WO2010029955A1 - 積層板および複合成形体 - Google Patents
積層板および複合成形体 Download PDFInfo
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- WO2010029955A1 WO2010029955A1 PCT/JP2009/065772 JP2009065772W WO2010029955A1 WO 2010029955 A1 WO2010029955 A1 WO 2010029955A1 JP 2009065772 W JP2009065772 W JP 2009065772W WO 2010029955 A1 WO2010029955 A1 WO 2010029955A1
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- WIPO (PCT)
- Prior art keywords
- aluminum alloy
- plate
- resin
- polypropylene resin
- laminated
- Prior art date
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
- B29C44/1228—Joining preformed parts by the expanding material
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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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
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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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
- 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
- B32B5/18—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 features of a layer of foamed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D29/00—Superstructures, understructures, or sub-units thereof, characterised by the material thereof
- B62D29/001—Superstructures, understructures, or sub-units thereof, characterised by the material thereof characterised by combining metal and synthetic material
- B62D29/002—Superstructures, understructures, or sub-units thereof, characterised by the material thereof characterised by combining metal and synthetic material a foamable synthetic material or metal being added in situ
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
- Y10T156/10—Methods of surface bonding and/or assembly therefor
- Y10T156/1002—Methods of surface bonding and/or assembly therefor with permanent bending or reshaping or surface deformation of self sustaining lamina
- Y10T156/1043—Subsequent to assembly
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24628—Nonplanar uniform thickness material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
Definitions
- the present invention relates to a lightweight laminated plate and a composite molded body that are suitable for automobile bodies and parts, etc., and have excellent shape stability after cold forming.
- the laminate referred to in the present invention is formed by laminating aluminum alloy plates on both sides of a core foamable resin. This laminated board is cold-formed (plastically processed) and then foamed by heating the core material foamable resin to form a composite molded body.
- pure aluminum-based 1000 series including 1200 series and 8079 series described later
- aluminum alloys are also referred to as aluminum alloys.
- a foamable resin (foamable resin) is sandwiched between two flat aluminum alloy plates with an adhesive resin interposed therebetween, and the material is laminated. Bond and integrate as a laminate. Thereafter, the material laminate is formed into a desired shape by a forming process (plastic processing) such as pressing or roll forming. After the molding or before the molding, the foamable resin is foamed by heating at a foaming temperature of the foamable resin higher than that at the time of adhesion.
- the foamable resin means a resin that foams by heating or a resin that can be foamed by heating.
- the foaming ratio of the foamed resin is controlled to achieve different foaming. It has been proposed to laminate a foamed resin having a magnification (see Patent Document 1). Further, in order to suppress exfoliation of the foamable resin layer after foaming, it has also been proposed to interpose an adhesive layer and a non-foamable resin layer between the aluminum alloy plate and the foamable resin layer ( Patent Document 2).
- a lightweight composite plate can also be applied to the field of automobile body panels, the weight of the vehicle body can be reduced, and fuel consumption and maneuverability can be improved.
- outer panels such as hoods and doors, inner panels, roof panels, undercover panels, or car body panels such as deck boards and bulkheads, as is well known, have a relatively large area of 2 m 2 or more.
- it has a complicated shape and a large molding area. For this reason, even steel plates that are actually used as automotive body panel materials and aluminum alloy plates that are inferior in formability to steel plates are relatively difficult to perform press forming such as stretch forming and draw forming. There is a case.
- Patent Document 3 A foamed resin laminated soundproof board having vibration damping performance and the like, and a manufacturing method thereof have also been proposed.
- Such a foamed resin laminated soundproof board can reduce the thickness of the laminated board as long as the foamable resin is kept in an unfoamed state. For this reason, after laminating this unfoamed foamable resin into a predetermined panel shape by press molding or the like, the composite panel is heated to the resin foaming temperature to make the foamable resin a foamed resin, and the thickness is increased. It can be increased. As a result, the laminated plate can be press-molded into a predetermined shape while ensuring the size and shape accuracy without being limited by the shape, construction location, and weight. Further, by increasing the thickness of the foamable resin, it is possible to enhance the rigidity imparting effect and the vibration damping performance, and to exhibit the soundproof performance.
- the above-described automotive body panel having a relatively large area is formed of a single metal plate (single unit) that has been remarkably thinned to, for example, 2.0 mm or less in order to reduce weight.
- the production side of the automobile body panel is It is preferable to use the same molding press or the same molding conditions as the molding.
- the thickness of the material laminate cannot be increased to more than 3.4 mm in order to reduce the weight of the automobile body panel.
- the thickness of the foamable resin layer which is lower in density than the metal plate side, is increased in order to reduce weight and ensure bending rigidity. It is necessary to make the side plate thickness relatively thin. Therefore, the thickness of each metal plate constituting the material laminated plate needs to be 1.0 mm or less even with a relatively light aluminum alloy plate. However, as described later, the forming limit of such a thin metal plate is significantly reduced as the thickness is reduced.
- the moldability of the core foamable polypropylene resin alone is by no means good.
- the above-described cold press molding of an automobile body panel having a relatively large area is a processing into a three-dimensional shape. Compared to the processing to the two-dimensional shape, the processing to the three-dimensional shape requires much more elongation and elastic modulus.
- conventional foamed resins have been selected with emphasis on smoothness and aesthetics, and are not intended for cold press formability to such a three-dimensional shape.
- cold forming with a single foamed resin is difficult in terms of molding itself and shape stability of the molded body. For this reason, it is common knowledge in the conventional resin field that molding processing of a foamed resin alone into a panel or the like needs to be performed warmly or hotly.
- the present invention is a laminated plate in which a thin aluminum alloy plate having a remarkably reduced molding limit is laminated on both sides of a core foamable polypropylene resin that is poorly moldable.
- An object of the present invention is to provide a laminated sheet that can be cold formed and has excellent shape stability after the forming.
- the gist of the laminate of the present invention is that an aluminum alloy plate is laminated on both sides of a core material expandable polypropylene resin, and the core material expandable polypropylene resin is foamed by heating after molding.
- the sheet thickness of the expandable polypropylene resin is 0.5 to 1.4 mm
- the aluminum alloy sheet is classified according to the quality standard defined by the JISH0001 standard.
- a tempered material selected from T4 materials are examples of the aluminum alloy sheet.
- the thickness of the entire laminated plate is 2.4 mm or less
- the thickness of the aluminum alloy plate is 0.05 to 0.5 mm
- the thickness of the core foamable polypropylene resin is 0. It is preferably 5 to 1.4 mm.
- the aluminum alloy plate of the laminated plate is selected from 1000 series, 3000 series, 5000 series, and 6000 series aluminum alloys.
- the aluminum alloy is 6000 series, it is preferably selected from O material or T4 material.
- the aluminum alloy is 5000 series, it is preferably selected from O material or H32 material to H34 material.
- the gist of the composite molded body of the present invention is that the above-mentioned laminated plate is molded in the cold, and then the core material expandable polypropylene resin is foamed by heating.
