塑性樹脂からなる線条体１を直交するように並設することによって面状としてその交点を接合した交差結合布（ソフ）であってもよいし、その他上記の熱可塑性樹脂からなる線条体１で形成された編物でもよい。
　織布の目付は、５０～５００ｇ／ｍ２のものが好ましく、より好ましくは５０～４００ｇ／ｍ２である。 (Cloth-like body)
The cloth-like body 10 used in the present invention is preferably a woven cloth (for example, plain weave, twill weave, satin weave, leno weave, modified weave, etc.) woven using the filamentary body 1. It may be a cross-bonded cloth (soft) in which the crossing points of the strips 1 are joined in a plane by arranging the strips 1 perpendicularly, or the strips 1 made of the thermoplastic resin described above may be used. Knitted fabrics are also acceptable.
The basis weight of the woven fabric is preferably 50-500 g/m 2 , more preferably 50-400 g/m 2 .
　織布の織密度は、経糸及び緯糸がそれぞれ５本／インチ以上であることが、成形品の強度を保持するうえで望ましい。織密度の上限は糸の種類によって異なり、特に限定されるものではないが、好ましくは５本～３０本／インチである。 The weave density of the woven fabric is preferably 5 threads/inch or more for each of the warp and weft threads in order to maintain the strength of the molded product. The upper limit of the weave density varies depending on the type of yarn, and is not particularly limited, but is preferably 5 to 30 yarns/inch.
　（被覆層）
　図１において、被覆層３は、複数の布状体２を積層してなる積層物の一方の面に設けられている。また図２においては、被覆層３は、複数の布状体２を積層してなる積層物の両方の面に設けられている。 (coating layer)
In FIG. 1, the coating layer 3 is provided on one surface of a laminate obtained by laminating a plurality of cloth-like bodies 2 . Moreover, in FIG. 2, the coating layers 3 are provided on both surfaces of a laminate formed by laminating a plurality of cloth-like bodies 2 .
　被覆層３は、布状体２と同一素材のフィルムが好ましく、例えば、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリエチレンテレフタレート等のポリエステル、ポリアミドなどのフィルムを好ましく用いることができる。 The coating layer 3 is preferably a film made of the same material as the cloth-like body 2. For example, a film of polyolefin such as polypropylene or polyethylene, polyester such as polyethylene terephthalate, or polyamide can be preferably used.
　これらのフィルムを被覆層３に用いれば、軽量で耐衝撃性に優れ、融点が低く加工し易く、延伸線条体との溶融接着性に優れるので好ましく、中でも、ポリオレフィンが好ましく、より好ましくはポリプロピレンである。
　被覆層３は、公知の押出ラミネート法、熱ラミネート法、カレンダー法、コーティング法、浸漬法等により、布状体２（織布）の両面もしくは片面に形成できる。 It is preferable to use these films for the coating layer 3 because they are lightweight, have excellent impact resistance, have a low melting point, are easy to process, and have excellent melt adhesiveness to the stretched filament. Among them, polyolefin is preferable, and polypropylene is more preferable. is.
The coating layer 3 can be formed on both sides or one side of the cloth-like body 2 (woven fabric) by a known extrusion lamination method, heat lamination method, calendering method, coating method, dipping method, or the like.
　本実施形態は、被覆層が積層されたクロス積層体が、熱圧着により、被覆層３が溶融してなる溶融ポリマーが布状体の低融点樹脂成分と同一の成分であることによって、布状体２に含侵して、布状体２と被覆層３との層間接着が強固になった積層体を形成することができる。 In the present embodiment, the cloth laminated body having the coating layer laminated thereon is formed by thermocompression bonding so that the molten polymer obtained by melting the coating layer 3 is the same component as the low-melting resin component of the cloth-like body. By impregnating the body 2, it is possible to form a laminate in which the interlayer adhesion between the cloth-like body 2 and the coating layer 3 is strengthened.
　そして、形成された積層体が、被覆層の融点以上に加熱された後に、所定形状の成形品の金型にセットされ、金型により押圧されると、被覆層が流動して、金型隙間の公差部分を埋めるように作用し、その結果、金型による押圧力が、被覆層３を介して均一化にされ、金型隙間の公差による部分的な押圧ムラをなくすことができ、さらに外観不良もなくすことができる。 Then, after the formed laminate is heated to the melting point of the coating layer or higher, it is set in a mold for a molded product having a predetermined shape, and when pressed by the mold, the coating layer flows and the gap between the molds As a result, the pressing force by the mold is made uniform through the coating layer 3, and partial unevenness in pressing due to the tolerance of the mold gap can be eliminated. Defects can be eliminated.
　被覆層３の厚さは、０．０２ｍｍ以上 １．０ｍｍ以下である。厚みが０．０２ｍｍ未満であると、製造困難である欠点があり、一方、厚みが大きくなり過ぎると、軽量性を損なう。 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 drawback that it is difficult to manufacture.
　また、被覆層３の粘度は、１５０℃における貯蔵弾性率が５．０×１０４以上１．０×１０８以下である特性を有することが好ましい。より好ましくは貯蔵弾性率が、１．０×１０５以上５．０×１０７以下、更に好ましくは、１．０×１０５以上３．０×１０７以下である特性を有する。 Moreover, the viscosity of the coating layer 3 preferably has a storage elastic modulus at 150° C. of 5.0×10 4 or more and 1.0×10 8 or less. More preferably, the storage elastic modulus is 1.0×10 5 or more and 5.0×10 7 or less, and still more preferably 1.0×10 5 or more and 3.0×10 7 or less.
　被覆層３の貯蔵弾性率は、例えば、以下の測定装置（動的粘弾性　温度分散測定）を用いて測定することができる。
　＜測定装置＞
　装置名：ＥＰＬＥＸＯＲ５００Ｎ（ネッチガボ社製）
　測定モード：引張モード
　周波数：１Ｈｚ
　環境：Ｎ２下
　温度範囲：－２０℃～１８０℃
　昇温速度：２℃／ｍｉｎ The storage elastic modulus of the coating layer 3 can be measured, for example, using the following measuring device (dynamic viscoelasticity temperature dispersion measurement).
<Measuring device>
Device name: EPLEXOR500N (manufactured by Netchigabo)
Measurement mode: Tensile mode Frequency: 1Hz
Environment: under N2 Temperature range: -20°C to 180°C
Heating rate: 2°C/min
　本発明において、線条体１と被覆層３を構成する樹脂成分は同一成分であり、かかる同一成分というのは、ポリプロピレン樹脂成分を共通して含むことである。 In the present invention, the resin component that constitutes the filamentary body 1 and the coating layer 3 is the same component, and the same component includes a polypropylene resin component in common.
　（接着層）
　接着層について、図４及び図５に基づいて説明する。図１～３と同一の符号は同一の構成であるため、その説明を省略し援用する。 (adhesive layer)
The adhesive layer will be described with reference to FIGS. 4 and 5. FIG. Since the same reference numerals as those in FIGS. 1 to 3 have the same configuration, the description thereof will be omitted and incorporated.
　図４及び図５は、図１の改良の他の例を示す概略断面図である。
　図４及び図５に示すように、布状体２と隣接する布状体２の間には、接着層４が介装されている。 4 and 5 are schematic sectional views showing another example of improvement of FIG. 1. FIG.
