WO2022186370A1 - 積層体及び積層体成形品の成形方法 - Google Patents
積層体及び積層体成形品の成形方法 Download PDFInfo
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- WO2022186370A1 WO2022186370A1 PCT/JP2022/009358 JP2022009358W WO2022186370A1 WO 2022186370 A1 WO2022186370 A1 WO 2022186370A1 JP 2022009358 W JP2022009358 W JP 2022009358W WO 2022186370 A1 WO2022186370 A1 WO 2022186370A1
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- Prior art keywords
- laminate
- molding
- molded product
- layer
- cloth
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Images
Classifications
-
- 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
-
- 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 method for molding a laminate and a molded laminate, and more particularly to a method for molding a laminate and a molded laminate having excellent molding cycle time.
- 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.
- (Claim 1) A plurality of cloth-like bodies made of filaments made of a thermoplastic resin are laminated, and a thickness of 0.02 mm or more made of the same component as the filamentary bodies is formed on at least one surface of the plurality of cloth-like bodies1 Laminated thermoplastic resin coating layers of 0 mm or less, A laminate, wherein the storage elastic modulus of the coating layer at 150° C. is 3.00 ⁇ 10 6 Pa or more and 1.00 ⁇ 10 8 Pa or less. (Claim 2) 2. The laminate according to claim 1, wherein said cloth-like body is laminated via an adhesive layer made of the same component. (Claim 3) 3.
- a top layer made of a thermoplastic resin having a thickness of 0.02 mm or more and 0.1 mm or less is laminated on the upper surface of the one coating layer via an adhesive layer. .
- (Claim 5) Press-molding the laminate according to any one of claims 1 to 4 with a male-female press machine, Then, the molded product obtained by the molding is demolded when the molded product temperature is in the range of 70 ° C. or higher and 120 ° C.
- a method for molding a laminate molded product characterized by cooling the temperature of the molded product to 60°C or lower.
- (Claim 6) 6.
- (Claim 7) 6.
- ADVANTAGE OF THE INVENTION it is possible to provide a laminate and a method for molding a laminate molded product which are excellent in the molding cycle time in which the mold can be demolded and the next molding cycle can be started without waiting for cooling to 60°C or less. can do.
- Schematic cross-sectional view showing an example of a laminate according to the present invention Schematic cross-sectional view showing another example of a laminate according to the present invention
- Diagram showing an example of the structure of the striatum Schematic cross-sectional view showing still another example of a laminate according to the present invention
- Schematic cross-sectional view showing still another example of a laminate according to the present invention Schematic cross-sectional view showing still another example of a laminate according to the present invention
- Schematic cross-sectional view showing still another example of a laminate according to the present invention Schematic cross-sectional view showing still another example of a laminate according to the present invention
- FIG. 1 is a schematic cross-sectional view showing an example of a laminate in which a coating layer 3 is laminated on one surface of a plurality of laminated cloth-like bodies 2, and FIG. 2 shows a plurality of laminated cloth-like bodies.
- 2 is a schematic cross-sectional view showing an example of improvement of FIG. 1 with coating layers 3, 3 laminated on both sides of 2;
- a plurality of cloth-like bodies 2 made of filaments 1 made of a thermoplastic resin are laminated, and a coating layer 3 is laminated on at least one surface of the plurality of cloth-like bodies, and then thermocompressed to be integrated. By doing so, the laminate of the present invention is obtained.
- 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 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 an example of a laminated 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 linear body 1. there is 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 low melting point portion.
- thermoplastic resins that make up the filaments include polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and the like. 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 2 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 filamentous body 1, but is made of a large number of thermoplastic resins. It may be a cross-bonded cloth (soft fabric) in which the filamentary bodies 1 are arranged perpendicularly so as to form a plane and joined at their intersections, or other filamentary bodies 1 formed of the above thermoplastic resin. Knitted fabrics may also be used.
- the basis weight of the woven fabric is preferably 30-500 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 plurality of laminated cloth-like bodies 2 . Also, in FIG. 2, the coating layer 3 is provided on both surfaces of the plurality of laminated cloth-like bodies 2 .
- the coating layer of the present invention has a storage elastic modulus at 150° C. of 3.00 ⁇ 10 6 Pa or more and 1.00 ⁇ 10 8 Pa or less.