- the inventors When the thickness of the aluminum alloy plate constituting the laminated plate is extremely thin, the inventors have confirmed that in the examples described later, as shown in FIGS. 4 to 7, compared with the case of a relatively thick plate. It has been found that the elongation is significantly reduced.
- the aluminum alloy is an O material of 3004, it is known from, for example, an aluminum handbook issued by the Japan Light Metal Association that it has an elongation of about 20% when the plate thickness is 1.6 mm.
- the elongation is remarkably reduced to about 3%.
- the same applies to other aluminum alloy systems such as 1000 series, 3000 series, 5000 series, and 6000 series.
- the inventors have combined the aluminum alloy plate whose plate thickness is so thin that the formability by itself is reduced in this way with the foamable polypropylene resin having low cold formability by itself, and the overall plate thickness is reduced. On the other hand, it was found that the cold formability is remarkably improved when a thin laminate is used.
- the results of the tensile test conducted by the inventors include, for example, a 3004 O-material aluminum alloy plate having a plate thickness of 0.05 mm (50 ⁇ m) on both sides of the core foamable polypropylene resin. The elongation of the laminated plate laminated and integrated with each other is improved to about 14% as in the examples described later.
- This lamination also brings about an effect of improving the shape stability of the foamable polypropylene resin side.
- the foamable polypropylene resin alone has a large elastic deformation rate (elastic deformation rate), so buckling ability to return to the original linear shape by plastic deformation by cold forming. Is high and shape stability is low.
- the aluminum alloy plate has a larger plastic deformation ratio (plastic deformation rate) than that of the expandable polypropylene resin. Therefore, the aluminum alloy plate has a predetermined shape by plastic deformation by cold forming. The buckling property to return to the linear shape is low. Therefore, by lamination, the proportion of plastic deformation (plastic deformation rate) of the expandable polypropylene resin is increased, and the shape stability is improved.
- FIG. 1 is a perspective view showing a laminated board of the present invention in which a core resin before foaming is laminated.
- FIG. 2 shows a state of the composite plate 1a in which the laminated plate 1 of FIG. 1 is heated as a flat plate to foam the foamable resin 3a to obtain the foamed resin 3b as the core material.
- FIG. 3 is a partial view showing a state of a composite molded body (heat ray shielding cover) 1b obtained by heating the laminated plate 1 of FIG. 1 after cold forming to foam the foamable resin 3a to form a foamed resin 3b as a core material. It is a cross-sectional perspective view.
- the laminate 1 of the present invention which is a material for the composite molded body of FIGS. 2 and 3, is an adhesive resin between two aluminum alloy plates 2a and 2b in order from the top of the figure. 4a, a foamable resin (unfoamed resin) 3a, and an adhesive resin 4b are stacked and sandwiched.
- the adhesive resin 4 is not essential when the foamable resin 3a itself has a sufficient adhesive effect with the aluminum alloy plates 2a and 2b. However, it is preferable to use the adhesive resin 4 in order to ensure the bonding strength required at the time of molding the laminated plate 1 and the necessary bonding strength as a composite molded body.
- FIG. 2 shows a flat plate-shaped composite molded body 1a
- FIG. 3 shows a HAT-shaped composite molded body 1b
- 2 and 3 show the composite molded bodies (molded panels) 1a and 1b obtained by heating the laminated plate 1 of FIG. 1 after cold forming to foam the foamable resin 3a to form a foamed resin 3b. Indicates the state.
- the composite molded body 1b shown in FIG. 3 simulates an under cover panel that is formed into an HAT type having a flat top portion (convex portion: cup) that is flat and has a relatively large area.
- the laminate of the present invention is intended for a thin laminate that is cold-formed into a panel shape. Therefore, thick laminates such as buildings and structures that are not coldly formed into a panel shape are outside the scope of the present invention.
- thick laminates such as buildings and structures that are not coldly formed into a panel shape are outside the scope of the present invention.
- the laminate of the present invention instead of a single metal plate for further weight reduction of a panel for an automobile body which is a specific application of the laminate of the present invention.
- the aluminum alloy plates 2a and 2b laminated on the laminated plate are required to have appropriate strength in order to improve the cold formability (molding property and shape stability after forming) of the laminated plate.
- the aluminum alloy plates 2a and 2b are tempered materials selected from O material, H22 material to H24 material, H32 material to H34 material, and T4 material, according to the quality code defined by the JISH0001 standard. .
- This appropriate strength is also necessary for the bending rigidity and bending strength of the composite molded body.
- the strength of the aluminum alloy plate depends on the component composition of the alloy, but is greatly affected by the tempering treatment.
- the other tempered materials have high strength, but the elongation is too low, and the cold formability of the laminate is reduced. It cannot be improved sufficiently.
- the aluminum alloy plate is 6000 series, it is preferably selected from O material or T4 material.
- the aluminum alloy plate is 5000 series, it is preferably selected from O material or H32 material to H34 material.
- the deformation amount ⁇ obtained by applying a load (molding load) to the laminated plate 1 during molding is an elastic deformation amount ⁇ E that becomes zero after the load is unloaded, and the deformation amount does not change even when the load is unloaded. It is the sum of the plastic deformation amount ⁇ P.
- the fact that it can be molded into a predetermined shape in the cold state means that immediately after unloading the molding load, the plastic deformation amount ⁇ P after the elastic deformation amount ⁇ E becomes zero becomes the target deformation amount ⁇ . It means to become.
- the proportion of plastic deformation (plastic deformation rate) of the expandable polypropylene resin is increased, and the shape stability is improved. For this reason, it is possible to perform cold molding such as press molding into a three-dimensional shape such as a panel for an automobile body having a relatively large area.
- the foamable resin 3a is sandwiched between the two aluminum alloy plates 2a and 2b, and the composite plate is molded while being constrained. For this reason, it becomes difficult to generate
- this lamination results in a structure in which the foamed core material foam resin 3b is sandwiched between the two aluminum alloy plates 2a and 2b.
- the thickness of the core material expandable polypropylene resin 3a (the thickness of the unfoamed resin layer) is defined below. That is, when the thickness of the laminated plate is 3.4 mm or less, the thickness of the core material expandable polypropylene resin is in the range of 0.5 to 1.4 mm. Further, when the thickness of the laminated plate is 2.4 mm or less, the thickness of the core material expandable polypropylene resin is in the range of 0.5 to 1.4 mm. In addition, when there is “variation" in the thickness of the unfoamed polypropylene resin layer depending on the part of the laminated board, the average value at the selected appropriate part of the laminated board is used.
- the thickness of the core foamable polypropylene resin 3a is too thin, the thickness of the core foam resin 3b is reduced, so that it is not as light as a single aluminum alloy plate having the same bending rigidity or bending strength. Therefore, the meaning of using a composite plate or a composite molded body is lost.
