WO2015146846A1 - かしめ部を有する繊維強化樹脂接合体、及びその製造方法 - Google Patents
かしめ部を有する繊維強化樹脂接合体、及びその製造方法 Download PDFInfo
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- WO2015146846A1 WO2015146846A1 PCT/JP2015/058533 JP2015058533W WO2015146846A1 WO 2015146846 A1 WO2015146846 A1 WO 2015146846A1 JP 2015058533 W JP2015058533 W JP 2015058533W WO 2015146846 A1 WO2015146846 A1 WO 2015146846A1
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- fiber
- reinforced resin
- joined body
- fibers
- caulking
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
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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
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/74—Joining plastics material to non-plastics material
- B29C66/742—Joining plastics material to non-plastics material to metals or their alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/30—Vehicles, e.g. ships or aircraft, or body parts thereof
- B29L2031/3002—Superstructures characterized by combining metal and plastics, i.e. hybrid parts
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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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—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
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- 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
- B32B2605/00—Vehicles
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16B—DEVICES FOR FASTENING OR SECURING CONSTRUCTIONAL ELEMENTS OR MACHINE PARTS TOGETHER, e.g. NAILS, BOLTS, CIRCLIPS, CLAMPS, CLIPS OR WEDGES; JOINTS OR JOINTING
- F16B17/00—Connecting constructional elements or machine parts by a part of or on one member entering a hole in the other and involving plastic deformation
- F16B17/008—Connecting constructional elements or machine parts by a part of or on one member entering a hole in the other and involving plastic deformation of sheets or plates mutually
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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.]
- Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
- Y10T428/24322—Composite web or sheet
- Y10T428/24331—Composite web or sheet including nonapertured component
- Y10T428/24339—Keyed
-
- 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.]
- Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
- Y10T428/24322—Composite web or sheet
- Y10T428/24331—Composite web or sheet including nonapertured component
- Y10T428/24339—Keyed
- Y10T428/24347—From both sides
Definitions
- the present invention relates to a fiber reinforced resin joined body including a reinforced fiber and a thermoplastic resin, and a manufacturing method thereof. More specifically, the present invention relates to a fiber-reinforced resin joined body having a caulking portion and good joining strength, and a method for producing the joined body, and can be suitably used for structural parts represented by automobiles.
- a fiber reinforced resin material when caulked, it has a tensile elastic modulus superior to that of general-purpose resins. Base material destruction depends on the strength and thickness of the base material.
- the umbrella portion breakage is a breakage due to the shearing force inside the shaft in a direction parallel to the shaft, and how to maintain the excellent shear strength is a design factor.
- An object of the present invention is to provide a novel fiber-reinforced resin joined body having excellent joining strength.
- an object of the present invention is to provide a fiber-reinforced resin joined body excellent in joining strength in a direction perpendicular to the joined part (joining surface) of two joined members (joint surface).
- Another object of the present invention is to provide a method for producing a fiber-reinforced resin joined body that can be produced efficiently in a short time because there is little energy loss due to joining.
- the present inventors obtain a target fiber-reinforced resin joined body by controlling the buckling strength of the protrusion used for caulking.
- the present invention has been found.
- the present invention is as follows.
- a fiber reinforced resin joined body configured to include a protrusion portion of the fiber reinforced resin molded body A penetrating through a through hole of the member B, and a caulked portion protruding from the through hole.
- a fiber-reinforced resin joined body characterized by comprising: [2] The fiber-reinforced resin joined body according to [1], wherein the tensile elastic modulus of the fiber-reinforced resin molded body A is in a range of 15 to 35 GPa.
- the protruding portion of the fiber reinforced resin molded article A containing at least one protruding portion containing a reinforcing fiber and a thermoplastic resin and having a buckling stress in the range of 80 to 450 MPa has at least one through hole.
- a method for manufacturing a fiber-reinforced resin joined body which includes a step of inserting into the through-hole of the member B and projecting the tip end portion of the protrusion from the through-hole, and a step of caulking the projecting tip portion.
- the step of caulking includes the step of pressurizing while heating the tip, and the method for producing a fiber-reinforced resin joined body according to [10].
- the fiber-reinforced resin joined body of the present invention has excellent joining strength in the peel direction even when the joining time is short.
- the fiber-reinforced resin joined body is suitable for use as a structural material for vehicles typified by automobiles and efficient. Manufacturing can be carried out.
- a fiber reinforced resin joined body can be manufactured efficiently in a short time.
- FIG. 1 is a schematic view showing a cross section of an example of the fiber-reinforced resin joined body of the present invention.
- the fiber-reinforced resin joined body of the present invention includes a fiber-reinforced resin molded body A containing at least one protrusion containing a reinforcing fiber and a thermoplastic resin and having a buckling stress in the range of 80 to 450 MPa, and at least A fiber reinforced resin joined body configured to include a member B having one through hole, wherein the protrusion of the fiber reinforced resin molded body A passes through the through hole of the member B, and A caulking portion is provided at a portion protruding from the through hole.
- the fiber reinforced resin molded product A is a molded product in which reinforced fibers are contained in a matrix made of a thermoplastic resin. Details will be described later.
- the type of the member B is not particularly limited as long as it has at least one through hole, and examples thereof include metals, resins, and ceramics.
- the metal include iron, aluminum, copper, titanium, and alloys thereof.
- the resin there are a synthetic resin and a non-synthetic resin (natural polymer), and any of a thermoplastic resin and a thermosetting (type) resin can be used as the synthetic resin.
- thermoplastic resins include general-purpose plastics such as polyethylene, polyvinyl chloride, polystyrene, ABS, acrylic resin, engineering such as polyamide, polycarbonate, polyphenylene ether, polyester (PET, PBT, etc.) and cyclic polyolefin (COP).
- thermosetting resin examples include epoxy resin, phenol resin, unsaturated polyester resin, melamine resin, urea resin, and curable polyimide resin.
- the resin may contain inorganic fibers such as glass fibers and carbon fibers, and organic fibers such as aramid fibers, polyester fibers, and polyamide fibers as reinforcing fibers.
- the member B is preferably at least one member selected from the group consisting of metals, resins, and resins containing reinforcing fibers. From the viewpoint of the balance between mechanical properties and light weight, the member B is a fiber reinforced resin molding. Similarly to the body A, it is preferably a fiber reinforced resin molded body containing reinforced fibers and a thermoplastic resin as a matrix, and the thermoplastic resin in the member B is contained in the fiber reinforced resin molded body A. More preferably, it is the same type of thermoplastic resin as the thermoplastic resin, and more preferably the same fiber-reinforced resin molded body as the fiber-reinforced resin molded body A described in detail below.
- the fiber reinforced resin molded product B including the reinforcing fiber as the member B and the thermoplastic resin as the matrix will be described as an example.
- the fiber reinforced resin molded products A and B used in the present invention comprise reinforcing fibers and a thermoplastic resin.
- a thermoplastic resin is used as a matrix, and reinforcing fibers are contained in the matrix.
- the reinforcing fiber contained in the fiber reinforced resin molded product A may be the same as or different from the reinforced fiber contained in the fiber reinforced resin molded product B depending on the purpose. Often it is convenient to be the same.
- the thermoplastic resin contained in the fiber reinforced resin molded product A may be the same as or different from the thermoplastic resin contained in the fiber reinforced resin molded product B. In many cases, it is convenient to be the same.
- the abundance (content) of the matrix in the fiber reinforced resin molded products A and B can be appropriately determined according to the type of matrix and the type of reinforcing fiber described below, and is not particularly limited. However, it is usually in the range of 3 to 1000 parts by mass with respect to 100 parts by mass of the reinforcing fibers. More preferred is 30 to 200 parts by mass, and still more preferred is 30 to 150 parts by mass.
- the matrix is less than 3 parts by mass with respect to 100 parts by mass of the reinforcing fibers, dry reinforcing fibers that are insufficiently impregnated in the production process described below may increase.
- the amount exceeds 1000 parts by mass the amount of reinforcing fibers is so small that it is often inappropriate as a structural material.
- the ratio of the matrix and the reinforcing fiber may be the same or different depending on the application.
- the fiber reinforced resin molded product A is, for example, a flat plate, a prism, a polyhedron, etc., having a flat part and a cross section of a polygon such as a quadrangle, and usually on the flat part with respect to the flat part. It is preferable to have a protrusion having a buckling stress in the range of 80 to 450 MPa in the vertical direction. Although the thickness of the said plane part may be the same or different, it is good that it is the same at the point of mechanical strength. The thickness of the flat portion is preferably in the range of 1 to 20 mm. Further, when the fiber reinforced resin molded product A is a flat plate, the thickness of the flat plate may be constant or different within a range of 1 to 20 mm.
- the fiber-reinforced resin molded body B is, for example, a flat plate, a prism, a polyhedron, etc., having a flat portion and a cross section of a polygon such as a quadrangle, and usually in the flat portion with respect to the flat portion. It is preferable to have at least one through hole in the vertical direction.
- the thickness of the fiber reinforced resin molded product B around the through hole is preferably in the range of 1 to 20 mm. Further, when the fiber reinforced resin molded product B is a flat plate, the thickness of the flat plate may be constant or different within a range of 1 to 20 mm.