As shown in FIGS. 4 and 5, an adhesive layer 4 is interposed between the cloth-like bodies 2 adjacent to each other.
　接着層４は、布状体２と布状体２との間に配置されて、これら布状体２と布状体２との間を接着する。この接着層４の存在により、得られる積層体の剛性を向上する機能を有する。 The adhesive layer 4 is arranged between the cloth-like bodies 2 and adheres the cloth-like bodies 2 to each other. The existence of this adhesive layer 4 has the function of improving the rigidity of the obtained laminate.
　接着層４は、熱可塑性樹脂により構成されるフィルムが好ましい。この熱可塑性樹脂として、低融点樹脂成分に、高融点樹脂成分を含有させたものを用いることできる。低融点樹脂成分に高融点樹脂成分を含有させると、接着層を剛性向上層として機能させることができる。 The adhesive layer 4 is preferably a film made of a thermoplastic resin. As this thermoplastic resin, a resin containing a high melting point resin component in a low melting point resin component can be used. When the low melting point resin component contains the high melting point resin component, the adhesive layer can function as a rigidity improving layer.
　本明細書において、「融点」というのは、ＤＳＣ測定（示差走査熱量測定；Differential scanning calorimetry）により融解ピーク温度として測定される温度のことである。
　言い換えれば、高融点樹脂成分は、低融点樹脂成分よりも融解ピーク温度が高い関係にある。接着層４は、これら樹脂に由来する２つの融解ピーク温度を示し得る。 As used herein, the term "melting point" refers to a temperature measured as a melting peak temperature by DSC measurement (Differential scanning calorimetry).
In other words, the high melting point resin component has a higher melting peak temperature than the low melting point resin component. The adhesive layer 4 can exhibit two melting peak temperatures derived from these resins.
　接着層４に用いられる低融点樹脂成分としては、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリエチレンテレフタレート等のポリエステルなどを好ましく挙げることができる。中でも、ポリオレフィンが好ましく、より好ましくはポリプロピレンである。 Polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like can be preferably used as the low-melting resin component used for the adhesive layer 4 . Among them, polyolefin is preferred, and polypropylene is more preferred.
　接着層４に用いられる高融点樹脂成分としては、低融点樹脂成分よりも融点が高いものであればよいが、ポリプロピレン、ポリエチレン等のポリオレフィン、ポリエチレンテレフタレート等のポリエステルなどを好ましく挙げることができる。中でも、ポリプロピレンが特に好適である。 The high-melting point resin component used in the adhesive layer 4 should have a higher melting point than the low-melting point resin component, and preferably includes polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like. Among them, polypropylene is particularly suitable.
　接着層４に用いられる低融点樹脂成分及び高融点樹脂成分が、それぞれポリプロピレンから選択される場合は、例えば、低融点樹脂成分としてランダムポリプロピレンを用い、高融点樹脂成分としてホモポリプロピレンを用いることができる。また、低融点樹脂成分として比較的低融点のランダムポリプロピレンを用い、高融点樹脂成分として比較的高融点のランダムポリプロピレンを用いることもできる。 When the low melting point resin component and the high melting point resin component used in the adhesive layer 4 are each selected from polypropylene, for example, random polypropylene can be used as the low melting point resin component and homopolypropylene can be used as the high melting point resin component. . Alternatively, a relatively low melting point random polypropylene may be used as the low melting point resin component, and a relatively high melting point random polypropylene may be used as the high melting point resin component.
　ランダムポリプロピレンは、モノマー成分としてのプロピレンと、α－オレフィン（例えば、エチレン、１－ブテン、１－ペンテン、１－ヘキセン、４－メチル－１－ペンテン、１－ヘプテン、１－オクテン等のプロピレン以外のα－オレフィン）とが、ランダムに共重合したものである。 Random polypropylene includes propylene as a monomer component and α-olefins (e.g., ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, etc. other than propylene. α-olefin) is randomly copolymerized.
　α－オレフィンは、例えば、全モノマー成分に対して、好ましくは２０重量％以下、より好ましくは１０重量％以下の割合で用いることができる。所望の融点を示すように、α－オレフィンの割合を調整することができる。 The α-olefin can be used, for example, in a proportion of preferably 20% by weight or less, more preferably 10% by weight or less, relative to all monomer components. The proportion of α-olefin can be adjusted to provide the desired melting point.
　ランダムポリプロピレンの融点は、上述したように、例えば、α－オレフィンの割合を調整すること等により設定することができる。具体的には、例えば、低融点樹脂成分として用いるランダムポリプロピレンよりもα－オレフィンの割合が小さいものを高融点樹脂成分として用いることができる。 The melting point of random polypropylene can be set, for example, by adjusting the proportion of α-olefin, as described above. Specifically, for example, the random polypropylene used as the low-melting resin component can have a lower α-olefin ratio as the high-melting resin component.
　接着層４としては、低融点樹脂成分のペレットと高融点樹脂成分のペレットとを、両樹脂成分の融点以上の温度で混練し、インフレーション成形等により形成されたフィルムを用いることができる。 As the adhesive layer 4, it is possible to use a film formed by kneading pellets of a low-melting resin component and pellets of a high-melting resin component at a temperature above the melting point of both resin components, and by inflation molding or the like.
　接着層４において、高融点樹脂成分の含有量は、例えば、５重量％～５０重量％の範囲であることが好ましく、１０重量％～３０重量％の範囲であることが更に好ましい。 In the adhesive layer 4, the content of the high melting point resin component is, for example, preferably in the range of 5 wt% to 50 wt%, more preferably in the range of 10 wt% to 30 wt%.
　また、接着層４における低融点樹脂成分と高融点樹脂成分の重量比率は、５：９５～５０：５０の範囲であることが好ましく、１０：９０～３０：７０の範囲であることが更に好ましい。 The weight ratio of the low melting point resin component and the high melting point resin component in the adhesive layer 4 is preferably in the range of 5:95 to 50:50, more preferably in the range of 10:90 to 30:70. .
　接着層４の厚さは、例えば、布状体の厚さや、布状体を構成する線条体の太さ等に応じて適宜設定可能であるので限定的ではないが、１０μｍ～５００μｍの範囲であることが好ましく、２０μｍ～３００μｍの範囲であることが更に好ましい。 The thickness of the adhesive layer 4 is not limited because it can be set appropriately according to the thickness of the cloth-like body and the thickness of the filamentary bodies constituting the cloth-like body, for example, but is in the range of 10 μm to 500 μm and more preferably in the range of 20 μm to 300 μm.
　（第１の態様の積層体）
　図１の例では、３枚の布状体２を積層しており、表面に被覆層３を有している。具体的には、被覆層３／布状体２／布状体２／布状体２からなる積層体の例である。 (Laminate of the first aspect)
In the example of FIG. 1, three cloth-like bodies 2 are laminated and have a coating layer 3 on the surface. Specifically, it is an example of a laminate composed of coating layer 3/fabric body 2/fabric body 2/fabric body 2. FIG.
　図２の例では、３枚の布状体２を積層しており、両面に被覆層３を有している。具体的には、被覆層３／布状体２／布状体２／布状体２／被覆層３からなる積層体の例である。 In the example of FIG. 2, three cloth-like bodies 2 are laminated and have coating layers 3 on both sides. Specifically, it is an example of a laminate composed of coating layer 3/fabric body 2/fabric body 2/fabric body 2/coating layer 3. FIG.