- the foamable polypropylene resin 3a if the thickness of the core foamable polypropylene resin 3a is too thick, the effect of the relatively thin aluminum alloy plate (as a laminated plate) is reduced by half, which is not much different from the foamable polypropylene resin alone. For this reason, the foamable polypropylene resin having a large elastic deformation ratio (elastic deformation rate) has the original linear shape even when it can be formed into a predetermined shape by plastic deformation by cold forming. The buckling property to return is increased and the shape stability is decreased. Moreover, if the plate thickness of the core material expandable polypropylene resin 3a is too thick, the plate thickness of the core material foam resin 3b becomes too thick.
- the expansion ratio of the core material expandable polypropylene resin 3a to the core material foam resin 3b (after expansion) is preferably about 2 to 20 times. Accordingly, it is possible to ensure that the composite molded body having a relatively large area such as an automobile body panel has both light weight, bending rigidity and bending strength. If this expansion ratio is too small, the composite molded body will not be lighter than an aluminum alloy plate having the same bending rigidity or bending strength, and there is a high possibility that the meaning of using the composite plate or composite molded body will disappear. On the other hand, if the expansion ratio is too large, there is a high possibility that the bending rigidity and bending strength of the composite plate or composite molded body in use will be significantly reduced.
- the olefin random copolymer (A) is 90 to 99% by weight
- the melt flow rate (MFR, ASTM D1238, 230 ° C., 2.16 kg load) is 0.1 to 50 g / 10 min
- a resin composition consisting of ⁇ 10 parts by weight is preferred.
- the propylene content of the propylene / ⁇ -olefin random copolymer (A) is 90 to 99.9 mol%, preferably 92 to 95 mol%.
- Examples of the ⁇ -olefin copolymerized with propylene include at least one ethylene or an ⁇ -olefin having 4 to 20 carbon atoms.
- Such a propylene / ⁇ -olefin copolymer (A) typically includes a solid titanium catalyst and a catalyst mainly composed of an organometallic compound, or a metallocene catalyst using a metallocene compound as one component of the catalyst. It can be produced by copolymerizing propylene and ⁇ -olefin under the following conditions.
- the melt flow rate (MFR, ASTM D1238, 230 ° C., 2.16 kg load) of the propylene / ⁇ -olefin random copolymer (B) used for the expandable polypropylene resin 3a is 0.1 to 50 g / 10 min, preferably 1-20 g / 10 min.
- the melting point of the propylene / ⁇ -olefin copolymer (B) measured by a differential scanning calorimeter (DSC) is 100 ° C. or less, preferably 40 to 95 ° C., more preferably 50 to 90 ° C.
- foaming agent (C) used for the expandable polypropylene resin 3a either an organic foaming agent or an inorganic foaming agent can be used.
- organic foaming agent for example, azo compounds, nitroso compounds, sulfonyl hydrazide compounds and other compounds can be used.
- foamable components those that foam by heating to 120 ° C. or higher, more preferably 150 ° C. or higher are preferable.
- the addition amount of the inorganic foaming agent is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the resin composition comprising (A) and (B).
- the radical generator (D) preferably has a decomposition temperature for obtaining a half-life of 1 minute (min) higher than the melting point of the propylene / ⁇ -olefin copolymer (B). It is preferably higher than the melting point of the ⁇ -olefin copolymer (A). In addition, it is practically preferable that the decomposition temperature for obtaining a half-life of 100 hours (hr) of the radical generator (D) is 40 ° C. or higher.
- organic peroxides include 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, acetyl peroxide, tertiary butyl peroxide (2-ethyl hexaoxy).
- 2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexane and (2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexyne-3) are preferable.
- the crosslinking aid (E) used in the present invention is an unsaturated compound, oxime compound, nitroso compound, maleimide compound or the like having one or more double bonds.
- the radical generator (D) causes the propylene / ⁇ -olefin copolymer (B) and the polymer radical generated by hydrogen abstraction of the propylene / ⁇ -olefin copolymer (A) to undergo a cleavage reaction. Reacts quickly with the crosslinking aid (E).
- the crosslinking aid (E) stabilizes polymer radicals and at the same time crosslinks the propylene / ⁇ -olefin copolymer (B) and the propylene / ⁇ -olefin copolymer (A), and Each of them functions to increase the crosslinking efficiency independently.
- Specific examples of these compounds include triallyl cyanurate, triallyl isocyanurate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, diallyl phthalate, pentaerythritol triacrylate, neopentyl glycol diacrylate, and 1,6-hexane.
- Polyfunctional monomers such as diol dimethacrylate and divinylbenzene, oxime compounds such as quinonedioxime and benzoquinonedioxime, para-nitrosophenol, N, N-meta-phenylenebismaleimide, and two or more of these A mixture is mentioned. Of these, triallyl isocyanurate and trimethylolpropane trimethacrylate are preferred.
- the thermal decomposition temperature of these materials is approximately 400 ° C., and in order to add the thermal decomposition type foaming agent to the resin and uniformly disperse it, the melting point of the propylene / ⁇ -olefin copolymer (A) is 10 ° C. or more. It is necessary to knead the blowing agent at a high temperature. Further, in order to prevent foaming of the foaming agent from starting during kneading, it is preferable to set the foaming temperature to 170 ° C. to 300 ° C., which is 10 ° C. or more higher than the kneading temperature and sufficiently lower than the thermal decomposition temperature. In this way, by heating at 170 ° C. to 300 ° C., the expandable polypropylene resin 3a can be uniformly foamed without being deteriorated.
- the adhesive resins 4a and 4b are made of an adhesive resin capable of bonding (having adhesive strength) to the expandable polypropylene resin 3a and the aluminum alloy plates 2a and 2b.
- a heat fusion type thermoplastic resin mainly composed of polypropylene acid-modified with maleic anhydride or the like is preferably used.
- the properties of the composite molded body can be made to have higher functionality and multifunction. For example, if a highly vibration-damping resin is used as the foamable polypropylene resin and the adhesive resin, the vibration damping performance and sound insulation performance are enhanced. Moreover, if a conductive substance is used, welding performance will increase. When a metal powder is added as a conductive substance to the expandable polypropylene resin 3a and the adhesive resin 4, the resin becomes high density. As a result, the sound insulation performance is improved and the weldability can be improved.
- foamable polypropylene resins and adhesive resins may be films or sheets. Also, either foamed polypropylene resin or adhesive resin (in this case, the other may be a film or a sheet), or both in a molten state or in a solvent state, are rolled or sprayed. It may be applied by, for example. In this application, it is preferable that there is a step of drying after the application.
- Expandable polypropylene resin First, the above-described polypropylene resins (A) and (B) and the pyrolytic foaming agent (C) constituting the expandable polypropylene resin 3a are kneaded. If necessary, the radical generator (D) and the crosslinking aid (E) described above may be added. Moreover, you may add the substance which provides adhesive strength, damping property, and heat resistance, and the metal powder for electroconductivity improvement. These materials are sufficiently kneaded and then formed into a film or a sheet. When filmed, it is wound into a coil. At this time, the kneading temperature of the material is preferably set to be 10 ° C. or lower than the thermal decomposition temperature of the foaming agent used. If it does so, even if the temperature of resin rises by kneading
- Adhesive resin First, the resin material constituting the adhesive resin 4 is kneaded.