- the type of reinforcing fiber used in the present invention can be appropriately selected according to the type of matrix, the use of the fiber-reinforced resin joined body of the present invention, and the like, and is not particularly limited. For this reason, as the reinforcing fiber used in the present invention, any of inorganic fibers and organic fibers can be preferably used.
- the inorganic fibers include carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers, silicon carbide fibers (silicon carbide fibers), ceramic fibers, alumina fibers, natural fibers, mineral fibers such as basalt, and boron fibers. , Boron nitride fiber, boron carbide fiber, and metal fiber.
- the metal fiber include aluminum fiber, copper fiber, brass fiber, stainless steel fiber, and steel fiber.
- As said glass fiber what consists of E glass, C glass, S glass, D glass, T glass, quartz glass fiber, borosilicate glass fiber, etc. can be mentioned.
- organic fibers examples include fibers made of resin materials such as aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate.
- resin materials such as aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate.
- two or more kinds of reinforcing fibers may be used in combination.
- a plurality of types of inorganic fibers may be used in combination
- a plurality of types of organic fibers may be used in combination
- inorganic fibers and organic fibers may be used in combination.
- the mode in which a plurality of types of organic fibers are used in combination include a mode in which aramid fibers and fibers made of other organic materials are used in combination.
- the aspect which uses together a carbon fiber and an aramid fiber can be mentioned, for example.
- carbon fibers as the reinforcing fibers. This is because the carbon fiber can obtain the fiber-reinforced resin joined body of the present invention that is lightweight and excellent in strength.
- the carbon fibers are generally polyacrylonitrile (PAN) based carbon fibers, petroleum / coal pitch based carbon fibers, rayon based carbon fibers, cellulosic carbon fibers, lignin based carbon fibers, phenol based carbon fibers, and vapor growth systems. Although carbon fiber etc. are known, in the present invention, any of these carbon fibers can be suitably used.
- the present invention it is preferable to use polyacrylonitrile (PAN) -based carbon fiber in terms of excellent tensile strength.
- PAN polyacrylonitrile
- the tensile elastic modulus is preferably in the range of 100 to 600 GPa, more preferably in the range of 200 to 500 GPa, and in the range of 230 to 450 GPa. Is more preferable.
- the tensile strength is preferably in the range of 2000 to 10000 MPa, more preferably in the range of 3000 to 8000 MPa.
- the reinforcing fiber used in the present invention may have a sizing agent attached to the surface.
- the type of the sizing agent can be appropriately selected according to the type of the reinforcing fiber and the matrix, and is not particularly limited.
- the form of the reinforcing fiber used in the present invention is not particularly limited, and may be, for example, a woven fabric, a knitted fabric, a unidirectional material, a continuous fiber, a discontinuous fiber having a specific length, or a combination thereof.
- the fiber reinforced resin molded product A having the protrusions it is preferable to use reinforcing fibers in a form in which the reinforcing fibers are easily contained in the protrusions in a single molding.
- the form of the reinforcing fiber contained in the fiber reinforced resin molded products A and B in the present invention may be the same or different.
- the fiber length of the reinforcing fiber used in the present invention can be appropriately determined according to the type of the reinforcing fiber, the type of the matrix, the orientation state of the reinforcing fiber in the fiber reinforced resin molded products A and B, and the like. It is not particularly limited. Therefore, in the present invention, continuous fibers may be used or discontinuous fibers may be used depending on the purpose. Alternatively, a combination of continuous fibers and discontinuous fibers may be used. When discontinuous fibers are used, the average fiber length is usually preferably in the range of 0.1 mm to 500 mm, and particularly preferably in the range of 1 mm to 100 mm.
- the average fiber lengths of the reinforcing fibers contained in the fiber reinforced resin molded products A and B in the present invention may be the same or different.
- injection molding and compression molding press molding
- the length of the reinforcing fibers contained in the molding material is preferably in the range of 0.1 to 10 mm.
- the reinforcing fibers contained in the molding material preferably sheet material
- One sheet material may be used, or a plurality of sheet materials may be laminated.
- reinforcing fibers having different fiber lengths may be used in combination.
- the reinforcing fiber used in the present invention may have a single peak in the fiber length distribution or may have a plurality of peaks.
- the average fiber length of the reinforced fibers is obtained, for example, by measuring the fiber length of 100 fibers randomly extracted from the fiber reinforced resin molded products A and B to the 1 mm unit using a caliper or the like, and obtaining it based on the following formula: be able to. Extraction of the reinforced fibers from the fiber reinforced resin molded products A and B is performed by, for example, subjecting the fiber reinforced resin molded products A and B to a heat treatment of about 500 ° C. ⁇ 1 hour and removing the resin in the furnace.
- Weight average fiber length: Lw ( ⁇ Li 2 ) / ( ⁇ Li)
- the number average fiber length and the weight average fiber length are the same value.
- either the number average fiber length or the weight average fiber length may be adopted, but it is often the weight average fiber length that can more accurately reflect the physical properties of the fiber reinforced resin material.
- the fiber diameter of the reinforcing fiber used in the present invention may be appropriately determined according to the type of the reinforcing fiber, and is not particularly limited.
- the average fiber diameter is usually preferably in the range of 3 ⁇ m to 50 ⁇ m, more preferably in the range of 4 ⁇ m to 12 ⁇ m, and in the range of 5 ⁇ m to 8 ⁇ m. More preferably.
- the average fiber diameter is usually preferably in the range of 3 to 30 ⁇ m.
- the said average fiber diameter shall point out the diameter of the single yarn of a reinforced fiber.
- the reinforcing fiber when the reinforcing fiber is in the form of a fiber bundle, it refers to the diameter of the reinforcing fiber (single yarn) constituting the fiber bundle, not the diameter of the fiber bundle.
- the average fiber diameter of the reinforcing fibers can be measured by, for example, a method described in JIS R7607: 2000.
- the reinforcing fiber used in the present invention may be in the form of a single yarn consisting of a single yarn, or in the form of a fiber bundle consisting of a plurality of single yarns.
- the reinforcing fiber used in the present invention may be only a single yarn, may be a fiber bundle, or a mixture of both.
- the fiber bundle shown here indicates that two or more single yarns are close to each other by a sizing agent or electrostatic force. When a fiber bundle is used, the number of single yarns constituting each fiber bundle may be substantially uniform or different in each fiber bundle.
- the number of single yarns constituting each fiber bundle is not particularly limited, but is usually in the range of 10 to 100,000.
- carbon fibers are in the form of fiber bundles in which thousands to tens of thousands of filaments are gathered.
- the entangled portions of the fiber bundles are locally thick and it may be difficult to obtain thin fiber reinforced resin molded products A and B.
- this invention when using a carbon fiber as a reinforced fiber, it is good to use it by widening or opening the carbon fiber bundle.
- the degree of widening and the degree of opening of the reinforcing fibers contained in the fiber reinforced resin molded products A and B in the present invention may be the same or different.
- the opening degree of the fiber bundle after opening is not particularly limited, but the opening degree of the fiber bundle is controlled, and a specific number or more of carbon fibers are controlled. It is preferable that the carbon fiber bundle which consists of, and the carbon fiber (single yarn) and / or carbon fiber bundle of less than that are included.
- the carbon fiber bundle (A) constituted by the number of critical single yarns or more defined by the following formula (1) and the other opened carbon fibers, that is, the state of the single yarn or the criticality It is preferably composed of a fiber bundle composed of less than the number of single yarns.
- Critical number of single yarns 600 / D (1) (Where D is the average fiber diameter ( ⁇ m) of the carbon fiber)
- the critical single yarn number defined by the above formula (1) is 86 to 120.
- a carbon fiber bundle having a number exceeding the critical number of single yarns is excellent in self-supporting property, and thus can be a suitable reinforcing material having excellent handling properties and excellent fluidity during molding.
- carbon fiber bundles composed of a number less than the critical number of single yarns are often cotton-like because of their low self-supporting properties. For this reason, handling properties and fluidity during molding tend to be reduced.
- the ratio of the carbon fiber bundle (A) to the total amount of carbon fibers in the fiber reinforced resin molded product A or B or both is preferably more than 0 Vol% and less than 99 Vol%, and more than 20 Vol% and less than 99 Vol% It is more preferable that it is 30 Vol% or more and less than 95 Vol%, and it is most preferable that it is 50 Vol% or more and less than 90 Vol%.
- the fiber reinforced resin molded product A or B or both by coexisting a carbon fiber bundle composed of carbon fibers of a specific number or more and other opened carbon fibers or carbon fiber bundles in a specific ratio. This is because it is possible to increase the abundance of carbon fibers in the inside, that is, the fiber volume content (Vf).
- the degree of carbon fiber opening can be set within the target range by adjusting the fiber bundle opening conditions. For example, when the fiber bundle is opened by blowing air onto the fiber bundle, the degree of opening can be adjusted by controlling the pressure of the air blown onto the fiber bundle. In this case, by increasing the air pressure, the degree of opening is increased (the number of single yarns constituting each fiber bundle is small), and by reducing the air pressure, the degree of opening is reduced (constituting each fiber bundle). The number of single yarns to be increased).