　図１の態様との差異は、図２では最下層に被覆層３を有している点である。
　これらの積層体は、積層された布状体２の少なく一方の面に、被覆層３を積層し、積層体の熱圧着時、被覆層３を構成するポリマーが軟化もしくは一部が溶融する温度まで加熱され、ラミネートシートの被覆層３を互いに融着或いは被覆層３を軟化させて織布の間に侵入もしくは織布に融着されると共に、布状体２に用いる線条体１の表面層１０１を構成する低融点樹脂成分が融解し、複数の布状体２同士が熱圧着されて一体化される。その際、残った線条体１の基層１００を構成する高融点樹脂成分が、布状体２の繊維成分として残存する。この繊維成分が成形品の強度を増強する作用を呈するので好ましい。 The difference from the embodiment of FIG. 1 is that FIG. 2 has a covering layer 3 as the bottom layer.
These laminates are obtained by laminating a coating layer 3 on at least one surface of the laminated cloth-like body 2, and when the laminate is thermocompression bonded, the temperature at which the polymer constituting the coating layer 3 softens or partially melts. to fuse the coating layers 3 of the laminate sheet to each other or to soften the coating layers 3 to enter between or fuse to the woven fabrics, and the surface of the filamentous body 1 used for the cloth-like body 2 The low-melting-point resin component forming the layer 101 is melted, and the plurality of cloth-like bodies 2 are thermally compressed to be integrated. At that time, the high melting point resin component constituting the base layer 100 of the filamentous body 1 remains as the fiber component of the cloth-like body 2 . This fiber component is preferred because it acts to increase the strength of the molded article.
　本形態において、織布の枚数は、好ましくは２～２０枚、さらに好ましくは２～１０枚であり、枚数は成形品の目的や用途に合わせて適宜選択することができ、重ね合せる方向も任意である。成形品に適度な強度（堅さ）や耐衝撃性を付与する観点からは、織布は少なくとも２枚以上用いることが好ましい。 In this embodiment, the number of woven fabrics is preferably 2 to 20, more preferably 2 to 10, and the number can be appropriately selected according to the purpose and application of the molded product, and the overlapping direction is also arbitrary. is. From the viewpoint of imparting appropriate strength (hardness) and impact resistance to the molded product, it is preferable to use at least two woven fabrics.
　次に、図４の例では、布状体と隣接する布状体とを、接着層を介して積層しており、表面に被覆層を有している。具体的には、被覆層３／布状体２／接着層４／布状体２／接着層４／布状体２からなる積層体の例である。 Next, in the example of FIG. 4, a cloth-like body and an adjacent cloth-like body are laminated via an adhesive layer, and have a coating layer on the surface. Specifically, it is an example of a laminate composed of coating layer 3/fabric body 2/adhesive layer 4/fabric body 2/adhesive layer 4/fabric body 2. FIG.
　図５の例は、被覆層３／布状体２／接着層４／布状体２／接着層４／布状体２／被覆層３からなる積層体の例である。 The example of FIG. 5 is an example of a laminate consisting of coating layer 3/fabric body 2/adhesive layer 4/fabric body 2/adhesive layer 4/fabric body 2/coating layer 3. FIG.
　図４の態様との差異は、図５では最下層に被覆層３を有している点である。
　本形態においては、積層された布状体２の少なく一方の面に、被覆層３を積層し、熱圧着すると、被覆層３を構成するポリマーが軟化もしくは一部が溶融する温度まで加熱され、ラミネートシートの被覆層３を互いに融着或いは被覆層３を軟化させて織布の間に侵入もしくは織布に融着されると共に、織布と接着フィルムを重ね合せたものが、フィルムの融点以上かつ織布の融点未満の温度、即ち、接着フィルムを構成するポリマーが軟化もしくは一部が溶融する温度まで加熱され、織布と接着フィルムとが圧着され、一体化することで、積層体シートを作製する。 The difference from the embodiment of FIG. 4 is that FIG. 5 has a coating layer 3 as the bottom layer.
In this embodiment, when the coating layer 3 is laminated on at least one surface of the laminated cloth-like body 2 and thermocompression bonded, the polymer constituting the coating layer 3 is heated to a temperature at which it softens or partially melts, The covering layers 3 of the laminate sheet are fused together or the covering layers 3 are softened and penetrated between the woven fabrics or fused to the woven fabrics. In addition, the woven fabric and the adhesive film are heated to a temperature 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, and the woven fabric and the adhesive film are pressure-bonded and integrated to form a laminate sheet. make.
　本形態においては、複数の布状体２同士が、同一成分からなる接着層４を介して積層してなることが好ましい。布状体と接着層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことが好ましい。 In this embodiment, it is preferable that a plurality of cloth-like bodies 2 are laminated with adhesive layers 4 made of the same component interposed therebetween. The same component contained in the cloth-like body and the adhesive layer preferably includes a polypropylene resin component in common.
　本形態においても、線条体に低融点樹脂成分と高融点樹脂成分とが含まれる場合には、図１の態様と同様に、積層体の熱圧着時、布状体２に用いる線条体１の表面層１０１を構成する低融点樹脂成分が融解し、更に、上述のように接着フィルムが溶融して、複数の布状体２同士が熱圧着されて一体化される。その際、残った線条体１の基層１００を構成する高融点樹脂成分が、繊維成分として残存する。 Also in this embodiment, when the filaments contain a low-melting point resin component and a high-melting point resin component, the filaments used for the cloth-like body 2 during thermocompression bonding of the laminate are used in the same manner as in the embodiment of FIG. The low-melting-point resin component constituting the surface layer 101 of 1 is melted, and furthermore, the adhesive film is melted as described above, and the plurality of cloth-like bodies 2 are thermocompressed and integrated. At that time, the high melting point resin component constituting the base layer 100 of the remaining filamentous body 1 remains as a fiber component.
　本態様においても、図１に示す態様と同様に、織布の枚数は、好ましくは２～２０枚、さらに好ましくは２～１０枚であり、枚数は成形品の目的や用途に合わせて適宜選択することができ、重ね合せる方向も任意である。成形品に適度な強度（堅さ）や耐衝撃性を付与する観点からは、織布は少なくとも２枚以上用いることが好ましい。 In this embodiment, similarly to the embodiment shown in FIG. 1, the number of woven fabrics is preferably 2 to 20, more preferably 2 to 10, and the number is appropriately selected according to the purpose and application of the molded product. and the direction of superimposition is arbitrary. From the viewpoint of imparting appropriate strength (hardness) and impact resistance to the molded product, it is preferable to use at least two woven fabrics.
　積層体を形成する熱圧着手法は格別限定されず、公知の押出ラミネート成形法、熱ラミネート法、カレンダー成形法、プレス成形法等を採用することができる。 The thermocompression bonding method for forming the laminate is not particularly limited, and known extrusion lamination molding methods, heat lamination methods, calendar molding methods, press molding methods, etc. can be employed.
　また、形成された積層体からの所定形状の成型品への成形方法としては、プレス成形、スタンピング成形、プラグアシスト圧空成形、圧空成形、真空圧空成形、真空プレス成形、プラグアシスト真空成形、真空成形等が挙げられる。 Methods for forming a molded article having a predetermined shape from the formed laminate include press molding, stamping molding, plug-assisted pressure forming, pressure forming, vacuum pressure forming, vacuum press molding, plug-assisted vacuum forming, and vacuum forming. etc.