- This material is a resin to which a material for imparting adhesive strength / damping property or a metal powder for imparting conductivity is added as necessary. These materials are sufficiently kneaded and then formed into a film or a sheet. In the case of film formation, it is wound into a coil and laminated separately, or is applied to the surface of an aluminum alloy plate.
- the foamable polypropylene resin film or sheet and the adhesive resin may be wound in a coil after being thermally fused and integrated.
- the foamable polypropylene resin and the adhesive resin are integrated so that the surface of the foamable resin is covered with the adhesive resin by two-type three-layer extrusion molding. May be used.
- the adhesive resin film 4 and the foamable resin film 3a are made of an aluminum alloy by stretching from the two coils. It can be laminated on the plate 2 at the same time.
- the expandable polypropylene resin 3a is in an unfoamed state and has a small thickness, it can be coiled. Therefore, since it can convey in a coil shape and can be extended from a coil at a construction place, a construction place is not restrict
- Laminate production The simplest method is to laminate aluminum alloy plates 2a and 2b, which are cut plates, adhesive resin film 4 which is also cut plates, and expandable polypropylene-based resin film 3a in order to form a laminated plate. is there. However, if it is possible in terms of equipment, it may be laminated continuously to form a laminated sheet. That is, both the aluminum alloy plates 2a and 2b are unwound from the coil, while the expandable polypropylene resin film and the adhesive polypropylene resin film are unwound from the coil and stretched. An adhesive resin film may be simultaneously laminated between the aluminum alloy plates 2a and 2b.
- the aluminum alloy plate 2 and the expandable polypropylene resin 3a in FIG. 1 are bonded together via an adhesive resin, and the material laminate 1 is formed.
- the temperature of this hot roll is lower than the foaming temperature of the expandable polypropylene resin 3a, and is generally set in the vicinity of the melting point of the expandable polypropylene resin and the adhesive resin.
- the manufactured laminated board 1 is cold-molded so as to have a shape of a predetermined composite molded body (panel) 1a, 1b.
- forming method press forming such as bulging forming, drawing forming, bending forming or bending can be used.
- Heating foaming
- the composite molded body formed into a predetermined shape by this molding process is heated to the foaming temperature, whereby the expandable polypropylene resin 3a foams to become the foamed resin 3b, and the composite molded bodies 1a and 1b are obtained.
- Heating can be performed after cold forming using a convection heat transfer type heating furnace such as a batch or continuous gas furnace or electric furnace. Since the aluminum alloy has a high heat ray reflectivity, a far-infrared heating furnace cannot be used as it is, but a heat ray absorbing layer such as a coating or an organic film is formed on at least one outer surface of the aluminum alloy plates 2a and 2b. It is possible to heat even a far-infrared heating furnace.
- the foamable polypropylene resin 3a is heated and foamed to form the foamed resin 3b without transfer, and is softened by heating.
- the foamed resin 3b can be cooled and hardened.
- a composite molded body that is foamed from a flat composite plate and has high rigidity can be produced in a short time.
- the composite molded body is soft immediately after heating and foaming, and cooling time is required to maintain the shape after molding.
- the shape is not destroyed by cooling in the same mold as molding that does not require transfer. Thus, productivity can be improved.
- the foamable polypropylene resin 3a of the laminate 1 is first foamed and then the laminate 1 is molded, the above-described lamination of the aluminum alloy plates 2a and 2b and the expandable polypropylene resin film 3a is performed.
- the effect is halved. That is, the effect of homogenizing the strain distribution of the aluminum alloy sheet whose elongation is extremely reduced to 10% or less of the foamed resin 3b after foaming is significantly lower than that of the unfoamed core material foamable resin 3a. As a result, the cold formability of the laminate 1 is significantly reduced.
- Example 1 The laminate 1 shown in FIG. 1 was manufactured, and a tensile test was performed by simulating cold forming while the foamable polypropylene resin 3a remained unfoamed. This is designated as Invention Example A. Further, the laminated plate 1 (Invention A) is heated to foam the expandable polypropylene resin 3a, and the composite plate (flat plate) 1a formed as the core material foamed resin 3b is similarly pulled by simulating cold forming. Tested. This is referred to as Comparative Example B. Further, as Reference Example C, a single plate of only the aluminum alloy plate 2a or 2b (plate thickness 0.05 mm) was subjected to a tensile test in the same manner by simulating cold forming.
- the curve A is the invention example A
- the curve B is the comparative example B
- the curve C is the reference example C.
- the horizontal axis positions indicated by the circles in the curves A, B, and C indicate the maximum strain (also referred to as elongation:%) between both ends of the parallel part of each test piece.
- FIGS. 5 to 7 show changes in strain distribution over time according to the positions of the test pieces of Invention Example A, Comparative Example B, and Reference Example C during these tensile tests.
- 5 shows Invention Example A
- FIG. 6 shows Comparative Example B
- FIG. 7 shows Reference Example C.
- the vertical axis represents the strain amount (%)
- the horizontal axis represents the position of each test piece.
- each position of the test piece over a length of about 60 mm is shown at ⁇ 4 or ⁇ 5 in the horizontal direction of the horizontal axis, centering on ⁇ 0 of the fractured portion (generally near the center) of the test piece.
- a to C shown on the left side indicate the values of A to C between both ends of the parallel part of the test piece in FIG.
- the total board thickness of the laminated board 1 was 1.1 mm. 2.
- a JIS3004 aluminum alloy single plate O material having a thickness of 0.05 mm (50 ⁇ m) was used.
- the total thickness of the aluminum alloy plates 2a and 2b is 0.1 mm.
- the core foamable polypropylene resin 3a is obtained by kneading the following materials (A) to (E) at 155 ° C. and extruding it into a sheet, and uses a sheet having an average plate thickness of 1.0 mm. It was.
- the adhesive resins 4a and 4b a modified polyolefin-based hot-melt adhesive resin film having a melting point of 140 ° C. and a thickness of 0.05 mm was used in common with each example. The total thickness of the adhesive resin film is 0.1 mm.
- the laminated plate 1 was manufactured as a square planar shape having a length (L direction): 600 mm and a width (LT direction): 1100 mm in common with each example. From this, a strip-shaped test piece (25 mm ⁇ 50 mmGL) of No. 5 of JISZ2201 was collected and subjected to a tensile test. The tensile test was performed at room temperature of 25 ° C. based on JISZ2241 (1980) (metal material tensile test method). The tensile speed was 200 mm / min, and the test was performed at a constant speed until the test piece broke.
- the elongation of the unfoamed laminated board 1 which is the invention example A in which the aluminum alloy thin plates are laminated is as high as about 14%.
- the measurement result of the elongation by the tensile test is 17 to 18%. It was about as high as it was.
- Comparative Example B shown in FIG.
- the elongation of Comparative Example B is about 5%, which is not much different from Reference Example C of the aluminum alloy thin plate.