- the average number of fibers (N) in the carbon fiber bundle (A) can be appropriately determined within a range not impairing the object of the present invention, and is particularly limited. It is not a thing.
- the above N is usually preferably in the range of 1 ⁇ N ⁇ 12000, and more preferably satisfies the following formula (2). 0.6 ⁇ 10 4 / D 2 ⁇ N ⁇ 1.0 ⁇ 10 5 / D 2 (2) (Where D is the average fiber diameter ( ⁇ m) of the carbon fiber)
- the average number of fibers in the carbon fiber bundle (A) is in the range of 240 to less than 4000, and preferably 300 to 2500. More preferably, it is 400 to 1600. Further, when the average fiber diameter of the carbon fibers is 7 ⁇ m, the average number of fibers in the carbon fiber bundle (A) is in the range of 122 to 2040, preferably 150 to 1500, more preferably 200. ⁇ 800.
- the average number of fibers (N) in the carbon fiber bundle (A) is 0.6 ⁇ 10 4 / D 2 or less, it becomes difficult to obtain a fiber having a high reinforcing fiber volume content (Vf), and has excellent strength. It becomes difficult to obtain a fiber-reinforced resin molded article having the same. Further, when the average number of fibers (N) in the carbon fiber bundle (A) is 1.0 ⁇ 10 5 / D 2 or more, a locally thick portion is generated, which tends to cause voids. Furthermore, the fiber reinforced resin molded product that satisfies the above requirements has the advantage that it can be easily obtained as a fiber reinforced resin molded product A that forms a convex portion on the surface.
- the number of critical fibers and the average number of fibers (N) in the carbon fiber bundle (A) of the reinforcing fibers contained in the fiber-reinforced resin molded product A or B or both in the present invention are the same or different. May be.
- the ratio of the carbon fiber bundle having a thickness of 100 ⁇ m or more in the fiber reinforced resin molded body is less than 3% of the total number of carbon fiber bundles (A). preferable. If the carbon fiber bundle having a thickness of 100 ⁇ m or more is less than 3%, it is preferable because the thermoplastic resin is easily impregnated into the fiber bundle. More preferably, the proportion of carbon fiber bundles having a thickness of 100 ⁇ m or more is less than 1%. In order to make the proportion of carbon fiber bundles having a thickness of 100 ⁇ m or more less than 3%, it is possible to control by widening the fibers used and using thin fibers.
- thermoplastic resins and thermosetting resins are known as typical matrices used for fiber reinforced resin molded products.
- a thermoplastic resin is used as a matrix constituting the fiber reinforced resin molded product A.
- a thermosetting resin may be used in combination as long as the main component is a thermoplastic resin.
- the thermoplastic resin is not particularly limited, and has a desired softening point or melting point while considering excellent mechanical properties and productivity according to the use of the fiber-reinforced resin joined body of the present invention. It can be appropriately selected and used.
- the thermoplastic resin those having a softening point in the range of 180 ° C. to 350 ° C. are usually used, but are not limited thereto.
- thermoplastic resin examples include polyolefin resin, polystyrene resin, thermoplastic polyamide resin, polyester resin, polyacetal resin (polyoxymethylene resin), polycarbonate resin, (meth) acrylic resin, polyarylate resin, polyphenylene ether resin, polyimide
- thermoplastic resin examples include resins, polyether nitrile resins, phenoxy resins, polyphenylene sulfide resins, polysulfone resins, polyketone resins, polyether ketone resins, thermoplastic urethane resins, fluorine resins, and thermoplastic polybenzimidazole resins.
- polyolefin resin examples include polyethylene resin, polypropylene resin, polybutadiene resin, polymethylpentene resin, vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, and polyvinyl alcohol resin.
- polystyrene resin examples include polystyrene resin, acrylonitrile-styrene resin (AS resin), acrylonitrile-butadiene-styrene resin (ABS resin), and the like.
- polyamide resin examples include polyamide 6 resin (nylon 6), polyamide 11 resin (nylon 11), polyamide 12 resin (nylon 12), polyamide 46 resin (nylon 46), polyamide 66 resin (nylon 66), and polyamide 610. Resin (nylon 610) etc. can be mentioned.
- polyester resin examples include polyethylene terephthalate resin, polyethylene naphthalate resin, boribylene terephthalate resin, polytrimethylene terephthalate resin, and liquid crystal polyester.
- Examples of the (meth) acrylic resin include polymethyl methacrylate.
- Examples of the modified polyphenylene ether resin include modified polyphenylene ether.
- Examples of the thermoplastic polyimide resin include thermoplastic polyimide, polyamideimide resin, polyetherimide resin, and the like.
- Examples of the polysulfone resin include a modified polysulfone resin and a polyethersulfone resin.
- Examples of the polyetherketone resin include polyetherketone resin, polyetheretherketone resin, and polyetherketoneketone resin.
- fluororesin, polytetrafluoroethylene etc. can be mentioned, for example.
- thermoplastic resin used in the present invention may be only one type or two or more types.
- modes in which two or more types of thermoplastic resins are used in combination include modes in which thermoplastic resins having different softening points or melting points are used in combination, modes in which thermoplastic resins having different average molecular weights are used in combination, and the like. However, this is not the case.
- various fibrous or non-fibrous fillers of organic fibers or inorganic fibers, flame retardants, UV-resistant agents are provided within the range not impairing the object of the present invention.
- Stabilizers, release agents, pigments, softeners, plasticizers, surfactants and other additives may be included.
- the adhesion strength between the reinforcing fiber and the thermoplastic thermoplastic resin is preferably 5 MPa or more in the strand tensile shear test.
- this strength is a method of changing the surface oxygen concentration ratio (O / C) of the carbon fiber, or a method of increasing the adhesion strength between the carbon fiber and the matrix by adding a sizing agent to the carbon fiber. Can be improved.
- thermoplastic resin used as the matrix exhibits high water absorption
- the temperature of the thermoplastic resin to be heated at the time of molding is preferably a melting temperature + 15 ° C. or higher and a decomposition temperature ⁇ 30 ° C. or lower. If the heating temperature is below that range, the resin will not melt, making it difficult to mold, and if it exceeds that range, decomposition of the resin may proceed.
- a conventionally known method can be used.
- long fiber pellets that is, molten thermoplastic resin is adjusted to a predetermined viscosity, impregnated into continuous fibrous reinforcing fibers, and then cut.
- the method of manufacturing to a predetermined shape with an injection molding machine using the pellet obtained at the process is mentioned.
- a base material such as a unidirectionally arranged sheet (UD sheet) in which continuous fiber strands are aligned in parallel, a woven fabric, discontinuous reinforcing fibers, and the like is placed in a mold, and then heated.
- a method of cooling after injecting and impregnating a thermoplastic resin and injecting and impregnating a thermoplastic resin heated and melted may be mentioned.
- die with a reinforced fiber, heating, and pressing as a thermoplastic resin is also mentioned.
- prescribed temperature, and pressing is also preferable.
- the heating temperature is preferably in the range of the melting temperature of the thermoplastic resin + 15 ° C. or higher and the decomposition temperature ⁇ 30 ° C. or lower.
- a base material contained in a woven fabric, a knitted fabric, a UD material, a papermaking sheet or a reinforcing fiber mat is laminated in a single layer or a plurality of layers and heated and pressed.
- thermoplastic resin may be supplied at the time of manufacturing the reinforcing fiber mat, but after the manufacturing of the reinforcing fiber mat, a layer made of a thermoplastic resin (film, nonwoven fabric) on at least one surface of the reinforcing fiber mat. , Sheets, etc.), these are heated and pressed, and the reinforcing fiber mat is impregnated with a thermoplastic resin. That is, the above-mentioned fiber reinforced resin molded article is manufactured by once forming two or more kinds of the same or different base materials by press molding, and further laminating other same or different base materials or layers and press-molding them again. May be.
- the reinforcing fiber mat includes a thermoplastic resin.
- the reinforcing fiber mat includes a powdery, fibrous, or massive thermoplastic resin, or the reinforcing fiber mat includes a thermoplastic resin.
- stacked can be mentioned.
- the thermoplastic resin layer may be formed by depositing a powdery, fibrous, or lump-shaped thermoplastic resin, or may be formed of a sheet-like or film-like thermoplastic resin. Good.
- the above-mentioned reinforcing fiber mat means a sheet-like or mat-like shape in which reinforcing fibers are deposited or entangled.
- Reinforcing fiber mats include two-dimensional isotropic reinforcing fiber mats in which the long axis direction of the reinforcing fibers is randomly dispersed in the in-plane direction, and the long axis direction of the reinforcing fibers is entangled in a cotton shape. Examples thereof include a three-dimensional isotropic reinforcing fiber mat that is randomly dispersed in each direction of XYZ.
- the base material may include reinforcing fibers having different arrangement states in one base material.
- the reinforcing fibers having different arrangement states are included in one base material, for example, (i) an aspect in which reinforcing fibers having different arrangement states are arranged in the in-plane direction of the base material, (ii) the base material
- positioned can be mentioned.
- a base material has the laminated structure which consists of a some layer, the aspect from which the arrangement state of the reinforcement fiber contained in each layer (iii) differs can be mentioned.
- an embodiment in which the above embodiments (i) to (iii) are combined can also be exemplified.