- the storage elastic modulus of the coating layer can be measured, for example, using a measuring device (EPLEXOR500N (manufactured by Netschgabo): dynamic viscoelasticity temperature dispersion measurement).
- the covering layer 3 is preferably a film made of the same material as the cloth-like body.
- polyolefins such as polypropylene and polyethylene, polyesters such as polyethylene terephthalate, and polyamide films can be preferably used. Among them, polyolefins are preferable and more preferable. is polypropylene.
- the storage elastic modulus of the coating layer 3 is within the range of the present invention, it can be removed from the mold without waiting for cooling to 60° C. or less, and the next molding cycle can be started. do.
- 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 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 resin component constituting the filamentous body 1 and the coating layer 3 is the same component, and such an identical component means that the polypropylene resin component is commonly included.
- the cloth-like bodies 2 and adjacent cloth-like bodies 2 are laminated via an adhesive layer 4 made of the same component as that of the cloth-like bodies 2 .
- the same component contained in the cloth-like body 2 and the adhesive layer 4 preferably includes a polypropylene resin component in common.
- 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
- random polypropylene can be used as the low melting point resin component and homopolypropylene can be used as the high melting point resin component.
- Another embodiment in which the low-melting resin component and the high-melting resin component used in the adhesive layer 4 are each selected from polypropylene is that a relatively low-melting random polypropylene is used as the low-melting resin component, and a high-melting resin is used. Random polypropylene with a relatively high melting point can also be used as a 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 a coating layer 3 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.
- the low-melting point resin component that constitutes the surface layer of the filaments used in the cloth-like body is melted, and the plurality of cloth-like bodies are thermocompressed and integrated.
- the filamentary body component composed of the remaining high melting point resin component remains as the fibrous component of the cloth-like body, it exhibits an effect of increasing the strength of the molded product, which is preferable.
- 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 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. 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.
- the laminate of the present embodiment is heated to a temperature at which the polymer constituting the coating layer is softened or partially melted by thermocompression bonding, and the coating layers of the laminate sheet are fused to each other or softened to form a woven fabric. It is integrated with the fabric by intruding into it or being fused to the woven fabric, and the fabric-like body and the adhesive film are superimposed at a temperature above the melting point of the film and below the melting point of the woven fabric, that is, constitute the adhesive film.
- the polymer is heated to a temperature at which it softens or partially melts, and the cloth-like body and the adhesive film are integrated, thereby firmly bonding between the coating layer and the cloth-like body and between the cloth-like body and the adjacent cloth-like body. be done.
- 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.
- 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.
- FIGS. 1, 2, 4 and 5 An improved example of the laminate shown in FIGS. 1, 2, 4 and 5 will be described with reference to FIGS. 6, 7 and 8.
- This improved example includes a mode in which a top layer made of a thermoplastic resin having a thickness of 0.02 mm or more and 0.1 mm or less is laminated on the upper surface of the one coating 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.
- 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 .
- a top layer 5 made of a thermoplastic resin having a thickness of 0.02 mm or more and 0.1 mm or less is laminated on the upper surface of one coating layer 3 with an adhesive layer 6 interposed therebetween. is preferred.
- the adhesive layer 6 uses at least one adhesive selected from acrylic adhesives, urethane adhesives, epoxy adhesives, vinyl acetate adhesives, styrene-butadiene rubber adhesives, and silicone adhesives. It is preferably an adhesive layer formed by
- the method of providing the adhesive layer 6 is not particularly limited, but spraying, dip coating, brush coating, etc. can be exemplified.
- 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 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 is useful when it is desired to make the interlayer adhesion with the top layer 5 stronger. Furthermore, when forming the adhesive layer 6 using an adhesive, after forming the laminate precursor once, the adhesive layer 6 is formed and the top layer 5 is laminated. When the thermoplastic resin layer 7 is used, it is useful in that it can be formed collectively without forming a laminate precursor.
- the polar group-containing thermoplastic resin layer 7 is preferably a resin layer formed using modified polyolefin, and the modified polyolefin is obtained by acid-modifying polyolefin using an organic acid having a carboxyl group. is preferred.
- the polar group-containing thermoplastic resin layer 7 is a resin layer formed using a modified polyolefin (hereinafter referred to as a modified polyolefin layer 7 if necessary), an acid-modified modified polypropylene, or an acid At least one selected from modified modified polyethylene can also be used.