- the unfoamed laminated board 1 of Invention Example A having an elongation of about 14% can be cold-molded such as press-molding and has excellent shape stability. Therefore, these results support that there is an effect of improving the formability by the above-described lamination of the aluminum alloy plates 2a and 2b and the expandable polypropylene resin film 3a. That is, even a laminated plate in which a thin aluminum alloy plate having a remarkably reduced molding limit is laminated on both surfaces of a core foaming resin, which is inferior in moldability by itself, can be molded and after molding. It can be proved that a laminate having excellent shape stability can be provided.
- Example 2 Regarding the cold formability of the laminate 1 of the present invention, in particular, the shape stability after cold forming that was not backed up in Example 1, the crack limit forming height and the shape stability after forming were determined by an overhang forming test. And evaluated. These results are shown in Tables 1 and 2.
- Table 1 shows the lamination conditions and cold formability of the laminate 1 of the present invention.
- Table 2 shows that the aluminum alloy plate and the foamable resin film constituting the laminated plate are each a single plate (single plate), and the conditions and cold formability are shown.
- the production conditions of the laminated plates of Invention Examples 1 to 12 in Table 1 and the single plate of Comparative Example in Table 2 are the same as the production conditions of the laminated plate 1 of Example 1. However, the following example is different from the manufacturing conditions of the laminated plate 1 of Example 1 only in the part described below.
- Invention Example 13: MFR 2.1 g / 10 min propylene homopolymer
- Invention Example 14: MFR 2.0 g / 10 min propylene block copolymer [Prime Polypro J-702LJ manufactured by Prime Polymer Co., Ltd.]
- MFR 1.6 g / 10 min propylene homopolymer 40 parts by weight
- MFR 0.54 g / 10 min propylene block copolymer 20 parts by weight [Prime Polypro B-150M, Prime Polymer Co., Ltd.]
- MFR 55.0 g / 10 min propylene block copolymer 40 parts by weight [Prime Polypro J-739EP manufactured by Prime Polymer Co., Ltd.]
- the comparative example foamable resin of Table 2 was as follows.
- Foamable resin of Comparative Example 24 the same as the foamable resin of Invention Examples 1-14.
- Foamable resin of Comparative Example 25 Same as the foamable resin of Invention Example 15.
- Foamable resin of Comparative Example 26 Same as the foamable resin of Invention Example 16.
- Expandable resin of Comparative Example 27: MFR 54 g / 10 min propylene block copolymer [Prime Polypro J-739E manufactured by Prime Polymer Co., Ltd.]
- the thickness of the foamable resin film 3a of the laminated plate 1 is constant at 1.0 mm.
- the aluminum alloy plates 2a and 2b JIS 8079 series (0.1% Si-1.0% Fe-pure Al alloy for foil of balance Al), 1200 series and 3004 series aluminum alloy plates are used, Various plate thicknesses were also changed.
- the material of the aluminum alloy plate used is described as “anything”, which means the standard alloys “8079”, “1200”, “3004”, and “5052” of the described numbers. is there.
- Crack limit molding height First, the laminate 1 was cut into test pieces having a length of 180 mm and a width of 110 mm. Then, using a spherical overhanging punch having a diameter of 101.6 mm, using R-303P as a lubricant, overhanging is performed at a wrinkle pressing pressure of 200 kN and a punching speed of 240 mm / min, and the height (mm) when the test piece breaks is determined.
- the crack limit molding height test was performed. Each sample was tested three times and the average value was adopted. The larger the crack limit molding height, the better the stretch formability. For example, in order to satisfy the stretch moldability required for the above-described automotive molded panels, it should be 15 mm or more. That's fine.