- the orientation state of the reinforcing fibers in the present invention may be either the one-way arrangement or the two-dimensional random dispersion. Further, it may be an irregular arrangement intermediate between the one-directional arrangement and the two-dimensional random dispersion (a dispersion state in which the long axis directions of the reinforcing fibers are not arranged completely in one direction and are not completely random).
- the reinforcing fiber may be dispersed so that the long axis direction of the reinforcing fiber has an angle with respect to the in-plane direction of the entire base material, and the fibers are arranged so as to be intertwined in a cotton shape.
- the fibers may be dispersed as in bi-directional woven fabrics such as plain weave and twill weave, multi-axial woven fabrics, non-woven fabrics, mats, knits, braids, paper made of reinforced fibers, and the like.
- the reinforcing fibers are arranged two-dimensionally randomly on the surface of at least one of the above-mentioned base materials, particularly the surface having the protrusions, from the viewpoint of moldability. It is preferable.
- the orientation mode of the reinforcing fiber in the base material is, for example, a tensile test based on an arbitrary direction of the base material and a direction orthogonal thereto, and after measuring the tensile elastic modulus, the value of the measured tensile elastic modulus It can be confirmed by measuring a ratio (E ⁇ ) obtained by dividing a larger one by a smaller one. It can be evaluated that the closer the modulus ratio is to 1, the more reinforced fibers are two-dimensionally dispersed. It is said to be isotropic when the ratio of the modulus of elasticity in two orthogonal directions divided by the smaller one does not exceed 2, and isotropic when this ratio does not exceed 1.3. Rated as excellent.
- a base material in the present invention when such a base material having excellent isotropy (isotropic base material) is used, it is excellent in moldability, shaping followability to a mold, mechanical characteristics, etc. Since the joined_body
- the orientation aspect of the reinforced fiber in the case of using an isotropic substrate is also maintained in the fiber reinforced resin molded body in the present invention.
- Basis weight of the reinforcing fibers in the substrate is not particularly limited, it is usually, 25g / m 2 ⁇ 10000g / m 2.
- the thickness of the substrate used in the present invention is not particularly limited, but is usually preferably in the range of 0.01 mm to 100 mm, preferably in the range of 0.01 mm to 10 mm, and in the range of 0.1 to 5 mm. The inside is more preferable.
- the said thickness does not point out the thickness of each layer, but shall refer to the thickness of the whole base material which totaled the thickness of each layer. .
- the substrate used in the present invention may have a single layer structure composed of a single layer, or may have a laminated structure in which a plurality of layers are laminated.
- the aspect in which the base material has the laminated structure may be an aspect in which a plurality of layers having the same composition are laminated, or an aspect in which a plurality of layers having different compositions are laminated. Good.
- the aspect in which the base material has the laminated structure may be an aspect in which layers having mutually different reinforcing fiber arrangement states are laminated.
- a mode for example, a mode in which a layer in which reinforcing fibers are unidirectionally arranged and a layer in which reinforcing fibers are two-dimensionally randomly arranged can be exemplified.
- a sandwich structure including an arbitrary core layer and a skin layer laminated on the front and back surfaces of the core layer may be used.
- the fiber reinforced resin molded products A and B in the present invention are preferably produced by a method of press molding using the above isotropic base material, and are excellent in productivity and isotropic.
- An isotropic base material is press-molded by heat compression, and then a plate-like precursor (A ′, B ′) of easy-to-handle fiber reinforced resin molded products A, B is first manufactured by cooling or the like.
- a plate-like precursor A ′, B ′
- these precursors may be heated and laminated or heated after lamination, and then press-molded again to produce fiber reinforced resin molded products A and B having a desired thickness, shape, and surface properties.
- the above isotropic substrates or precursors are softened by heating to a temperature of the softening point of the thermoplastic resin constituting them + 30 ° C. to 100 ° C., and then placed in a mold and pressed. At that time, it is preferable to apply a pressure of 0.1 to 20 MPa, preferably 0.2 to 15 MPa, and more preferably 0.5 to 10 MPa as a pressurizing condition. When the pressure is less than 0.1 MPa, the isotropic substrate or the precursor may not be sufficiently pushed out, and a springback or the like may occur and the mechanical strength of the fiber reinforced resin molded product may be lowered.
- the temperature in the mold depends on the type of the thermoplastic resin, but since the molten thermoplastic resin is cooled and solidified, a fiber reinforced resin molded product is formed.
- the resin is crystalline, it is preferably 20 ° C. or less from the crystal melting temperature, and when the resin is amorphous, the glass transition temperature.
- the temperature is usually 120 to 180 ° C, preferably 125 to 170 ° C, and more preferably 130 to 160 ° C.
- a specific example of the method for producing the fiber reinforced resin molded products A and B in the present invention is shown below. 1) a step of cutting the reinforcing fiber, 2) opening the cut reinforcing fiber, 3) A step of obtaining a reinforced fiber resin molded body precursor by heating and compressing after mixing the opened reinforcing fiber and a fibrous or particulate thermoplastic resin serving as a matrix to form an isotropic substrate, 4) Step of molding the precursor
- strands made of a plurality of carbon fibers are continuously slit along the fiber length direction as necessary to form a plurality of narrow strands having a width of 0.05 to 5 mm.
- the carbon fibers are continuously cut to an average fiber length of 3 to 100 mm, and the carbon fibers are deposited in layers on a breathable conveyor net or the like in a state where the cut carbon fiber bundles are blown with gas and opened. It is possible to obtain a reinforcing fiber mat that is randomly distributed randomly in the in-plane direction.
- thermoplastic resin is deposited on the breathable conveyor net almost simultaneously with the carbon fibers, or a molten thermoplastic resin is supplied in a film form on the carbon fiber layer of the mat.
- an isotropic substrate containing a thermoplastic resin can be produced.
- the carbon fiber bundle (A) in which the carbon fiber bundles are converged more than the critical single yarn number defined by the above formula (1) and the carbon fiber bundles less than the critical single yarn number (B 1 ) and / or carbon fiber monofilament (B 2 ) is mixed so that the ratio of the carbon fiber bundle (A) in the isotropic substrate to the total amount of carbon fibers is 20 to 99 Vol%, preferably 30 To 99 Vol%, particularly preferably 50 to 90 Vol%.
- the size of the fiber bundle to be subjected to the cutting step for example, the width of the bundle
- the size of the fiber bundle to be subjected to the cutting step for example, the width of the bundle
- the size of the fiber bundle to be subjected to the cutting step for example, the width of the bundle
- it can be controlled by adjusting the number of fibers per width.
- an isotropic substrate containing carbon fibers and a thermoplastic resin in a fibrous, particulate, or molten state can be obtained. Subsequently, it is excellent in productivity to produce by press molding using this isotropic substrate, and fiber reinforced resin molded products A and B excellent in in-plane isotropy can be produced. Further, as described above, the isotropic substrate is once heated to a temperature at which the thermoplastic resin melts, and then pressed to obtain a planar carbon fiber resin molded body precursor (A ′, B ′), and then The target carbon fiber resin molding may be manufactured by press molding again.
- the precursor (A ′, B ′) is obtained as a surface shape such as a sheet or a mat, but includes a material having a certain thickness.
- the carbon fibers are not oriented in a specific direction, and are in-plane isotropic in which the carbon fibers are dispersed and arranged in a random direction. It is a molded product.
- the isotropic property of the carbon fiber in the in-plane direction of the isotropic substrate is maintained.
- Such isotropy of the fiber reinforced resin joined body can be quantitatively evaluated by obtaining a ratio of tensile elastic moduli in two directions orthogonal to each other.
- the fiber reinforced resin molded product A used in the present invention has at least one protrusion. This protrusion is inserted into a penetration portion of member B described later, and a portion protruding above the penetration portion is caulked to form a caulking portion.
- the protrusions in the fiber reinforced resin molded product A have a buckling stress in the range of 80 to 450 MPa.
- buckling strength is less than 80 MPa, buckling occurs when caulking a portion of the protruding portion protruding from the penetrating portion of the member B (hereinafter sometimes referred to as a protruding portion), so that the caulking takes a short time.
- the unmelted portion (undeformed portion) of the protruding portion existing inside the caulking portion increases, and the bonding strength decreases.
- the buckling stress exceeds 450 MPa, the change in the shape of the protruding portion is reduced by caulking, and caulking in a short time becomes difficult, making it difficult to put it into practical use.
- a compression test can be obtained according to JIS K7181: 2011.
- the buckling stress of the protrusion is preferably in the range of 100 to 400 MPa, more preferably 110 to 350 MPa.
- the protruding portion of the fiber reinforced resin molded body A is inserted into the penetrating portion of the member B, and the portion protruding above the penetrating portion (the portion protruding above the fiber reinforced resin molded body A) is heated.
- the part of the shape deformed like an umbrella shape by being pressurized. Since this caulking portion is usually shaped like an umbrella, it may be referred to as an umbrella portion as described above.
- the method for controlling the buckling stress of the protrusion in the range of 80 to 450 MPa, but it can be achieved, for example, by controlling the diameter, height, and shape of the protrusion.