　所定形状の成形品を成形する前に、熱圧着により積層体シートを作製することは好ましい。この場合、熱圧着温度は、延伸線条体を構成するポリマーの結晶化を低下させないために、ポリマーの融点未満とすることが望ましい。例えば、被覆層を構成するポリマーがポリエチレンの場合、熱圧着温度は１１５～１２５℃程度が好ましい。また、被覆層を構成するポリマーがポリプロピレンの場合、熱圧着温度は１１５～１６５℃程度が好ましい。 It is preferable to produce a laminate sheet by thermocompression bonding before molding a molded product of a predetermined shape. In this case, the thermocompression bonding temperature is desirably lower than the melting point of the polymer so as not to reduce the crystallization of the polymer constituting the stretched filament. For example, when the polymer forming the coating layer is polyethylene, the thermocompression bonding temperature is preferably about 115 to 125°C. Further, when the polymer constituting the coating layer is polypropylene, the thermocompression bonding temperature is preferably about 115 to 165.degree.
　第１態様の積層体は、上述したように、シート状の積層体の被覆層の融点以上に加熱された後に、所定形状の金型にセットし、金型により押圧されると、溶融した被覆層３の樹脂が流動して、金型隙間の公差を埋めるように作用する。この結果、金型による積層体への押圧力が、被覆層を介して均一され、金型隙間の公差による部分的な押圧ムラをなくすことができ、外観不良をなくすことができる。 As described above, the laminate of the first aspect is set in a mold of a predetermined shape after being heated to the melting point or higher of the coating layer of the sheet-like laminate, and when pressed by the mold, the molten coating The resin of layer 3 flows and acts to close the mold gap tolerance. As a result, the pressing force applied to the laminate by the mold is made uniform through the coating layer, and partial unevenness in pressing force due to the tolerance of the gap between molds can be eliminated, thereby eliminating poor appearance.
〔第２態様〕
　本発明の積層体の第２態様は、熱可塑性樹脂製の線条体からなる複数の布状体を積層してなるクロス積層体の少なくとも一方の面に、前記線条体と同一成分からなる厚さ０．０２ｍｍ以上 １．０ｍｍ以下の熱可塑性樹脂の被覆層と、０．０２ｍｍ以上１．０ｍｍ以下の熱可塑性樹脂からなるトップ層が順に積層してなることを特徴とする。 [Second aspect]
In a second aspect of the laminate of the present invention, a cloth laminate formed by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin is provided on at least one surface of the cloth laminate with the same component as the filaments. It is characterized by laminating a thermoplastic resin coating layer having a thickness of 0.02 mm or more and 1.0 mm or less and a thermoplastic resin top layer having a thickness of 0.02 mm or more and 1.0 mm or less in this order.
　本発明の好ましい態様としては、前記複数の布状体同士が、同一成分からなる接着層を介して積層してなることであり、前記布状体と接着層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことである。 In a preferred embodiment of the present invention, the plurality of cloth-like bodies are laminated via an adhesive layer made of the same component, and the same component contained in the cloth-like body and the adhesive layer is polypropylene resin. It is to contain ingredients in common.
　また前記被覆層と、前記トップ層が、接着剤層を介して順に積層してなることが好ましく、前記接着剤層は、アクリル系接着剤、ウレタン系接着剤、エポキシ系接着剤、酢酸ビニル系接着剤、スチレン・ブタジエンゴム系接着剤、シリコーン系接着剤から選ばれる少なくとも１種の接着剤を用いて形成された接着剤層であることが好ましい。 The coating layer and the top layer are preferably laminated in order via an adhesive layer. The adhesive layer is preferably formed using at least one adhesive selected from adhesives, styrene-butadiene rubber-based adhesives, and silicone-based adhesives.
　また本発明は、被覆層と、トップ層が、極性基含有熱可塑性樹脂層を介して順に積層してなることが好ましい。また前記極性基含有熱可塑性樹脂層が、変性ポリオレフィンを用いて形成されて樹脂層であることが好ましく、前記変性ポリオレフィンは、ポリオレフィンに、カルボキシル基を有する有機酸を用いて酸変性されたものであることが好ましい。 In addition, in the present invention, it is preferable that the coating layer and the top layer are laminated in order with the polar group-containing thermoplastic resin layer interposed therebetween. Further, the polar group-containing thermoplastic resin layer is preferably a resin layer formed using a modified polyolefin, and the modified polyolefin is a polyolefin acid-modified using an organic acid having a carboxyl group. Preferably.
　以下、図６～図８に基づいて、第２態様について説明する。
　この態様の特徴は、図６～図８に示すように、トップ層５を有する点である。 The second mode will be described below with reference to FIGS. 6 to 8. FIG.
A feature of this embodiment is that it has a top layer 5, as shown in FIGS.
　（トップ層）
　トップ層５としては、布状体及び被覆層と同一素材のものが好ましく、例えば無延伸ポリプロピレンフィルム、二軸延伸ポリプロピレンフィルム、無延伸ポリエチレンフィルム、ポリエステルフィルム、ポリアミドフィルムが挙げられ、中でも、無延伸ポリプロピレン、二軸延伸ポリプロピレンが好ましく、より好ましくは二軸延伸ポリプロピレンである。 (top layer)
The top layer 5 is preferably made of the same material as the cloth-like body and the covering layer. Polypropylene and biaxially oriented polypropylene are preferred, and biaxially oriented polypropylene is more preferred.
　本実施形態において、トップ層５は、着色されていてもよい。トップ層５の着色方法としては、トップ層５自体が顔料、塗料で着色してもよいし、トップ層５の被覆層３側に着色した印刷層を設けてもよい。 In this embodiment, the top layer 5 may be colored. As a method for coloring the top layer 5 , the top layer 5 itself may be colored with a pigment or paint, or a colored printed layer may be provided on the coating layer 3 side of the top layer 5 .
　（接着剤層）
　またこの態様において、トップ層５と被覆層３との間には、図７に示すように、接着剤層６を有していてもよい。 (adhesive layer)
In this embodiment, an adhesive layer 6 may be provided between the top layer 5 and the coating layer 3, as shown in FIG.
　接着剤は、格別限定されないが、例えば、アクリル系接着剤、ウレタン系接着剤、エポキシ系接着剤、酢酸ビニル系接着剤、スチレン・ブタジエンゴム系接着剤、シリコーン系接着剤などを用いることができる。 The adhesive is not particularly limited, but for example, an acrylic adhesive, a urethane adhesive, an epoxy adhesive, a vinyl acetate adhesive, a styrene/butadiene rubber adhesive, a silicone adhesive, or the like can be used. .
　接着剤層６を設ける方法は、格別限定されないが、スプレー、浸漬塗布、刷毛塗り等を例示することができる。 The method of providing the adhesive layer 6 is not particularly limited, but spraying, dip coating, brush coating, etc. can be exemplified.