- Shape stability The shape stability was evaluated by visually evaluating the amount of buckling when the molded product that had been stretched was left unloaded and left unsatisfactory.
- the O material is known to have an elongation of about 40% when the plate thickness is 1.6 mm.
- the plate thickness is reduced to 0.05 mm (50 ⁇ m)
- the elongation is remarkably reduced to about 5% as in the case of the O material of the 3000 series aluminum alloy plate.
- Invention Examples 3 to 8 and 11 to 16 have a crack limit forming height of 13 mm or more even when the aluminum alloy plate is thinned to 1.0 mm or less, and shape stability after cold forming is improved. Is also excellent.
- the crack limit molding height was 13 mm or more (even if molding was possible)
- the shape stability is inferior, and cold forming is difficult because of the stretchability required for forming the panel.
- the unfoamed laminated board 1 which is an example of the invention can be cold-molded such as press-molding and has excellent shape stability. Therefore, the moldability improvement effect by lamination
- the present invention enables cold molding such as press molding into a three-dimensional shape such as the automobile body panel having a relatively large area, and is excellent in shape stability after molding.
- Laminates can be provided.
- a laminated sheet for a composite molded body having excellent bending rigidity and bending strength can be provided. Therefore, the present invention is suitable for automobile body panels having a relatively large area, such as outer panels such as hoods and doors, inner panels, roof panels, undercover panels, deck boards, and bulkheads.
- 1 Laminated plate
- 1a Composite molded body
- 1b Composite molded body
- 2 Aluminum alloy plate
- 3a (Core material) Expandable polypropylene resin (film)
- 3b (Core material) foamed resin
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- Architecture (AREA)
- Structural Engineering (AREA)
- Chemical & Material Sciences (AREA)
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- Transportation (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Body Structure For Vehicles (AREA)
Abstract
Description
本発明積層板は、冷間でパネル形状に成形される薄い積層板を対象とする。したがって、冷間でパネル形状に成形されない、建築物や構造物のような厚い積層板は本発明の対象外である。前記した通り、本発明積層板の具体的な用途である自動車車体用パネルなどのさらなる軽量化のために、金属板単板の代わりに本発明積層板を用いて複合成形体を得る場合には、プレス成形工程や軽量化のために、板厚が金属板単板よりもあまりに厚くなった素材積層板を用いることはできない。即ち、自動車車体用パネルの製作側は、金属板単板の成形時と同じ成形プレス、あるいは同じプレス成形条件を用いたい。また、金属板単板の代替としては、自動車車体用パネルをより軽量化させることが望まれる。
このような薄い積層板に積層されるアルミニウム合金板2a、2bの各板厚も、薄いほど好ましく、好ましくは0.05~1.0mmの範囲、より好ましくは0.05~0.5mmの範囲である。ただ、アルミニウム合金板2a、2bの板厚が、片側一方だけでも0.05mm未満の場合には板厚が薄すぎるため、芯材発泡樹脂を発泡させた自動車車体パネルなどの比較的大きな面積を有する複合成形体としての使用状態での曲げ剛性および曲げ強度が著しく低下する。一方、アルミニウム合金板2a、2bの板厚が、片側一方だけでも1.0mm、厳しくは0.5mmを超えた場合には、重量が重くなり、軽量化が犠牲となって、複合成形体とする意味自体が失われる。
積層板に積層されるアルミニウム合金板2a、2bは、積層板の冷間成形性(成形加工性、成形後の形状安定性)の向上のために、適正な強度が必要である。このため、アルミニウム合金板2a、2bは、JISH0001規格にて規定される質別記号で、O材、H22材~H24材、H32材~H34材及びT4材から選択される調質処理材とする。この適正な強度は、複合成形体としての曲げ剛性や曲げ強度にも必要である。アルミニウム合金板の強度は、勿論、合金の成分組成にもよるが、調質処理による影響が大きい。特に、1000系、3000系、5000系、6000系などのアルミニウム合金系においては、これ以外の調質処理材は、強度が高くなる反面、伸びが低すぎて、積層板の冷間成形性を十分に向上できない。ここで、アルミニウム合金板が6000系の場合には、O材またはT4材から選択されることが好ましい。また、アルミニウム合金板が5000系の場合には、O材またはH32材~H34材から選択されることが好ましい。
このように、2枚のアルミニウム合金板2a、2bの間に、未発泡状態の発泡性樹脂3aと接着用樹脂4bとを積層した(挟み込む)場合、前記した通り、アルミニウム合金板単体、発泡性樹脂単体の場合に比して、冷間成形性向上効果と冷間成形後の形状安定性の向上効果がもたらされる。アルミニウム合金板と発泡性ポリプロピレン系樹脂との積層化によって、アルミニウム合金板が薄板である場合でも、その歪み分布が均一化する。このため、冷間成形において、大きな局所的な伸びが生じないか、あるいは大きな局所的な伸びが生じるまでの時間が遅くなるので、冷間成形中のアルミニウム合金薄板が短時間には破断しなくなる。
以上のような積層板の構成を前提にして、以下に、本発明では、芯材発泡性ポリプロピレン系樹脂3aの板厚(未発泡樹脂層の厚み)を規定する。即ち、積層板の板厚が3.4mm以下である場合には、芯材発泡性ポリプロピレン系樹脂の板厚は0.5~1.4mmの範囲である。また、積層板の板厚が2.4mm以下である場合には、芯材発泡性ポリプロピレン系樹脂の板厚は0.5~1.4mmの範囲である。なお、積層板の部位により、未発泡ポリプロピレン系樹脂層の厚みに「ばらつき」がある場合には、積層板の選択された適当部位における平均値とする。
芯材発泡性ポリプロピレン系樹脂3aの、芯材発泡樹脂3b(発泡後)への発泡倍率は2~20倍程度とすることが好ましい。これによって、自動車車体パネルなどの比較的大きな面積を有する複合成形体の、軽量化と曲げ剛性および曲げ強度の兼備を保証できる。この発泡倍率が小さすぎると、曲げ剛性か曲げ強度が同じアルミニウム合金板単体に比して複合成形体が軽量とはならず、複合板や複合成形体を使う意味がなくなる可能性が高い。一方、この発泡倍率が大きすぎると、複合板や複合成形体の使用状態での曲げ剛性および曲げ強度が著しく低下する可能性が高い。