- the buckling stress tends to increase as the diameter of the protrusion increases and the height decreases. If the height of the protrusion is shortened, it becomes difficult to increase the volume of the caulking portion. Therefore, it is necessary to select an appropriate range according to the design. Also, the buckling stress tends to increase as the root becomes thicker than the tip of the protrusion.
- the shape of the protrusion is not particularly limited, and specific examples include a columnar shape, a conical shape, a prismatic shape, a pyramid shape, and a trapezoidal shape. Among them, a columnar shape, a conical shape, a pyramid shape, and a trapezoidal shape can be suitably used because the number of elements depending on the mold drawing angle during molding is reduced.
- the diameter is selected from the range of 4 to 12 mm
- the height of the portion protruding from the member B is preferably selected from the range of 6 to 15 mm.
- the protrusion part protrudes and squeezes from the penetration part of the fiber reinforced resin molded object B
- the protrusion part is In the case of a cylindrical shape, a range of 0.8 to 1.2 times the diameter of the cylinder is preferable.
- the buckling stress tends to increase as the tensile elastic modulus of the fiber-reinforced resin molded article increases.
- the tensile elastic modulus of the fiber reinforced resin molded product A is not particularly limited.
- the target buckling stress can be achieved by controlling the tensile elastic modulus in the range of 15 to 35 GPa.
- the range of the tensile elastic modulus of the fiber reinforced resin molded product A is more preferably 20 to 35 GPa.
- the said tensile elastic modulus For example, it is achieved by controlling the tensile elastic modulus of reinforcing fiber, the content of reinforcing fiber, the (average) fiber length of reinforcing fiber, and the fiber diameter of reinforcing fiber it can.
- the higher the tensile elastic modulus of the reinforcing fiber the higher the tensile elastic modulus of the fiber reinforced resin molded product A.
- the fluidity of the fiber reinforced resin molded product A during molding and caulking decreases. Therefore, it is necessary to select an appropriate range.
- the longer the fiber length of the reinforcing fiber and the smaller the fiber diameter of the reinforcing fiber the higher the tensile elastic modulus of the fiber-reinforced resin molded product A. If the fiber length is too long, the fiber-reinforced resin molding during molding and caulking is performed. Since the fluidity of the body A decreases, it is necessary to select an appropriate range.
- the fiber reinforced resin molded product A it is preferable that some or all of the plurality of reinforcing fibers included in the protrusions are included in the fiber reinforced resin molded product A other than the protrusions.
- the fact that part or all of the reinforcing fibers contained in the inside of the protruding portion is contained in the fiber reinforced resin molded product A other than the protruding portion means that the carbon fiber existing inside the protruding portion is such a protrusion. It is in a state of entering into a portion other than the portion (that is, the fiber reinforced resin molded product A excluding the protruding portion).
- the reinforcing fiber straddles (passes through) the bottom surface of the protrusion (the part obtained by horizontally cutting the root of the protrusion). That is, it is preferable that at least one reinforcing fiber among the reinforcing fibers exists over the protruding portion of the fiber-reinforced resin molded body A and the portion other than the protruding portion. More preferably, the reinforcing fiber in the fiber reinforced resin molded product A enters the protruding portion, and returns to the fiber reinforced resin molded product A again. Since this state leads to an improvement in strength at the base of the protrusion, it is suitable for increasing the buckling strength of the protrusion.
- Such a state can be confirmed, for example, by observing the cross section of the protrusion with a photograph or the like.
- a technique for causing some or all of the plurality of reinforcing fibers contained in the protrusions to be included in the fiber reinforced resin molded product A other than the protrusions as one of the techniques There is a method for controlling the fiber length of the reinforcing fiber. By increasing the fiber length of the reinforcing fiber to some extent, the reinforcing fiber can be included in the fiber-reinforced resin molded product A other than the protrusions.
- the reinforcing fiber easily enters the protruding portion, depending on the diameter of the protruding portion.
- the fiber length of the reinforcing fiber is 1 mm as a lower limit and 20 times the diameter of the protruding portion as an upper limit.
- the method for controlling the fluidity is not particularly limited. Specifically, the resin selection, the fiber length of the reinforcing fiber, the control of the fiber diameter, the control of the fiber bundle, the control of the addition amount of the reinforcing fiber, and molding.
- Examples include control of temperature and molding pressure.
- As a technique for increasing fluidity generally, the resin viscosity is decreased, the fiber length is shortened, the fiber diameter is increased, the fiber bundle is increased, the addition amount is decreased, the molding temperature is increased, and the molding pressure is increased. Will be raised.
- some of these methods lead to lowering the mechanical strength of the fiber-reinforced resin molded product, and therefore it is preferable to select them appropriately according to the design.
- limiting in particular as a method of providing a projection part in the fiber reinforced resin molded object A For example, the shape which forms a projection part beforehand in the metal mold
- Examples thereof include a method of heat-welding to A and bonding using an adhesive.
- the strength at the base of the protrusions is improved.
- the buckling strength of a projection part can be raised, it is a preferable method to integrally mold the fiber reinforced resin molding A and a projection part.
- the member B used in the present invention has at least one through hole.
- the size and shape of the through hole may be such that the protruding portion of the fiber reinforced resin molded product A can be completely inserted and protruded from the through hole to such an extent that it can be caulked.
- the shape of the through hole may be selected in accordance with the shape of the protrusion, and is preferably designed to be larger than the shape of the fiber reinforced resin molded product A.
- the method for obtaining the through hole is not particularly limited, but for example, a method of drilling with a drill, an end mill, a water jet, a laser, or the like, a portion that corresponds to the through hole in advance in the mold is pressed using a punching blade. Examples of the method include molding.
- the shape of the fiber-reinforced resin joined body of the present invention is not particularly limited.
- the fiber-reinforced resin joined body may be composed of a planar or rod-shaped fiber reinforced resin molded body A and a fiber reinforced resin molded body B of the same shape.
- the fiber reinforced resin molded body A may have two or more protrusions, and all of the protrusions may be inserted into the two or more through parts of the fiber reinforced resin molded body B and crimped.
- one protrusion of the fiber reinforced resin molded product A having one or more protrusions is one penetration in the fiber reinforced resin molded product B having one or more protrusions and one or more penetrations.
- the one or more protrusions of the fiber reinforced resin molded product B may be inserted and caulked into the penetrating portion of the third molded product.
- the cross tensile strength in the fiber-reinforced resin joined body of the present invention is preferably 1.5 kN or more.
- the cross tensile strength can be controlled in the same manner as the tensile elastic modulus of the fiber reinforced resin molded product A described above. It is preferable to use the above-described carbon fiber as the reinforcing fiber.
- the caulking portion in the fiber-reinforced resin joined body of the present invention is caulked by heating and compressing (the heating method will be described later).
- the caulking portion in the present invention includes a portion where the protruding portion derived from the protruding portion of the fiber reinforced resin molded body A melts and deforms into an umbrella shape, and a portion where the molten portion remains unmelted (undeformed portion, undissolved portion).
- the unmelted portion is a portion derived from the portion where the protruding portion protrudes from the through hole. That is, it is a portion of the protrusion that has not melted.
- the caulking portion has a ratio of the unmelted portion inside thereof, that is, the relationship between the length (L1) of the undeformed portion (unmelted portion) derived from the protruding portion inside the caulking portion and the height (L2) of the caulking portion.
- the following formula is preferably satisfied (see FIG. 1). 0 ⁇ L1 / L2 ⁇ 0.6 If the relationship between L1 and L2 is within the above range, it is possible to preferably use since there is a tendency to obtain excellent bonding strength.
- the method for controlling the length of the unmelted portion is not particularly limited. Specifically, there is a method for controlling the buckling stress of the protruding portion within the above-mentioned range or controlling the caulking conditions.
- the caulking conditions include the heating temperature of the protrusion, the pressure applied to the protrusion, and the caulking time, but the length of the unmelted portion increases as the caulking time is shortened by increasing the pressure applied to the protrusion. There is a tendency.
- the above relationship in the caulking portion more preferably satisfies the following formula. 0 ⁇ L1 / L2 ⁇ 0.5
- the caulking portions L1 and L2 can be obtained by caulking the caulking portion.
- the caulking portion in the fiber-reinforced resin joined body of the present invention has excellent mechanical characteristics because the protrusion of the fiber-reinforced resin molded body A has good buckling stress as described above. Therefore, when the caulking part is broken by applying a load, the umbrella part is often broken. In the case of umbrella fracture, the fracture state is shear fracture in a direction parallel to the axis, and the joint strength greatly depends on the amount of unmelted portion in the caulking portion. Since the fiber-reinforced resin joined body of the present invention is caulked as described above, it has excellent joint strength. However, depending on the application, the caulked portion may be further reinforced by other joining methods such as an adhesive. May be.
- the caulking portion is preferably in contact with the surface of the member B, but may not be in contact as long as the bonding strength can be maintained. Further, the protruding portion may or may not be in contact with the inner surface of the through hole of the member B.
- the fiber-reinforced resin joined body of the present invention is basically composed of a fiber-reinforced resin molded product A and a member B.
- One fiber-reinforced resin molded product A includes a reinforcing fiber and a thermoplastic resin as a matrix, and has at least one protrusion.
- the member B has at least one through hole, and preferably includes a reinforcing fiber and a thermoplastic resin as a matrix.