- a modified polyolefin layer 7 a resin layer formed using a modified polyolefin (hereinafter referred to as a modified polyolefin layer 7 if necessary)
- an acid-modified modified polypropylene, or an acid At least one selected from modified modified polyethylene can also be used.
- 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;
- Carboxylic anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride and succinic anhydride.
- 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 interlayer adhesion is inferior when the modified polyolefin layer 7 is laminated between the cloth-like body 2 and the copolyamide layer, which is not preferable.
- 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.
- the melt viscosity decreases due to significant main chain scission.
- the modified polyolefin layer 7 is laminated between the cloth-like body and the copolyamide layer, the interlayer adhesion is poor.
- the resin layer formed of modified polyolefin may contain other resin such as unmodified polyolefin in addition to the modified polyolefin described above, as long as the effect of the present invention is not impaired.
- the form of the resin layer formed of the modified polyolefin is not particularly limited, and can be, for example, a film-like or sheet-like one, or a melted state for extrusion lamination or the like. From the viewpoint of versatility, a film-like or sheet-like one is preferable.
- FIG. 9A shows the pressing process.
- a male-female press machine comprising a female die 81 and a male die 82 is used.
- the laminate 83 described above is mounted between the female mold 81 and the male mold 82, and is press-molded by the press machine 8 so that the molded product temperature is 150 to 170°C.
- the press molding is finished, the mold is opened as shown in FIG. .
- the storage modulus of the coating layer is lower than the range of the present invention at the time of demolding, the coating layer will float during demolding. For this reason, conventionally, it was necessary to remove the mold after cooling to 60° C. or lower. In other words, since the mold cannot be demolded until it is cooled to 60° C. or less, the next pressing operation cannot be performed, which poses a problem of a large loss in the molding cycle.
- the temperature of the molded article can be cooled to 60° C. or lower as shown in FIG. 9(C).
- the molded article when the temperature of the molded article is cooled to 60° C. or lower, the molded article can be cooled while maintaining its shape along the straightening mold 84 .
- the molded article when the temperature of the molded article is cooled to 60° C. or lower, the molded article can be cooled while being attached to the male mold 82 of the male-female press machine.
- the coating layer does not float during demolding, there is no problem when demolding and cooling the molded product to a temperature of 60° C. or less, so that the molding cycle can proceed smoothly. As shown in , the laminate molded article can be completed.
- the top layer and the coating layer are firmly adhered to each other when the laminate including the top layer is removed from the mold. Since there is no occurrence of floating, there is no problem when removing from the mold and cooling the temperature of the molded product to 60° C. or less, so that the molding cycle can proceed smoothly.
- Adhesive Layer As the adhesive layer, a 0.6 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.
- PP C Polypropylene
- This layered structure was hot-pressed with a hydraulic press at a press temperature of 145 ° C. and a pressure of 1 MPa for 2 minutes, and then cooled and pressed with a hydraulic press at a press temperature of 20 ° C. and a pressure of 5 MPa for 2 minutes.
- a sheet-like laminated body of Example 1 was obtained.
- PP A polypropylene
- PP B polypropylene
- MFR polypropylene
- Comparative example 2 A laminate of Comparative Example 2 was obtained in the same manner as in Example 1, except that polypropylene (PP C) was replaced with polypropylene (PP B) and the content was changed to 45% by weight.
- FIG. 10 shows photographs of molded articles obtained by molding the laminates of Examples and Comparative Examples shown in Table 1 after demolding.
- FIG. 10(A) is a photograph of a molded product obtained by molding the laminate of Comparative Example 1 after demolding
- FIG. 10(C) is a photograph after demolding of the molded product obtained by molding the laminate of Example 1
- FIG. 2 is a photograph of a molded product obtained by molding the laminate of No. 2 after demolding.
- the storage elastic modulus at 150° C. of the coating layer having a thickness of 110 ⁇ m is 3.00 ⁇ 10 6 Pa or more and 1.00 ⁇ 10 8 Pa or less, even if the mold is demolded at a demolding temperature of 120° C. A molded product with an excellent surface appearance could be obtained without causing the floating of the coating layer (see FIGS. 10(C) and 10(D)). For this reason, it was confirmed that even at a high demolding temperature, it was possible to obtain a molded product with an excellent surface appearance, and as a result, it was possible to shorten the molding cycle time.