積層板の芯材発泡性樹脂3aは、ランダム共重合ポリプロピレン系樹脂(R.PP)、ホモポリプロピレン系樹脂(H.PP)、共重合ポリプロピレン系樹脂(B.PP)の一種以上からなることが好ましい。これらのポリプロピレン系樹脂は、他の樹脂に比して、伸びが低下したアルミニウム合金薄板の歪み分布を均一化する成形性向上効果が大きい。即ち、前記調質処理材であるアルミニウム合金薄板と組み合わされて積層された場合に、成形可能性や形状安定性などの成形性向上効果が大きい。
プロピレン・α-オレフィンランダム共重合体(A)のプロピレン含量は、90~99.9モル%、好ましくは92~95モル%である。プロピレンとともに共重合されるα-オレフィンとしては、少なくとも1種以上のエチレンないしは炭素数4~20のα-オレフィンが挙げられる。このようなプロピレン・α-オレフィン共重合体(A)は、典型的には固体状チタン触媒と有機金属化合物を主成分とする触媒、またはメタロセン化合物を触媒の一成分として用いたメタロセン触媒の存在下でプロピレンとα-オレフィンを共重合させることによって製造することができる。
プロピレン・α-オレフィン共重合体(B)は、公知の立体規則性触媒を用いてプロピレンと他のα-オレフィンを共重合することによって得ることができるが、特にメタロセン触媒を用いて共重合されたものが、成形体のベタツキが少ないために望ましい。プロピレンとともに共重合されるα-オレフィンとしては、エチレン、1-ブテン、1-ペンテンをはじめとする少なくとも1種以上の炭素数2~20のα-オレフィン(プロピレンを除く)が挙げられる。プロピレン・α-オレフィン共重合体(B)のα-オレフィン含量としては、5~50モル%、好ましくは10~35モル%のものが使用される。このようなプロピレン・α-オレフィン共重合体(B)は、例えば国際公開番号WO95/14717に記載されているような触媒を用いて製造することができる。
有機発泡剤としては、例えば、アゾ化合物、ニトロソ化合物、スルホニルヒドラジド化合物およびその他の化合物などが使用可能である。具体的には、アゾジカルボンアミド、アゾジカルボン酸バリウム、アゾビスイソブチロニトリル、N,N’-ジニトロソペンタメチレンテトラミン、p-トルエンスルホニルヒドラジド、p,p’-オキシビス(ベンゼンスルホニルヒドラジド)、ヒドラゾジカルボンアミド、ジフェニルスルホン-3,3ジスルホニルヒドラジド、p-トルエンスルホニルセミカルバジド、トリヒドラジノトリアジン、ビウレアなどが挙げられる。
無機発泡剤としては、炭酸水素ナトリウム、炭酸亜鉛など、さらには熱膨張性マイクロカプセルなどが挙げられる。これらの発泡性成分の中でも、120℃以上、より好ましくは150℃以上に加熱することにより発泡するものが好ましい。尚、上記発泡剤は1種単独、または2種以上を組み合わせて使用しても良い。無機発泡剤の添加量は、(A)および(B)からなる樹脂組成物100重量部に対し、0.1~10重量部が好ましく、より好ましくは0.5~5重量部である。
本発明に用いられるラジカル発生剤(D)としては、有機ペルオキシド、有機ペルオキシエステルが主として用いられる。ラジカル発生剤(D)は、1分(min)の半減期を得るための分解温度が、前記プロピレン・α-オレフィン共重合体(B)の融点よりも高いことが好ましく、更には前記プロピレン・α-オレフィン共重合体(A)の融点よりも高いことが好ましい。
なお、前記ラジカル発生剤(D)の100時間(hr)の半減期を得るための分解温度は、40℃以上であることが実用上好ましい。
これらのうちでは、2,5‐ジメチル‐2,5‐ジ(ターシヤリーブチルペルオキシ)ヘキサン、(2,5‐ジメチル‐2,5‐ジ(ターシヤリーブチルペルオキシ)ヘキシン‐3)が好ましい。
これらの化合物としては具体的には、トリアリルシアヌレート、トリアリルイソシアヌレート、エチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、ジアリルフタレート、ペンタエリスリトールトリアクリレート、ネオペンチルグリコールジアクリレート、1,6‐ヘキサンジオールジメタクリレート、ジビニルベンゼン等の多官能性モノマー、キノンジオキシム、ベンゾキノンジオキシム、等のオキシム化合物、パラ‐ニトロソフエノール、N,N‐メタ‐フエニレンビスマレイミド、および、これらの2種以上の混合物が挙げられる。
これらのうちでは、トリアリルイソシアヌレート、トリメチロールプロパントリメタクリレートが好ましい。
接着用樹脂4a、4bは、発泡性ポリプロピレン系樹脂3aとアルミニウム合金板2a、2bとの接着が可能な(接着強度を有する)接着用樹脂からなる。接着用樹脂4a、4bとしては、無水マレイン酸などで酸変性させたポリプロピレンを主成分とする、熱融着タイプの熱可塑性樹脂が好適に用いられる。
樹脂応用例として、無機系や金属系のフィラーや添加剤を含有させることにより、複合成形体の特性をより高機能、多機能とすることができる。例えば、発泡性ポリプロピレン系樹脂、接着用樹脂として、制振性の高い樹脂を用いれば、制振性能や遮音性能が高まる。また、導電性物質を用いれば、溶接性能が高まる。上記の発泡性ポリプロピレン系樹脂3aや接着用樹脂4に導電性物質として金属粉末が添加されると、樹脂は高密度となる。これにより、遮音性能が高まるとともに、溶接性が向上できる。
これら発泡性ポリプロピレン系樹脂、接着用樹脂は、フィルムあるいはシートであっても良い。また、発泡性ポリプロピレン系樹脂、接着用樹脂のうち、何れか一方(この場合、他方はフィルムあるいはシートでよい)、または両方を、溶融状態または溶媒に溶解させた状態のものを、ロールやスプレーなどで塗布してもよい。なお、この塗布の場合には、塗布後に乾燥する工程があることが好ましい。
ここで、積層板や複合成形体の製造方法について、以下に説明する。
はじめに、発泡性ポリプロピレン系樹脂3aを構成する、前記したポリプロピレン系樹脂(A)、(B)、及び熱分解型発泡剤(C)を混練する。必要に応じて、前記した、ラジカル発生剤(D)、架橋助剤(E)を添加してもよい。また、接着強度、制振性、耐熱性を付与する物質や、導電性向上のための金属粉末を添加してもよい。これらの材料は、十分混練された後、フィルムあるいはシート化される。フィルム化された場合には、コイル状に巻かれる。このとき、上記材料の混練温度は、用いられる発泡剤の熱分解温度よりも10℃以上低く設定されていることが好ましい。そうすると、混練されることで樹脂の温度が上昇しても、発泡が起こることを防止することができる。
はじめに、接着用樹脂4を構成する樹脂材料を混練する。この材料は、接着強度・制振性付与する材質や、導電性を付与するための金属粉末が必要に応じて添加された樹脂である。これらの材料は、十分混練された後、フィルム化あるいはシート化される。フィルム化の場合には、コイル状に巻かれて別途積層されるか、アルミニウム合金板の表面に塗布される。
切り板とされたアルミニウム合金板2a、2bと、同じく切り板とされた接着用樹脂フィルム4と、発泡性ポリプロピレン系樹脂フィルム3aとを、順に積層して、積層板となす方法が最も簡便である。ただ、設備的に可能であれば、連続的に積層して積層板をなしてもよい。即ち、アルミニウム合金板2a、2bの両方をコイルから巻き出し、一方で、上記発泡性樹脂フィルムおよび接着用ポリプロピレン系樹脂フィルムを、各々コイルから巻き出して引き伸ばしながら、上記発泡性ポリプロピレン系樹脂フィルムおよび接着用系樹脂フィルムをアルミニウム合金板2a、2bの間に同時に積層してもよい。これらの積層後、例えば熱ロールなどにより挟み込んで加熱すれば、図1におけるアルミニウム合金板2と発泡性ポリプロピレン系樹脂3aとが、接着用樹脂を介して、一体に接着され、素材積層板1が製作できる。この熱ロールの温度は、発泡性ポリプロピレン系樹脂3aの発泡温度よりも低く、概ね発泡性ポリプロピレン系樹脂および接着用樹脂の融点近傍に設定される。これにより、元来、接着性のないポリオレフィンからなる発泡性ポリプロピレン系樹脂と、アルミニウム合金板表面に出来た水酸化皮膜とを変性ポリオレフィンにより接着することができる。この結果として、冷間成形に必要なアルミニウム合金板と発泡性ポリプロピレン系樹脂との界面の接着強度を確保することが出来る。
製造された積層板1は、所定の複合成形体(パネル)1a、1bの形状となるように、冷間成形される。成形加工の方法としては、張出成形、絞り成形、曲げ成形などのプレス成形や曲げ加工が使用可能である。