- the protruding portion of the fiber reinforced resin molded product A is inserted into the through hole of the member B, and the protruding portion (projecting portion) is caulked. When caulking, it is preferable to pressurize while heating the protrusion, and it can be manufactured by cooling and solidifying after the deformation is completed.
- the method of heating the protrusion includes a method of heating by contacting a heater such as a hot plate, a method of heating by infrared rays, and a method of heating by vibrating with ultrasonic waves.
- the method of heating with infrared rays can selectively heat the portion of the protruding portion that is desired to be deformed, and is suitable for controlling the length of the unmelted portion of the protruding portion.
- the method of heating with ultrasonic waves can be used preferably because it can be caulked in a short time. At this time, when fixing the position of the fiber reinforced resin molded product A and the member B and fixing the welding position, a jig called an anvil is often used.
- the umbrella shape of the caulking portion after caulking can be specifically determined by the shape of the jig used for caulking.
- the volume of the jig is determined by adjusting the volume of the protrusion used for caulking.
- the weldable portion of the protrusion is preferably 1.1 to 1.2 times the jig used for caulking.
- the fiber-reinforced resin joined body of the present invention may have one caulking portion, but may have two or more.
- each value in a present Example was calculated
- the cross tensile strength of the fiber reinforced resin joined body was determined in 1987 No. Measured according to 406-87. Specifically, the cross tensile strength was measured at a test piece size of 25 mm ⁇ 75 mm ⁇ 2.5 mm and a tensile speed of 5 mm / s.
- the buckling stress of the protrusion was measured by a compression test in accordance with JIS K7181: 2011.
- the tensile elastic modulus of the fiber reinforced resin molded product A was measured by a tensile test according to JIS K7161: 1994.
- the length (L1) of the undeformed portion (undissolved portion) of the projecting portion inside the caulking portion and the height (L2) of the caulking portion are determined based on the broken sample after the test described in (1) above. It measured with the caliper, and the ratio (L1 / L2) of the undissolved portion of the protruding portion inside the caulking portion was calculated.
- a slitter having a disk-shaped blade made of cemented carbide and arranged at intervals of 0.5 mm was used for the carbon fiber separating apparatus.
- a rotary cutter using a cemented carbide and a spiral knife arranged on the surface was used.
- the pitch of the blade was set to 20 mm, and the carbon fiber was cut to a fiber length of 20 mm.
- the strand that passed through the cutter was introduced into a flexible transportation pipe arranged directly under the rotary cutter, and subsequently introduced into a fiber opening device.
- the opening device nipples made of SUS304 having different diameters were welded to produce a double pipe.
- a small hole was provided in the inner tube of the double tube, and compressed air was supplied to the outer tube using a compressor. At this time, the wind speed from the small hole was 100 m / sec.
- a taper pipe whose diameter increases downward is welded to the lower part of the pipe.
- Nylon 6 resin was supplied from the side surface of the tapered tube. Then, an air-permeable support body (hereinafter referred to as a fixing net) that moves in a certain direction is installed at the lower part of the taper tube outlet, and suction is performed by a blower from below, and the flexible net is placed on the fixing net. A mixture of the cut carbon fiber and nylon 6 resin was deposited in a strip shape while reciprocating the transport pipe and the taper pipe in the width direction. Then, the apparatus is operated with the carbon fiber supply rate set to 500 g / min and the nylon 6 resin supply rate set to 530 g / min, and a mat-like structure in which carbon fibers and thermoplastic resin are mixed on the fixing net. An isotropic substrate was obtained.
- a fixing net air-permeable support body
- the carbon fibers in the isotropic substrate were two-dimensionally randomly dispersed and oriented.
- This isotropic base material was heated at 2.0 MPa for 5 minutes in a press apparatus heated to 260 ° C. using a mold having a concave portion on the upper portion, and a flat plate (I) having a thickness of 2.3 mm was obtained. Obtained.
- the carbon fibers in the molded plate (I) were a mixture of single yarns and fiber bundles partially opened.
- the carbon fibers were isotropically dispersed in the plane direction in the molded plate (I).
- the number of critical single yarns was 86, and the average number of fibers was 420.
- Production of fiber-reinforced resin molded plate using isotropic substrate Fibers were produced in the same manner as in Production Example 1 except that the carbon fiber supply rate was 340 g / min, the nylon 6 resin supply rate was 530 g / min, the carbon fiber basis weight was 1200 g / m 2 , and the nylon 6 resin basis weight was 1500 g / m 2.
- a reinforced resin molded plate was produced.
- a reinforced resin molded plate was produced.
- Example 1 The molded plate (I) obtained in Production Example 1 is cut into a size of 200 mm ⁇ 100 mm, dried with a hot air dryer at 120 ° C. for 4 hours, and then the temperature of the molded plate (I) is increased to 280 ° C. with an infrared heater. The temperature rose. A mold having 8 holes (concave portions) having an outer circumference of 200 mm ⁇ 100 mm, ⁇ (diameter) 6 mm, and depth 10 mm was set at 140 ° C., and the heated molded plate (I) was introduced into the mold. .
- This molded plate (I ′) had a tensile elastic modulus of 26 GPa.
- the buckling stress of the protrusion was 120 MPa.
- a molded plate (I ′′) having a size of 200 mm ⁇ 100 mm was obtained using a flat plate mold having an outer periphery of 200 mm ⁇ 100 mm. This was cut into 25 mm ⁇ 75 mm, and a ⁇ 6 mm through hole was processed in the center.
- the fiber-reinforced resin joined body was prepared by caulking at 60 ⁇ m and a pressure of 1500 kN for 1 second. This fiber reinforced resin joined body had a cross tensile strength of 2.5 kN. Moreover, the ratio of the undissolved part in the protrusion part inside the caulking part to the height of the caulking part of the sample after the test was 0.45. In addition, it was confirmed by observing the cross section of the protruding portion with an optical microscope that a part of the carbon fibers contained in the protruding portion had entered the molding plate (I ′) other than the protruding portion.
- Example 2 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the molded plate obtained in Production Example 2 was used.
- the tensile modulus of the molded plate having the protrusions was 22 GPa.
- the buckling stress of the protrusion was 100 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 2.1 kN.
- the ratio of the unmelted portion in the protruding portion inside the caulking portion to the height of the caulking portion of the sample after the test was 0.35.
- Example 3 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the molded plate obtained in Production Example 3 was used.
- the tensile modulus of the molded plate having the protrusions was 18 GPa.
- the buckling stress of the protrusion was 85 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 1.8 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.30.
- Example 4 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the shape of the protrusion was ⁇ 8 mm and the height was 8 mm, and the shape of the through hole was ⁇ 8 mm.
- the tensile modulus of the molded plate having the protrusions was 26 GPa.
- the buckling stress of the protrusion was 160 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 3.0 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.4.
- Example 5 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the shape of the protrusion was ⁇ 10 mm and the height was 6 mm, and the shape of the through hole was ⁇ 10 mm.
- the tensile modulus of the molded plate having the protrusions was 26 GPa.
- the buckling stress of the protrusion was 200 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 3.5 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.50.
- Example 6 A fiber reinforced resin joined body in the same manner as in Example 1 except that the shape of the protrusion is a trapezoidal shape having an upper side of 10 mm, a lower side of 22 mm, a thickness of 5 mm, and a height of 10 mm, and the shape of the through hole is 22 mm ⁇ 5 mm.
- the tensile modulus of the molded plate having the protrusions was 26 GPa.
- the buckling stress of the protrusion was 250 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 3.5 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.20.
- Example 7 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the applied pressure was 2500 N.
- the tensile modulus of the molded plate having the protrusions was 26 GPa.
- the buckling stress of the protrusion was 120 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 1.7 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.65.
- Example 1 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the molded plate obtained in Reference Example 1 was used.
- the tensile modulus of the molded plate having the protrusions was 13 GPa.
- the buckling stress of the protrusion was 70 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 1.4 kN.
- the ratio of the undissolved part in the protrusion part inside the caulking part to the height of the caulking part of the sample after the test was 0.45.
- Example 2 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the molded plate obtained in Reference Example 2 was used.
- the tensile modulus of the molded plate having the protrusions was 11 GPa.
- the buckling stress of the protrusion was 50 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 1.3 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.40.
- Example 3 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the molded plate obtained in Reference Example 3 was used.
- the tensile modulus of the molded plate having the protrusions was 8 GPa.
- the buckling stress of the protrusion was 30 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 1.0 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.40.
- a fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the shape of the protrusion was ⁇ 4 mm and the height was 12 mm, and the shape of the through hole was ⁇ 4 mm.
- the tensile modulus of the molded plate having the protrusions was 26 GPa.
- the buckling stress of the protrusion was 60 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 1.2 kN.
- the ratio of the undissolved part in the protrusion inside the caulking part to the height of the caulking part of the sample after the test was 0.70.
- Example 8 A fiber-reinforced resin joined body was obtained in the same manner as in Example 1 except that the molded plate obtained in Production Example 4 was used.
- the tensile modulus of the molded plate having the protrusions was 24 GPa.
- the buckling stress of the protrusion was 110 MPa.
- the cross tensile strength of the fiber-reinforced resin joined body was 2.3 kN.