　この接着剤層６の上面に設けるトップ層５としては、無延伸ポリプロピレン、二軸延伸ポリプロピレンフィルム、無延伸ポリエチレンフィルム、ポリエステルフィルム、ポリアミドフィルム、アクリルフィルム、塩化ビニルフィルムなどが挙げられる。 Examples of the top layer 5 provided on the upper surface of the adhesive layer 6 include unstretched polypropylene, biaxially stretched polypropylene film, unstretched polyethylene film, polyester film, polyamide film, acrylic film, and vinyl chloride film.
　本発明では、上述の説明のように、トップ層５を設ける場合、被覆層３の上に設ける場合と、接着剤層６の上に設ける場合には、トップ層の素材を変えることができる。 In the present invention, as described above, when the top layer 5 is provided, when it is provided on the coating layer 3 and when it is provided on the adhesive layer 6, the material of the top layer can be changed.
　図６及び図７に示す第２の態様において、布状体２と布状体２の間には、接着層４を設けてもよい。 In the second embodiment shown in FIGS. 6 and 7, an adhesive layer 4 may be provided between the cloth-like bodies 2 .
　接着層としては、図４、図５に示す接着層４と同一の構成の接着フィルムを用いることができる。 As the adhesive layer, an adhesive film having the same structure as the adhesive layer 4 shown in FIGS. 4 and 5 can be used.
　（極性基含有熱可塑性樹脂層）
　図８に示す態様の特徴は、被覆層３とトップ層５が極性基含有熱可塑性樹脂層７を介して順に積層されている点である。本実施形態の極性基含有熱可塑性樹脂層７は、トップ層５と結合をより強固にしたい場合に有用である。 (Polar group-containing thermoplastic resin layer)
The feature of the embodiment shown in FIG. 8 is that the coating layer 3 and the top layer 5 are laminated in order with the polar group-containing thermoplastic resin layer 7 interposed therebetween. The polar group-containing thermoplastic resin layer 7 of this embodiment is useful when it is desired to strengthen the bond with the top layer 5 .
　極性基含有熱可塑性樹脂層７は、変性ポリオレフィン層で構成されることが好ましい。 The polar group-containing thermoplastic resin layer 7 is preferably composed of a modified polyolefin layer.
　変性ポリオレフィンは、ポリオレフィンを変性した変性ポリオレフィンからなることが好ましい。 The modified polyolefin is preferably made of modified polyolefin obtained by modifying polyolefin.
　また、変性ポリオレフィン層７は、酸変性された変性ポリプロピレン、又は酸変性された変性ポリエチレンから選ばれる少なくとも一種を用いることもできる。 The modified polyolefin layer 7 can also use at least one selected from acid-modified polypropylene and acid-modified modified polyethylene.
　ポリオレフィンとしては、単独重合体であってもよいし、共重合体であってもよい。そのモノマーとしては、エチレン、プロピレンなどを例示でき、これらを単独又は２種以上混合して用いることができ、共重合体は、ランダム共重合体、交互共重合体、ブロック共重合体、グラフト共重合体のいずれであってもよい。本態様では、これらを単独で又は２種以上を混合して用いることができる。中でも、ポリオレフィンとしてポリプロピレン、ポリエチレンを用いることは特に好ましい。 The polyolefin may be a homopolymer or a copolymer. Examples of the monomer include ethylene, propylene, and the like, and these can be used singly or in combination of two or more. Any polymer may be used. In this aspect, these can be used alone or in combination of two or more. Among them, it is particularly preferable to use polypropylene and polyethylene as the polyolefin.
　ポリオレフィンの変性方法としては、酸変性する手法が挙げられる。酸変性する手法としては、ポリオレフィンに、カルボキシル基を有する有機酸をグラフト重合する方法等を用いることができる。 A method for modifying polyolefin includes a method of acid modification. As a technique for acid modification, a method of graft-polymerizing an organic acid having a carboxyl group to a polyolefin, or the like can be used.
　かかるグラフト重合により、ポリオレフィンに有機酸成分がグラフトされた酸変性ポリオレフィンが得られる。重合手法は、グラフト重合に限定されず、任意の方法を適宜選択して用いることができる。 By such graft polymerization, an acid-modified polyolefin in which an organic acid component is grafted onto polyolefin is obtained. The polymerization method is not limited to graft polymerization, and any method can be appropriately selected and used.
　有機酸の種類は格別限定されないが、カルボキシル基を少なくとも１以上有する、飽和又は不飽和のカルボン酸又は無水カルボン酸であることが好ましい。　 Although the type of organic acid is not particularly limited, it is preferably a saturated or unsaturated carboxylic acid or carboxylic anhydride having at least one carboxyl group.　
　有機酸として、例えば、
　（１）マレイン酸、フマル酸、メサコン酸、シトラコン酸、イタコン酸、アコニット酸、クロトン酸、コハク酸、シュウ酸、マロン酸、リンゴ酸、チオマリン酸、酒石酸、アジピン酸、クエン酸、ピメリン酸、スベリン酸、アゼライン酸、アクリル酸、テトラヒドロフタル酸、イソクロトン酸、エンドシス－ビシクロ（２．２．１）ヘプト－５－エン－２，３－ジカルボン酸及びセバシン酸等のカルボン酸；
　（２）無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水コハク酸等の無水カルボン酸
　が挙げられる。 As an organic acid, for example,
(1) maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, aconitic acid, crotonic acid, succinic acid, oxalic acid, malonic acid, malic acid, thiomarinic acid, tartaric acid, adipic acid, citric acid, pimelic acid, Carboxylic acids such as suberic acid, azelaic acid, acrylic acid, tetrahydrophthalic acid, isocrotonic acid, endocis-bicyclo(2.2.1)hept-5-ene-2,3-dicarboxylic acid and sebacic acid;
(2) Carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and succinic anhydride.
　有機酸は、１種を単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 The organic acids may be used singly or in combination of two or more.
　変性ポリオレフィンは、酸変性される場合、通常、有機酸をポリオレフィンに対して０．０１～１０重量％含むように変性することができる。 When the modified polyolefin is acid-modified, it can usually be modified to contain 0.01 to 10% by weight of the organic acid relative to the polyolefin.
　有機酸の含有量が０．０１重量％未満となる場合、変性ポリオレフィン層７が、クロス積層体と共重合ポリアミド層との間に積層される際、層間接着性に劣るため好ましくない。また、１０重量％を超える場合、分子架橋型のモノマーを主成分とするポリオレフィンに対して変性すると、ポリオレフィンの架橋が著しいために溶融粘度が増大し、分子切断型のモノマーを主成分とするポリオレフィンに対して変性すると、主鎖切断が著しくなるため溶融粘度が減少する。この結果、変性ポリオレフィン層７が、クロス積層体と共重合ポリアミド層との間に積層される際、層間接着性に劣る。 If the content of the organic acid is less than 0.01% by weight, it is not preferable because the interlayer adhesion is inferior when the modified polyolefin layer 7 is laminated between the cloth laminate and the copolymerized polyamide layer. Further, when the amount exceeds 10% by weight, if the polyolefin containing a molecularly crosslinked monomer as a main component is modified, the melt viscosity increases due to significant crosslinking of the polyolefin, and the polyolefin containing a molecularly cleaved monomer as a main component. When modified with respect to , the melt viscosity decreases due to significant main chain scission. As a result, when the modified polyolefin layer 7 is laminated between the cloth laminate and the copolymerized polyamide layer, the interlayer adhesion is poor.