- Example 3 Example 4, Comparative Example 3 and Comparative Example 4
- the molding conditions were changed as follows (changes are described below), Experiments of Example 3, Example 4, Comparative Example 3 and Comparative Example 4 were conducted in the same manner as above.
- Example 3 Using the laminate used in Example 1, with the outer periphery of the laminate held, heated in a constant temperature furnace until the surface of the laminate reached 170 ° C., and then press-molded with a mold heated to 100 ° C. After closing the mold for 1.5 minutes, the mold was opened and demolded to obtain a molded product.
- Example 4 The laminate used in Example 2 was used and tested in the same manner as in Example 3.
- Comparative Example 4 Using the laminate used in Comparative Example 2, the same test as in Example 3 was performed.
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Abstract
Description
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り、該複数の布状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を積層してなり、
該被覆層の150℃における貯蔵弾性率が3.00×106Pa以上1.00×108Pa以下であることを特徴とする積層体。
(請求項2)
前記布状体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1記載の積層体。
(請求項3)
0.02mm以上0.1mm以下の熱可塑性樹脂からなるトップ層が、前記一方の被覆層の上面に積層してなることを特徴とする請求項1又は2記載の積層体。
(請求項4)
0.02mm以上0.1mm以下の熱可塑性樹脂からなるトップ層が、接着剤層を介して前記一方の被覆層の上面に積層してなることを特徴とする請求項1又は2記載の積層体。
(請求項5)
請求項1~4の何れかに記載の積層体を雄雌型のプレス機でプレス成形し、
次いで、前記成形により得られた成形品の成形品温度が70℃以上120℃以下の範囲で脱型し、
次いで、成形品温度を60℃以下まで冷却することを特徴とする積層体成形品の成形方法。
(請求項6)
成形品温度を60℃以下まで冷却する際に、矯正型に沿わせて形状を保持した状態で冷却することを特徴とする請求項5記載の積層体成形品の成形方法。
(請求項7)
成形品温度を60℃以下まで冷却する際に、前記雄雌型のプレス機の雄型に着けたまま冷却することを特徴とする請求項5記載の積層体成形品の成形方法。
図1は、積層された複数の布状体2の一方の面に被覆層3を積層した積層体の例を示す概略断面図であり、図2は、積層された複数の布状体2の両方の面に被覆層3、3を積層した図1の改良の一例を示す概略断面図である。
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。
(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。
本発明に用いられる布状体2は、線条体1を用いて織製した織布(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。
図1において、被覆層3は、積層された複数の布状体2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、積層された複数の布状体2の両方の面に設けられている。
被覆層の貯蔵弾性率は、例えば、測定装置(EPLEXOR500N(ネッチガボ社製):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。
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、布状体2と同一成分からなる接着層4を介して積層されていることが好ましい。布状体2と接着層4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。
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。
(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;
が挙げられる。
次に、図9に基づいて、本発明に係る積層体成形品の成形方法について説明する。
プレス機8としては、雌型81と雄型82からなる雄雌型のプレス機が用いられる。
このため本発明では、図9(C)に示すように、成形品温度を60℃以下まで冷却することができる。
また別の態様として、成形品温度を60℃以下まで冷却する際に、前記雄雌型のプレス機の雄型82に着けたまま冷却することができる。
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。
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。
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。