- the ratio of the undissolved part in the protrusion part inside the caulking part to the height of the caulking part of the sample after the test was 0.45.
- the fiber-reinforced resin joined body of the present invention has excellent joint strength, and can be used for applications that require excellent weld strength, such as structural parts of automobiles. To ensure.
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Abstract
Description
また、本発明の他の目的は、接合によるエネルギーロスが少ないため短時間で効率的に製造する繊維強化樹脂接合体の製造方法を提供することにある。
強化繊維と熱可塑性樹脂とを含有し、かつ、座屈応力が80~450MPaの範囲にある少なくとも1つの突起部を有する繊維強化樹脂成形体Aと、少なくとも1つの貫通孔を有する部材Bとを含んで構成された繊維強化樹脂接合体であって、前記繊維強化樹脂成形体Aの突起部は前記部材Bの貫通孔内を貫通しており、かつ前記貫通孔から突き出した部分にかしめ部を有することを特徴とする、繊維強化樹脂接合体。
[2]
前記繊維強化樹脂成形体Aの引張弾性率が15~35GPaの範囲にある、[1]に記載の繊維強化樹脂接合体。
[3]
前記強化繊維のうち少なくとも1つの強化繊維が、前記繊維強化樹脂成形体Aの突起部と当該突起部以外の部分とに渡って存在する、[1]または[2]に記載の繊維強化樹脂接合体。
[4]
前記かしめ部が、内部に未変形部を有し、
前記未変形部の長さL1と、前記かしめ部の高さL2とが、下記式を満たす、[1]~[3]のいずれか1項に記載の繊維強化樹脂接合体。
0 < L1/L2 < 0.6
[5]
前記部材Bが、金属、樹脂、および強化繊維を含有する樹脂からなる群から選ばれる少なくとも一種の部材である、[1]~[4]のいずれか1項に記載の繊維強化樹脂接合体。
[6]
前記部材Bにおける前記強化繊維を含有する樹脂が熱可塑性樹脂である、[5]に記載の繊維強化樹脂接合体。
[7]
前記部材Bにおける前記熱可塑性樹脂が、前記繊維強化樹脂成形体Aに含有されている熱可塑性樹脂と同種の熱可塑性樹脂である、[6]に記載の繊維強化樹脂接合体。
[8]
前記かしめ部は、前記部材Bの表面と接触している、[1]~[7]のいずれか1項に記載の繊維強化樹脂接合体。
[9]
前記繊維強化樹脂成形体Aに含有されている前記強化繊維は不連続の繊維である、[1]~[8]のいずれか1項に記載の繊維強化樹脂接合体。
[10]
強化繊維と熱可塑性樹脂とを含有し、かつ、座屈応力が80~450MPaの範囲にある少なくとも1つの突起部を有する繊維強化樹脂成形体Aの前記突起部を、少なくとも1つの貫通孔を有する部材Bの前記貫通孔に挿入し、前記突起部の先端部を前記貫通孔から突き出す工程、および当該突き出した先端部をかしめる工程、を含む、繊維強化樹脂接合体の製造方法。
[11]
前記かしめる工程は、前記先端部を加熱しつつ加圧する工程を含む、[10]に記載の繊維強化樹脂接合体の製造方法。
[12]
前記加熱は、赤外線または超音波による加熱である、[11]に記載の繊維強化樹脂接合体の製造方法。
[13]
前記突起部の先端部に由来する未変形部の長さ(L1)とかしめ部の高さ(L2)との関係が下記式を満たすようにかしめる、[10]~[12]のいずれか1項に記載の繊維強化樹脂接合体の製造方法。
0 < L1/L2 < 0.6
また、本発明によれば、接合によるエネルギーロスが少ないため、繊維強化樹脂接合体を短時間で効率的に製造することができる。
上記繊維強化樹脂成形体Aは、熱可塑性樹脂からなるマトリクス中に強化繊維が含有されている成形体である。詳細については後述する。
本発明で使用する繊維強化樹脂成形体AおよびBは、強化繊維と熱可塑性樹脂とを含んでなるものである。具体的には、熱可塑性樹脂をマトリクスとし、そのマトリクス中に強化繊維が含有されている。繊維強化樹脂成形体Aに含まれる強化繊維は、目的に応じて、繊維強化樹脂成形体Bに含まれる強化繊維と同じであってもよいし、異なっていてもよいが、生産上の点から同じものであることが都合が良い場合が多い。繊維強化樹脂成形体Aに含まれる熱可塑性樹脂は、目的に応じて、繊維強化樹脂成形体Bに含まれる熱可塑性樹脂と同じであってもよいし、異なっていてもよいが、生産上の点から同一であることが都合が良い場合が多い。
本発明に用いられる強化繊維の種類は、マトリクスの種類や本発明の繊維強化樹脂接合体の用途等に応じて適宜選択することができるものであり、特に限定されるものではない。このため、本発明に用いられる強化繊維としては、無機繊維又は有機繊維のいずれであっても好適に用いることができる。
上記金属繊維としては、例えば、アルミニウム繊維、銅繊維、黄銅繊維、ステンレス繊維、スチール繊維を挙げることができる。
上記ガラス繊維としては、Eガラス、Cガラス、Sガラス、Dガラス、Tガラス、石英ガラス繊維、ホウケイ酸ガラス繊維等からなるものを挙げることができる。
上記有機繊維としては、例えば、アラミド、PBO(ポリパラフェニレンベンズオキサゾール)、ポリフェニレンスルフィド、ポリエステル、アクリル、ポリアミド、ポリオレフィン、ポリビニルアルコール、ポリアリレート等の樹脂材料からなる繊維を挙げることができる。
複数種の無機繊維を併用する態様としては、例えば、炭素繊維と金属繊維とを併用する態様、炭素繊維とガラス繊維を併用する態様等を挙げることができる。一方、複数種の有機繊維を併用する態様としては、例えば、アラミド繊維と他の有機材料からなる繊維とを併用する態様等を挙げることができる。さらに、無機繊維と有機繊維を併用する態様としては、例えば、炭素繊維とアラミド繊維とを併用する態様を挙げることができる。
上記炭素繊維としては、一般的にポリアクリロニトリル(PAN)系炭素繊維、石油・石炭ピッチ系炭素繊維、レーヨン系炭素繊維、セルロース系炭素繊維、リグニン系炭素繊維、フェノール系炭素繊維、気相成長系炭素繊維などが知られているが、本発明においてはこれらのいずれの炭素繊維であっても好適に用いることができる。
繊維強化樹脂成形体Aの製造方法は後述するが、本発明においては、例えば射出成形、圧縮成形(プレス成形)が好ましい。射出成形の場合、成形材料(好ましくはペレットの形態)に含まれる強化繊維の長さとしては、0.1~10mmの範囲が好ましい。圧縮成形の場合には、成形材料(好ましくはシート材料)に含まれる強化繊維としては、長さ1~100mmの範囲の不連続繊維、織物、編み物、一方向材などの連続繊維を挙げることが出来る。当該シート材料は、1枚であってもよいし、複数枚積層して用いてもよい。
強化繊維の平均繊維長は、例えば、繊維強化樹脂成形体AおよびBから無作為に抽出した100本の繊維の繊維長を、ノギス等を用いて1mm単位まで測定し、下記式に基づいて求めることができる。繊維強化樹脂成形体AおよびBからの強化繊維の抽出は、例えば、繊維強化樹脂成形体AおよびBに対し、500℃×1時間程度の加熱処理を施し、炉内にて樹脂を除去することによって行うことができる。
個数平均繊維長:Ln=ΣLi/j
(Li:強化繊維の単糸の繊維長、j:強化繊維の本数)
重量平均繊維長:Lw=(ΣLi2)/(ΣLi)
なお、ロータリーカッターで切断した場合など、繊維長が一定長の場合は数平均繊維長と重量平均繊維長は同じ値になる。
本発明において個数平均繊維長、重量平均繊維長のいずれを採用しても構わないが、繊維強化樹脂材の物性をより正確に反映できるのは、重量平均繊維長である事が多い。
例えば、強化繊維として炭素繊維が用いられる場合、平均繊維径は、通常、3μm~50μmの範囲内であることが好ましく、4μm~12μmの範囲内であることがより好ましく、5μm~8μmの範囲内であることがさらに好ましい。
一方、強化繊維としてガラス繊維を用いる場合、平均繊維径は、通常、3μm~30μmの範囲内であることが好ましい。
ここで、上記平均繊維径は、強化繊維の単糸の直径を指すものとする。したがって、強化繊維が繊維束状である場合は、繊維束の径ではなく、繊維束を構成する強化繊維(単糸)の直径を指す。
強化繊維の平均繊維径は、例えば、JIS R7607:2000に記載された方法によって測定することができる。