　変性ポリオレフィン層７は、上述した変性ポリオレフィンの他に、無変性ポリオレフィン等の他の樹脂を本発明の効果を阻害しない範囲で含んでもよい。 In addition to the modified polyolefin described above, the modified polyolefin layer 7 may contain other resins such as unmodified polyolefin to the extent that the effects of the present invention are not impaired.
　変性ポリオレフィン層７の形態は格別限定されず、例えば、フィルム状やシート状のものや、押出ラミネート等に供するために溶融された状態とすることができる。汎用性の観点から、フィルム状やシート状のものが好ましい。 The form of the modified polyolefin layer 7 is not particularly limited. For example, it can be in the form of a film or a sheet, or in a molten state for use in extrusion lamination or the like. From the viewpoint of versatility, a film-like or sheet-like one is preferable.
　（添加剤）
　本発明において、クロス積層体に用いる線条体や接着層、変性ポリオレフィン層や共重合ポリアミド層、並びに、熱可塑性ポリウレタン系樹脂層には、目的に応じて各種の添加剤を添加することができる。具体的には、有機リン系、チオエーテル系等の酸化防止剤、ヒンダードアミン系等の光安定剤、ベンゾフェノン系、ベンゾトリアゾール系、ベンゾエート系等の紫外線吸収剤、帯電防止剤、ビスアミド系、ワックス系、有機金属塩系等の分散剤、アミド系、有機金属塩系等の滑剤、含臭素系有機系、リン酸系、メラミンシアヌレート系、三酸化アンチモン等の難燃剤、低密度ポリエチレン、線状低密度ポリエチレン等の延伸助剤、有機顔料、無機顔料、無機充填剤、有機充填剤、金属イオン系等の無機抗菌剤、有機抗菌剤等が挙げられる。 (Additive)
In the present invention, various additives can be added to the filaments, the adhesive layer, the modified polyolefin layer, the copolyamide layer, and the thermoplastic polyurethane resin layer used in the cloth laminate, depending on the purpose. . Specifically, antioxidants such as organic phosphorus and thioether, light stabilizers such as hindered amines, UV absorbers such as benzophenones, benzotriazoles and benzoates, antistatic agents, bisamides, waxes, Dispersants such as organometallic salts, lubricants such as amides and organometallic salts, bromine-containing organic agents, phosphoric acid agents, melamine cyanurate agents, antimony trioxide flame retardants, low-density polyethylene, linear low-density Examples include stretching aids such as density polyethylene, organic pigments, inorganic pigments, inorganic fillers, organic fillers, inorganic antibacterial agents such as metal ion-based agents, and organic antibacterial agents.
　（第２の態様の積層体）
　図６の例では、３枚の布状体２を積層しており、布状体２の少なくとも一方の面に、被覆層３を有し、被覆層３上に、トップ層５を有している。具体的には、トップ層５／被覆層３／布状体２／布状体２／布状体２からなる積層体の例である。図１に示す第１の形態の積層体に、更にトップ層５を有した積層体である。 (Laminate of the second aspect)
In the example of FIG. 6, three cloth-like bodies 2 are laminated, the cloth-like body 2 has a covering layer 3 on at least one surface, and a top layer 5 is provided on the covering layer 3. there is Specifically, it is an example of a laminate composed of top layer 5/coating layer 3/fabric body 2/fabric body 2/fabric body 2. FIG. It is a laminated body having a top layer 5 in addition to the laminated body of the first embodiment shown in FIG.
　この積層体は、被覆層３上に、トップ層を積層し、積層体の熱圧着時、被覆層３を構成するポリマーが軟化もしくは一部が溶融する温度まで加熱され、ラミネートシートの被覆層３を互いに融着或いは被覆層３を軟化させて織布の間侵入もしくは織布に融着されると共に、トップ層５と融着することによって、積層体を作製することができる。 In this laminate, the top layer is laminated on the coating layer 3, and when the laminate is thermocompression bonded, the polymer constituting the coating layer 3 is heated to a temperature at which it softens or partially melts, and the coating layer 3 of the laminate sheet is heated. can be fused to each other or by softening the cover layer 3 to penetrate between or fused to the woven fabric and fused to the top layer 5 to form a laminate.
　図７の例では、３枚の布状体２を積層しており、布状体２の少なくとも一方の面に、被覆層３を有し、被覆層３上に、接着剤層６を介してトップ層５を有している。具体的には、トップ層５／接着剤層６／被覆層３／布状体２／布状体２／布状体２からなる積層体の例である。図１に示す第１の形態の積層体に、更に接着剤層６、及びトップ層５を有した積層体である。 In the example of FIG. 7, three cloth-like bodies 2 are laminated, and a coating layer 3 is provided on at least one surface of the cloth-like body 2, and an adhesive layer 6 is disposed on the coating layer 3. It has a top layer 5 . Specifically, it is an example of a laminate composed of top layer 5 /adhesive layer 6 /coating layer 3 /fabric body 2 /fabric body 2 /fabric body 2 . This laminated body further includes an adhesive layer 6 and a top layer 5 in addition to the laminated body of the first embodiment shown in FIG.
　本実施形態において、接着剤を用いて接着剤層６を形成する場合には、まず、図１に示す第１の形態に示す積層体を作製する。 In this embodiment, when the adhesive layer 6 is formed using an adhesive, first, a laminate shown in the first embodiment shown in FIG. 1 is produced.
　次に、作製された積層体上に接着剤を付与して、接着剤層６を形成し、その接着剤層６の接着剤を介してトップ層５を接着させることにより、本態様の積層体が作製することができる。 Next, an adhesive is applied to the produced laminate to form an adhesive layer 6, and the top layer 5 is adhered via the adhesive of the adhesive layer 6, thereby obtaining a laminate of this embodiment. can be made.
　図８の例では、３枚の布状体２を積層しており、布状体２の少なくとも一方の面に、被覆層３を有し、被覆層３上に、極性基含有熱可塑性樹脂層７を介してトップ層５を有している。 In the example of FIG. 8, three cloth-like bodies 2 are laminated, a coating layer 3 is provided on at least one surface of the cloth-like body 2, and a polar group-containing thermoplastic resin layer is formed on the coating layer 3. It has a top layer 5 via 7 .
　この積層体は、被覆層３上に、極性基含有熱可塑性樹脂層７を積層し、極性基含有熱可塑性樹脂層７上にトップ層５を積層し、積層体を熱圧着すると、被覆層３を構成するポリマーが軟化もしくは一部が溶融する温度まで加熱され、ラミネートシートの被覆層３を互いに融着或いは被覆層３を軟化させて織布の間侵入もしくは織布に融着されると共に、極性基含有熱可塑性樹脂層７が溶融して、極性基によって、極性基含有熱可塑性樹脂層７と被覆層３、極性基含有熱可塑性樹脂層７とトップ層５が強固に融着されることによって、層間が結合され、本実施形態の積層体が作製される。 In this laminate, a polar group-containing thermoplastic resin layer 7 is laminated on the coating layer 3, a top layer 5 is laminated on the polar group-containing thermoplastic resin layer 7, and the laminate is thermocompression bonded to form the coating layer 3. is heated to a temperature at which the polymer that constitutes the The polar group-containing thermoplastic resin layer 7 is melted, and the polar group-containing thermoplastic resin layer 7 and the coating layer 3, and the polar group-containing thermoplastic resin layer 7 and the top layer 5 are strongly fused by the polar groups. The layers are bonded to each other to produce the laminate of the present embodiment.