この成形加工によって所定形状とされた複合成形体は、発泡温度まで加熱されることにより、発泡性ポリプロピレン系樹脂3aが発泡して発泡樹脂3bとなり、複合成形体1a、1bが得られる。加熱は、バッチ式または連続式のガス炉、電気炉などの対流伝熱方式の加熱炉を用いて、冷間成形後に行うことが出来る。アルミニウム合金は熱線反射率が高いために、そのままでは遠赤外線式の加熱炉を用いることが出来ないが、アルミニウム合金板2a、2bのうち少なくとも片側の外側表面に塗装や有機皮膜などの熱線吸収層を設けることにより、遠赤外線式加熱炉でも加熱することができる。また、加熱および/または冷却が可能な熱間プレスを用いれば、冷間でプレス成形した後、トランスファーなしで、発泡性ポリプロピレン系樹脂3aを加熱発泡して発泡樹脂3bとし、さらに加熱により柔らかくなっている発泡樹脂3bを冷却して硬くすることができる。これにより、平坦な複合板から発泡して高剛性になった複合成形体を短時間に生産することが出来る。さらに、加熱発泡直後は複合成形体が柔らかく、成形後の形状を維持するには冷却時間が必要であったが、トランスファーの必要がない成形と同一の金型内での冷却により形状を崩さないように短時間で取り出すことが出来るので、生産性を高めることができる。
図1に示した積層板1を製作し、発泡性ポリプロピレン系樹脂3aが未発泡のままで、冷間成形を模擬して引張試験した。これを、発明例Aとする。また、この積層板1(発明例A)を加熱して発泡性ポリプロピレン系樹脂3aを発泡させ、芯材発泡樹脂3bとした複合板(平板)1aを、冷間成形を模擬して同様に引張試験した。これを、比較例Bとする。更に、参考例Cとして、アルミニウム合金板2aか2bのみ(板厚0.05mm)の単板も、冷間成形を模擬して同様に引張試験した。
1.積層板1の合計板厚は、1.1mmとした。
2.積層板を構成するアルミニウム合金板2a、2bには、板厚0.05mm(50μm)の、JIS3004アルミニウム合金単板のO材を用いた。アルミニウム合金板2a、2bの板厚合計は0.1mmである。
3.芯材発泡性ポリプロピレン系樹脂3aは、以下の(A)~(E)の材料を155℃で混練してシート状に押出して得られたものであり、平均板厚1.0mmのシートを用いた。
(A)プロピレン・エチレン・ブテン-1ランダム共重合体(エチレン量=2.2wt%、ブテン-1量=3.7wt%、MFR=7g/10分、融点=130℃):95重量%。
(B)プロピレン・α-オレフィンランダム共重合体(三井化学(株)製タフマーXM7080、MFR=7g/10分、融点=83℃):5重量%。
(C)アゾジカルボンアミド(永和化成(株)製):(A)+(B)100重量部に対し、3重量部。
(D)ラジカル発生剤としてパーヘキサ25B(登録商標、日本油脂(株)製):(A)+(B)100重量部に対し0.05重量部。
(E)架橋助剤としてトリアリルイソシアヌレート:(A)+(B)100重量部に対し、0.5重量部。
4.接着用樹脂4a、4bは、各例とも共通して、融点140℃、厚み0.05mmの変性ポリオレフィン系のホットメルト接着樹脂フィルムを用いた。接着樹脂フィルムの板厚合計は0.1mmである。
積層板1は、各例とも共通して、長さ(L方向):600mm、幅(LT方向):1100mmとした四角の平面形状として製作した。ここから、JISZ2201の5号の短冊状試験片(25mm×50mmGL)を採取し、引張り試験を行った。引張り試験は、JISZ2241(1980)(金属材料引張り試験方法)に基づき、室温25℃で行った。引張り速度は200mm/分で、試験片が破断するまで一定の速度で行った。
図4に示すように、板厚0.05mmのアルミニウム合金薄板単板である参考例Cの伸びは、3%程度である(3004のO材単板は、前記した通り、板厚が1.6mmの場合には20%程度の伸びを有する)。また、図示はしないが、この参考例Cのアルミニウム合金板の板厚を0.08mmに厚くした場合でも、アルミニウム合金薄板単板の伸びは3%程度と増加しなかった。
また、ひずみ分布の時間毎の変化を示す図5~7を互いに比較対照すると、参考例C(アルミニウム合金薄板単板)の図7では、引張試験を開始して0.6~0.8秒の短時間の間に、試験片の中央部の破断位置ε0で、急激に大きな局所的な伸び(ε0位置での山)が生じて成長し、破断していた。即ち、参考例Cでは、短時間に大きな局所的な伸びが生じていた。これに対して、比較例Bの図6、発明例Aの図5の順に、引張試験開始後の局所的な伸び(ε0位置での山)の発生と成長とが、時間的に遅くなっていることが分かる。言い換えれば、試験片の平行部のどの点でのひずみがほぼ等しく長時間均一に伸びが進行していることが分かる。
本発明積層板1の冷間成形性、特に、前記実施例1で裏付けられなかった冷間成形後の形状安定性について、張出成形試験により、割れ限界成形高さと、成形後の形状安定性とを評価した。これらの結果を表1、2に示す。表1は本発明積層板1の積層条件と冷間成形性を示す。表2は、比較のために、積層板を構成するアルミニウム合金板や発泡性樹脂フィルムが各々単板(単独の板)であり、その条件と冷間成形性を示す。
発明例13:
MFR=2.1g/10分のプロピレン単独重合体
発明例14:
MFR=2.0g/10分のプロピレンブロック共重合体
[(株)プライムポリマー製プライムポリプロJ-702LJ]
発明例15~17:
MFR=1.6g/10分のプロピレン単独重合体40重量部
MFR=0.54g/10分のプロピレンブロック共重合体20重量部
[(株)プライムポリマー製 プライムポリプロB-150M]
MFR=55.0g/10分のプロピレンブロック共重合体40重量部
[(株)プライムポリマー製プライムポリプロJ-739EP]
比較例24の発泡性樹脂:発明例1~14の発泡性樹脂と同じ。
比較例25の発泡性樹脂:発明例15の発泡性樹脂と同じ。
比較例26の発泡性樹脂:発明例16の発泡性樹脂と同じ。
比較例27の発泡性樹脂:MFR=54g/10分のプロピレンブロック共重合体
[(株)プライムポリマー製プライムポリプロJ-739E]
はじめに、積層板1を、長さ180mm、幅110mmの試験片に切った。そして、直径101.6mmの球状張出しパンチを用い、潤滑剤としてR-303Pを用いて、しわ押え圧力200kN、パンチ速度240mm/分で張出し成形し、試験片が割れるときの高さ(mm)を求め、割れ限界成形高さ試験を行った。各サンプルに対して3回の試験を行い、その平均値を採用した。割れ限界成形高さが大きい程、張出し成形性に優れていることを意味し、例えば、前記した各用途の自動車用成形パネルに要求される張出し成形性を満足するためには、15mm以上であればよい。
形状安定性は、張出し成形した成形品を、除荷して放置した際のバックリング量を目視にて評価し、バックリング量が大きいものを×、小さいものを○として評価した。
Claims (5)
- 芯材発泡性ポリプロピレン系樹脂の両面にアルミニウム合金板が各々積層されてなり、成形後に前記芯材発泡性ポリプロピレン系樹脂を加熱により発泡させて複合成形体とする積層板であって、
この積層板全体の板厚が3.4mm以下であり、
前記アルミニウム合金板の板厚が0.05~1.0mmであるとともに、前記芯材発泡性ポリプロピレン系樹脂の板厚が0.5~1.4mmであり、
前記アルミニウム合金板が、JISH0001規格にて規定される質別記号で、O材、H22材~H24材、H32材~H34材及びT4材のうちから選択される調質処理材であることを特徴とする積層板。 - 前記積層板全体の板厚が2.4mm以下であり、
前記アルミニウム合金板の板厚が0.05~0.5mmであるとともに、前記芯材発泡性ポリプロピレン系樹脂の板厚が0.5~1.4mmであることを特徴とする請求項1に記載の積層板。 - 前記積層板の前記アルミニウム合金板が、1000系、3000系、5000系、6000系のアルミニウム合金のうちから選択されることを特徴とする請求項1に記載の積層板。
- 前記積層板の前記芯材発泡性ポリプロピレン系樹脂は、メルトフローレート(MFR、ASTM D1238、230℃、2.16Kg荷重)が0.1~50g/10分の範囲であるポリプロピレン系樹脂であり、該ポリプロピレン系樹脂は、ランダム共重合ポリプロピレン系樹脂、ホモポリプロピレン系樹脂、及びブロックポリプロピレン系樹脂のうち、少なくとも一種以上からなることを特徴とする請求項1に記載の積層板。
- 請求項1に記載の積層板を冷間にて成形した後に、加熱により前記芯材発泡性ポリプロピレン系樹脂を発泡させたことを特徴とする複合成形体。
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Also Published As
Publication number | Publication date |
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CN102149541A (zh) | 2011-08-10 |
US8722200B2 (en) | 2014-05-13 |
CN102149541B (zh) | 2016-06-01 |
US20110159261A1 (en) | 2011-06-30 |
JP2010064307A (ja) | 2010-03-25 |
JP4559513B2 (ja) | 2010-10-06 |
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