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、0.6mmのポリプロピレンフィルムを用いた。
被覆層は、ポリプロピレン(PP A)(プロピレン-エチレンランダム共重合体、MFR=2.0g/10分、密度=0.90g/ml)55重量%と、ポリプロピレン(PP C)(ホモポリプロピレン、MFR=0.5g/10分、密度=0.90g/ml)45重量%とをブレンドし、溶融してフィルム成形して、厚さ110μmのポリプロピレンフィルムを製造した。
<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
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、得られた被覆層を設けた。
層構成は、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。
実施例1において、被覆層のポリプロピレンフィルム(PP C)を、ポリプロピレン(PP D)(エチレン-プロピレンブロック共重合体、MFR=2.1g/10分、密度=0.90g/ml)に代える以外は実施例1と同様にして、実施例2の積層体を得た。
実施例1において、ポリプロピレン(PP A)の含有量を、70重量%に代え、実施例1で用いた被覆層のポリプロピレン(PP C)を、ポリプロピレン(PP B)(ホモポリプロピレン、MFR=2.0g/10分、密度=0.90g/ml)に代え、含有量を30重量%に代える以外は実施例1と同様にして、比較例1の積層体を得た。
実施例1において、ポリプロピレン(PP C)を、ポリプロピレン(PP B)に代え、含有量を45重量%とする以外は実施例1と同様にして、比較例2の積層体を得た。
上記のようにして得られた実施例1、実施例2、比較例1及び比較例2の積層体の外周を把持した状態で、赤外線ヒーターで、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、型開きし、脱型して成形品を得た。
脱型時の成形品の温度を測定し、表1に示す。
脱型時の成形品について、以下の基準で評価した。その結果を表1に示す。
〇:被覆層浮きは発生せずに表面の外観が優れた成型品を得ることができた
×:被覆層浮きが発生し、外観が歪んだ成型品になってしまっている
表1に示す実施例及び比較例の積層体を成形して得られた成形品の脱型後の写真を図10に示す。
図10において、図10(A)は比較例1の積層体を成形して得られた成形品の脱型後写真であり、図10(B)は比較例2の積層体を成形して得られた成形品の脱型後写真であり、図10(C)は実施例1の積層体を成形して得られた成形品の脱型後写真であり、図10(D)は実施例2の積層体を成形して得られた成形品の脱型後写真である。
このため、高い脱型時温度でも、表面の外観が優れた成型品を得ることができる結果、成形サイクルタイムを短縮することができることが確認できた。
実施例1、実施例2、比較例1及び比較例2の積層体から成型品を製造する成型品の製造試験において、以下の様に成型条件を変更し(変更点は以下に記した)、それ以外は同様にして、実施例3、実施例4、比較例3及び比較例4の実験を行った。
実施例1で使用した積層体を用い、積層体の外周を把持した状態で、恒温炉で、積層体表面が170℃になるまで加熱した後に、100℃に加熱された金型でプレス成形し、1.5分間閉型した後に、型開きし、脱型して成形品を得た。
実施例2で使用した積層体を用い、実施例3と同様に試験した。
比較例1で使用した積層体を用い、実施例3と同様に試験した。
比較例2で使用した積層体を用い、実施例3と同様に試験した。
比較例3及び4の場合には、比較例1及び2の場合と同様に、被覆層浮きが発生し、外観が歪んだ成型品になった。
これに対して、実施例3及び4の場合では、実施例1及び2の場合と同様に、被覆層浮きは発生せずに、表面の外観が優れた成型品を得ることができた。
このため、高い脱型時温度でも、表面の外観が優れた成型品を得ることができる結果、成形サイクルタイムを短縮することができることが確認できた。
100 基層
101 表面層
102 低融点部位
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
8 プレス機
81 雄型
82 雌型
83 積層体
84 矯正型
Claims (7)
- 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り、該複数の布状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を積層してなり、
該被覆層の150℃における貯蔵弾性率が3.00×106Pa以上1.00×108Pa以下であることを特徴とする積層体。 - 前記布状体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1記載の積層体。
- 0.02mm以上0.1mm以下の熱可塑性樹脂からなるトップ層が、前記一方の被覆層の上面に積層してなることを特徴とする請求項1又は2記載の積層体。
- 0.02mm以上0.1mm以下の熱可塑性樹脂からなるトップ層が、接着剤層を介して前記一方の被覆層の上面に積層してなることを特徴とする請求項1又は2記載の積層体。
- 請求項1~4の何れかに記載の積層体を雄雌型のプレス機でプレス成形し、
次いで、前記成形により得られた成形品の成形品温度が70℃以上120℃以下の範囲で脱型し、
次いで、成形品温度を60℃以下まで冷却することを特徴とする積層体成形品の成形方法。 - 成形品温度を60℃以下まで冷却する際に、矯正型に沿わせて形状を保持した状態で冷却することを特徴とする請求項5記載の積層体成形品の成形方法。
- 成形品温度を60℃以下まで冷却する際に、前記雄雌型のプレス機の雄型に着けたまま冷却することを特徴とする請求項5記載の積層体成形品の成形方法。
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JP2014218074A (ja) | 2013-04-11 | 2014-11-20 | 株式会社Kosuge | 成形品の製造方法 |
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