　本発明の第２の態様の積層体において、所定形状の金型にセットされ、金型により押圧されると、トップ層５は最外層となるため、金型隙間の公差によって、押圧ムラを生じても、トップ層５と布状体２との間の被覆層３が、溶融し、押圧力の大きな部分から押圧力の小さな部分に溶融して、被覆層成分が移動することによって、結果として、積層体のトップ層５を押圧する押圧力が被覆層３によって均一化され、外観不良の発生を防ぐことができる。 In the laminate of the second aspect of the present invention, when it is set in a mold of a predetermined shape and pressed by the mold, the top layer 5 becomes the outermost layer. However, the coating layer 3 between the top layer 5 and the cloth-like body 2 is melted, melted from a portion with a large pressing force to a portion with a small pressing force, and the components of the coating layer move, resulting in , the pressing force for pressing the top layer 5 of the laminate is made uniform by the covering layer 3, and the occurrence of poor appearance can be prevented.
　本発明の第１の態様の積層体、及び第２の態様の積層体によれば、雄雌の金型によるプレス成形において、金型隙間の公差による部分的な押圧ムラを防止して外観不良の発生しない積層体を製造できるために、スーツケースやアタッシュケース、カメラケース、楽器ケース等の外観性に優れた成形品を製造することができる。 According to the laminate of the first aspect and the laminate of the second aspect of the present invention, in press molding using male and female molds, partial pressing unevenness due to the tolerance of the mold gap is prevented, and the appearance is poor. Since it is possible to produce a laminate that does not generate , it is possible to produce moldings with excellent appearance, such as suitcases, attache cases, camera cases, musical instrument cases, and the like.
　以下、本発明の実施例について説明するが、本発明は、かかる実施例によって限定されない。 Examples of the present invention will be described below, but the present invention is not limited by such examples.
　実施例１
　１．積層体の作製
（１）布状体の作製
　＜２種３層ポリプロピレンフィルムの製造＞
　高融点ポリプロピレン（ＭＦＲ＝０．４ｇ／１０分、重量平均分子量Ｍｗ＝６３０，０００、融点１６４℃）と、低融点ポリプロピレン（プロピレン－エチレンランダム共重合体、ＭＦＲ＝７．０ｇ／１０分、重量平均分子量Ｍｗ＝２２０，０００、融点１２５℃）とを用い、インフレーション成形法によって、低融点ポリプロピレンを表層とし高融点ポリプロピレンを内層とした２種３層ポリプロピレンフィルムを製造した。 Example 1
1. Preparation of laminate (1) Preparation of cloth <Production of two-kind three-layer polypropylene film>
High melting point polypropylene (MFR = 0.4 g / 10 minutes, weight average molecular weight Mw = 630,000, melting point 164 ° C.) and low melting point polypropylene (propylene-ethylene random copolymer, MFR = 7.0 g / 10 minutes, weight (average molecular weight Mw = 220,000, melting point 125°C), and a two-kind three-layer polypropylene film having a surface layer of low-melting polypropylene and an inner layer of high-melting polypropylene was produced by the inflation molding method.
　＜フラットヤーンの製造＞
　得られたフィルムを、レザー（ｒａｚｏｒ）でスリットした。次いで、温度１１０～１２０℃の熱板上で７倍に延伸した後、温度１４５℃の熱風循環式オーブン内で１０％の弛緩熱処理を行い、糸巾４．５ｍｍ、繊度１７００デシテックス（ｄｔ）のフラットヤーンを得た。 <Production of flat yarn>
The resulting film was slit with a razor. Next, after stretching 7 times on a hot plate at a temperature of 110 to 120 ° C., a 10% relaxation heat treatment is performed in a hot air circulating oven at a temperature of 145 ° C. A yarn width of 4.5 mm and a fineness of 1700 decitex (dt). Got a flat yarn.
　＜布状体の製造＞
　得られたフラットヤーンを、スルーザー織機を用いて、経糸１５本／２５．４ｍｍ、緯糸１５本／２５．４ｍｍの綾織に織成することによって布状体を得た。 <Manufacturing of cloth-like body>
The obtained flat yarn was woven into a twill weave of 15 warps/25.4 mm and 15 wefts/25.4 mm using a sluzer loom to obtain a fabric.
　（２）接着層
　接着層としては、融点１２５℃の低融点ポリプロピレンに、融点１６１℃の高融点ポリプロピレンを含有させた、０．０６ｍｍのポリプロピレンフィルムを用いた。 (2) Adhesive Layer As the adhesive layer, a 0.06 mm polypropylene film containing a low melting point polypropylene having a melting point of 125° C. and a high melting point polypropylene having a melting point of 161° C. was used.
　（３）積層体の層構成
　得られた布状体３枚と、得られた接着層２枚を、布状体／接着層／布状体／接着層／布状体となるように交互に積層し、その布状体の上面に、被覆層とトップ層を順に設けた。被覆層は、ポリプロピレンフィルム０．１７ｍｍとし、トップ層は二軸延伸ポリプロピレンフィルム０．０４ｍｍとした。 (3) Laminate layer structure The three cloth-like bodies obtained and the two adhesive layers obtained were alternately arranged in a cloth-like body/adhesive layer/cloth-like body/adhesive layer/cloth-like body. A coating layer and a top layer were sequentially provided on the upper surface of the cloth-like body. The coating layer was a 0.17 mm polypropylene film, and the top layer was a 0.04 mm biaxially oriented polypropylene film.
　層構成は、トップ層／被覆層／布状体／接着層／布状体／接着層／布状体となるようにした。 The layer structure was made to be top layer/coating layer/fabric body/adhesive layer/fabric body/adhesive layer/fabric body.
　（４）積層体の製造
　油圧式プレス機でプレス温度１４５℃に設定し、圧力１ＭＰａで２分間加熱プレスした後、油圧式プレス機でプレス温度２０℃、圧力５ＭＰａで２分間冷却プレスして積層体を得た。 (4) Manufacture of laminated body Set the press temperature to 145 ° C. with a hydraulic press machine, heat press for 2 minutes at a pressure of 1 MPa, then cool press with a hydraulic press machine at a press temperature of 20 ° C. and a pressure of 5 MPa for 2 minutes to laminate. got a body
　得られた積層体の外周を把持した状態で、赤外線ヒータで、積層体表面が１６０℃になるまで加熱した後に、８０℃に加熱された金型でプレス成形し、２分間閉型した後に、脱型した。この結果、金型による押圧力が、被覆層を介して均一化にされ、金型隙間の公差による部分的な押圧ムラをなくすことができ、表面の外観に優れた成形物を得た。 With the outer periphery of the obtained laminate held, the surface of the laminate was heated with an infrared heater until it reached 160 ° C., then press-molded with a mold heated to 80 ° C., closed for 2 minutes, and then demolded. As a result, the pressing force by the mold was made uniform through the coating layer, and partial unevenness in pressing force due to the tolerance of the gap between the molds could be eliminated, thereby obtaining a molding with an excellent surface appearance.
　実施例２
　実施例１において、赤外線ヒータを、恒温炉に代え、積層体表面を、１７０℃に加熱し、１００℃に加熱された金型プレス成形し、１．５分間閉型した以外は、実施例１と同様に試験した。 Example 2
In Example 1, the infrared heater was replaced with a constant temperature furnace, and the surface of the laminate was heated to 170 ° C., press-molded with a mold heated to 100 ° C., and closed for 1.5 minutes. tested in the same way.
　実施例２においても、実施例１と同様に、金型による押圧力が、被覆層を介して均一化にされ、金型隙間の公差による部分的な押圧ムラをなくすことができ、表面の外観に優れた成形物を得た。 In Example 2, similarly to Example 1, the pressing force by the mold is made uniform through the coating layer, and partial unevenness in pressing due to the tolerance of the mold gap can be eliminated, and the appearance of the surface can be improved. A molded product with excellent ductility was obtained.
　１　線条体
　　１００　基層
　　１０１　表面層
　２　布状体
　３　被覆層
　４　接着層
　５　トップ層
　６　接着剤層
　７　極性基含有熱可塑性樹脂層 REFERENCE SIGNS LIST 1 striatal body 100 base layer 101 surface layer 2 cloth-like body 3 coating layer 4 adhesive layer 5 top layer 6 adhesive layer 7 polar group-containing thermoplastic resin layer

Claims (12)

  1. 　熱可塑性樹脂製の線条体からなる複数の布状体を積層してなるクロス積層体の少なくとも一方の面に、前記線条体と同一成分からなる厚さ０．０２ｍｍ以上 １．０ｍｍ以下の熱可塑性樹脂の被覆層が積層してなることを特徴とする積層体。 On at least one surface of a cloth laminate obtained by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin, a cloth having a thickness of 0.02 mm or more and 1.0 mm or less made of the same component as the filaments and having a thickness of 0.02 mm or more and 1.0 mm or less A laminate comprising a laminate of thermoplastic resin coating layers.
  2. 　前記線条体と前記被覆層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことを特徴とする請求項１記載の積層体。 The laminate according to claim 1, wherein the same component contained in the filaments and the coating layer includes a polypropylene resin component in common.
  3. 　前記複数の布状体同士が、同一成分からなる接着層を介して積層してなることを特徴とする請求項２記載の積層体。 The laminate according to claim 2, wherein the plurality of cloth-like bodies are laminated via an adhesive layer made of the same component.
  4. 　前記布状体と接着層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことを特徴とする請求項３記載の積層体。 The laminate according to claim 3, wherein the same component contained in the cloth-like body and the adhesive layer commonly contains a polypropylene resin component.
  5. 　熱可塑性樹脂製の線条体からなる複数の布状体を積層してなるクロス積層体の少なくとも一方の面に、前記線条体と同一成分からなる厚さ０．０２ｍｍ以上 １．０ｍｍ以下の熱可塑性樹脂の被覆層と、０．０２ｍｍ以上１．０ｍｍ以下の熱可塑性樹脂からなるトップ層が順に積層してなることを特徴とする積層体。 On at least one surface of a cloth laminate obtained by laminating a plurality of cloth-like bodies made of filaments made of a thermoplastic resin, a cloth having a thickness of 0.02 mm or more and 1.0 mm or less made of the same component as the filaments and having a thickness of 0.02 mm or more and 1.0 mm or less A laminate comprising a coating layer made of a thermoplastic resin and a top layer made of a thermoplastic resin having a thickness of 0.02 mm or more and 1.0 mm or less, which are laminated in this order.
  6. 　前記複数の布状体同士が、同一成分からなる接着層を介して積層してなることを特徴とする請求項５記載の積層体。 The laminate according to claim 5, wherein the plurality of cloth-like bodies are laminated via an adhesive layer made of the same component.
  7. 　前記布状体と接着層に含まれる同一成分は、ポリプロピレン樹脂成分を共通して含むことを特徴とする請求項６記載の積層体。 The laminate according to claim 6, wherein the same component contained in the cloth-like body and the adhesive layer commonly contains a polypropylene resin component.
  8. 　前記被覆層と、前記トップ層が、接着剤層を介して順に積層してなることを特徴とする請求項５記載の積層体。 The laminate according to claim 5, wherein the coating layer and the top layer are laminated in order via an adhesive layer.
  9. 　前記接着剤層は、アクリル系接着剤、ウレタン系接着剤、エポキシ系接着剤、酢酸ビニル系接着剤、スチレン・ブタジエンゴム系接着剤、シリコーン系接着剤から選ばれる少なくとも１種の接着剤を用いて形成された接着剤層であることを特徴とする請求項８記載の積層体。 The adhesive layer uses at least one adhesive selected from acrylic adhesives, urethane adhesives, epoxy adhesives, vinyl acetate adhesives, styrene-butadiene rubber adhesives, and silicone adhesives. 9. The laminate according to claim 8, wherein the adhesive layer is formed by
  10. 　前記被覆層と、前記トップ層が、極性基含有熱可塑性樹脂層を介して順に積層してなることを特徴とする請求項５記載の積層体。 The laminate according to claim 5, wherein the coating layer and the top layer are laminated in order via a polar group-containing thermoplastic resin layer.
  11. 　前記極性基含有熱可塑性樹脂層が、変性ポリオレフィンを用いて形成されて樹脂層であることを特徴とする請求項１０記載の積層体。 The laminate according to claim 10, wherein the polar group-containing thermoplastic resin layer is a resin layer formed using modified polyolefin.
  12. 　前記変性ポリオレフィンは、ポリオレフィンに、カルボキシル基を有する有機酸を用いて酸変性されたものであることを特徴とする請求項１１記載の積層体。 The laminate according to claim 11, wherein the modified polyolefin is a polyolefin acid-modified with an organic acid having a carboxyl group.
PCT/JP2022/009359 2021-03-05 2022-03-04 Laminate WO2022186371A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001260290A (en) * 2000-03-21 2001-09-25 Hagihara Industries Inc Soundproofing sheet made of polyolefin
JP2001293831A (en) * 2000-04-12 2001-10-23 Diatex Co Ltd Laminate sheet
JP2002067252A (en) * 2000-08-25 2002-03-05 Hagihara Industries Inc Laminated sheet
JP2014218074A (en) * 2013-04-11 2014-11-20 株式会社Ｋｏｓｕｇｅ Manufacturing method of molded article
JP2017196892A (en) * 2016-04-21 2017-11-02 萩原工業株式会社 Flat yarn laminate sheet for molding processing and molding processed article
WO2018143476A1 (en) * 2017-02-06 2018-08-09 ダイヤテックス株式会社 Laminate, laminate precursor, and laminate production method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001260290A (en) * 2000-03-21 2001-09-25 Hagihara Industries Inc Soundproofing sheet made of polyolefin
JP2001293831A (en) * 2000-04-12 2001-10-23 Diatex Co Ltd Laminate sheet
JP2002067252A (en) * 2000-08-25 2002-03-05 Hagihara Industries Inc Laminated sheet
JP2014218074A (en) * 2013-04-11 2014-11-20 株式会社Ｋｏｓｕｇｅ Manufacturing method of molded article
JP2017196892A (en) * 2016-04-21 2017-11-02 萩原工業株式会社 Flat yarn laminate sheet for molding processing and molding processed article
WO2018143476A1 (en) * 2017-02-06 2018-08-09 ダイヤテックス株式会社 Laminate, laminate precursor, and laminate production method

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