本発明に用いられる強化繊維は、単糸状のもののみであってもよく、繊維束状のもののみであってもよく、両者が混在していてもよい。ここで示す繊維束とは2本以上の単糸が集束剤や静電気力等により近接している事を示す。繊維束状のものを用いる場合、各繊維束を構成する単糸の数は、各繊維束においてほぼ均一であってもよく、あるいは異なっていてもよい。
一般的に、炭素繊維は、数千~数万本のフィラメントが集合した繊維束状となっている。強化繊維として炭素繊維を用いる場合に、炭素繊維をこのまま使用すると、繊維束の交絡部が局部的に厚くなり薄肉の繊維強化樹脂成形体AおよびBを得ることが困難になる場合がある。このため、本発明では、強化繊維として炭素繊維を用いる場合は、炭素繊維束を拡幅したり、又は開繊したりして使用するのがよい。本発明における繊維強化樹脂成形体AおよびBに含まれる強化繊維の拡幅の程度や開繊の程度は、同じであっても異なっていてもよい。
臨界単糸数=600/D (1)
(ここでDは炭素繊維の平均繊維径(μm)である)
臨界単糸数を上回る本数からなる炭素繊維束は、自立性に優れるためハンドリング性に優れ、かつ成形時の流動性にも優れた好適な強化材となり得る。逆に、臨界単糸数を下回る本数からなる炭素繊維束は、自立性が低いため綿状になる事が多い。そのため、ハンドリング性や成形時の流動性が低下する傾向がある。
炭素繊維の場合、上記Nは通常1<N<12000の範囲内とされることが好ましく、下記式(2)を満たすことがより好ましい。
0.6×104/D2<N<1.0×105/D2 (2)
(ここでDは炭素繊維の平均繊維径(μm)である)
一般的に、繊維強化樹脂成形体に用いられる代表的なマトリクスとしては、熱可塑性樹脂及び熱硬化性樹脂が知られているが、本発明においては、繊維強化樹脂成形体Aを構成するマトリクスとして熱可塑性樹脂を用いる。また、本発明においてはマトリクスとして、熱可塑性樹脂を主成分とする範囲において、熱硬化性樹脂を併用してもよい。
上記熱可塑性樹脂は特に限定されるものではなく、本発明の繊維強化樹脂接合体の用途等に応じた優れた機械特性や生産性などを考慮しつつ、所望の軟化点又は融点を有するものを適宜選択して用いることができる。
上記熱可塑性樹脂としては、通常、軟化点が180℃~350℃の範囲内のものが用いられるが、これに限定されるものではない。
上記ポリスチレン樹脂としては、例えば、ポリスチレン樹脂、アクリロニトリル-スチレン樹脂(AS樹脂)、アクリロニトリル-ブタジエン-スチレン樹脂(ABS樹脂)等を挙げることができる。
上記ポリアミド樹脂としては、例えば、ポリアミド6樹脂(ナイロン6)、ポリアミド11樹脂(ナイロン11)、ポリアミド12樹脂(ナイロン12)、ポリアミド46樹脂(ナイロン46)、ポリアミド66樹脂(ナイロン66)、ポリアミド610樹脂(ナイロン610)等を挙げることができる。
上記ポリエステル樹脂としては、例えば、ポリエチレンテレフタレート樹脂、ポリエチレンナフタレート樹脂、ボリブチレンテレフタレート樹脂、ポリトリメチレンテレフタレート樹脂、液晶ポリエステル等を挙げることができる。
上記変性ポリフェニレンエーテル樹脂としては、例えば、変性ポリフェニレンエーテル等を挙げることができる。
上記熱可塑性ポリイミド樹脂としては、例えば、熱可塑性ポリイミド、ポリアミドイミド樹脂、ポリエーテルイミド樹脂等を挙げることができる。
上記ポリスルホン樹脂としては、例えば、変性ポリスルホン樹脂、ポリエーテルスルホン樹脂等を挙げることができる。
上記ポリエーテルケトン樹脂としては、例えば、ポリエーテルケトン樹脂、ポリエーテルエーテルケトン樹脂、ポリエーテルケトンケトン樹脂を挙げることができる。
上記フッ素系樹脂としては、例えば、ポリテトラフルオロエチレン等を挙げることができる。
また、本発明で用いる繊維強化樹脂成形体A,B中には、本発明の目的を損なわない範囲で、有機繊維または無機繊維の各種繊維状または非繊維状のフィラー、難燃剤、耐UV剤、安定剤、離型剤、顔料、軟化剤、可塑剤、界面活性剤等の添加剤を含んでいてもよい。
本発明における繊維強化樹脂成形体A,Bを製造する方法は特に制限はなく、例えば、射出成形、押出成形、プレス成形などが挙げられる。射出成形、プレス成形の場合には、強化繊維を含むマトリクスを成形直前に加熱して可塑化し、金型へ導入する。加熱する方法としては、射出成形の場合はエクストルーダーなどが用いられ、プレス成形の場合は熱風乾燥機や赤外線加熱機などが用いられる。
なお、上記強化繊維マットとは、強化繊維が堆積し、または絡みあうなどしてシート状またはマット状になったものをいう。強化繊維マットとしては、強化繊維の長軸方向が面内方向においてランダムに分散した2次元等方性の強化繊維マットや、強化繊維が綿状に絡み合うなどして、強化繊維の長軸方向がXYZの各方向においてランダムに分散している3次元等方性の強化繊維マットが例示される。
1枚の基材中に異なる配列状態の強化繊維が含まれる態様としては、例えば、(i)基材の面内方向に配列状態が異なる強化繊維が配置されている態様、(ii)基材の厚み方向に配列状態が異なる強化繊維が配置されている態様を挙げることができる。また、基材が複数の層からなる積層構造を有する場合には、(iii)各層に含まれる強化繊維の配列状態が異なる態様を挙げることができる。さらに、上記(i)~(iii)の各態様を複合した態様も挙げることができる。
なかでも、強化繊維が、長軸方向が一方向に配列した一方向配列の基材や、上記長軸方向が面内方向において2次元ランダムに分散した配向状態にある等方性の基材が好適である。
上記基材における強化繊維の目付量は、特に限定されるものではないが、通常、25g/m2~10000g/m2である。
なお、本発明に用いられる基材が複数の層が積層された構成を有する場合、上記厚みは各層の厚みを指すのではなく、各層の厚みを合計した基材全体の厚みを指すものとする。
上記基材が上記積層構造を有する態様としては、同一の組成を有する複数の層が積層された態様であってもよく、又は互いに異なる組成を有する複数の層が積層された態様であってもよい。
また、上記基材が上記積層構造を有する態様としては、相互に強化繊維の配列状態が異なる層が積層された態様であってもよい。このような態様としては、例えば、強化繊維が一方向配列している層と、強化繊維が2次元ランダム配列している層を積層する態様を挙げることができる。
3層以上が積層される場合には、任意のコア層と、当該コア層の表裏面上に積層されたスキン層とからなるサンドイッチ構造としてもよい。
1)強化繊維をカットする工程、
2)カットされた強化繊維を開繊させる工程、
3)開繊させた強化繊維とマトリクスとなる繊維状又は粒子状又は溶融状態の熱可塑性樹脂を混合し等方性基材とした後、加熱圧縮して強化繊維樹脂成形体前駆体を得る工程、
4)当該前駆体を成形する工程
例えば、強化繊維として炭素繊維を用いる場合、複数の炭素繊維からなるストランドを、必要に応じ繊維長方向に沿って連続的にスリットして幅0.05~5mmの複数の細幅ストランドにした後、平均繊維長3~100mmに連続的にカットし、カットした炭素繊維束に気体を吹付けて開繊させた状態で、通気性コンベヤーネット等の上に層状に堆積させることにより、炭素繊維が面内方向において無秩序でランダムに分散した強化繊維マットを得ることができる。
本発明に用いる繊維強化樹脂成形体Aは少なくとも一つの突起部を有する。この突起部は後述の部材Bの貫通部に挿入され、この貫通部より上に突き出した部分がかしめられて、かしめ部となる。
突起部の内部に含まれる複数の強化繊維の一部または全部が、当該突起部以外の繊維強化樹脂成形体Aに含まれるようにする手法としては特に限定はないが、該手法の一つとして強化繊維の繊維長を制御する手法がある。強化繊維の繊維長をある程度長くすることで、突起部以外の繊維強化樹脂成形体Aに強化繊維を含ませることができる。逆に、強化繊維の繊維長をある程度短くすることで、突起部の径にも依存するが、突起部に強化繊維が進入しやすくなる。具体的には強化繊維の繊維長が1mmを下限とし、突起部の径の20倍を上限とするのが好ましい。
その他の手法としては、突起部を成形する際に、強化繊維が突起部に流動しやすくなるように制御するのが好ましい。前述の流動性を制御する手法としては、特に限定は無いが、具体的には樹脂の選定、強化繊維の繊維長、繊維径の制御、繊維束の制御、強化繊維の添加量の制御、成形温度、成形圧力の制御などが挙げられる。流動性を高める手法としては、一般的には樹脂の粘度を低下させる、繊維長を短くする、繊維径を太くする、繊維束を太くする、添加量を減らす、成形温度を上げる、成形圧力を上げる事となる。しかしながら、これらの手法の中には、繊維強化樹脂成形体の機械強度を下げる事に繋がるものもあるので、設計に応じて適宜選択するのが好ましい。
なお、突起部を繊維強化樹脂成形体Aに設ける方法としては、特に制限はなく、例えば、当該繊維強化樹脂成形体Aを成形するための金型に、あらかじめ突起部を形成するような形状を設けておき、当該繊維強化樹脂成形体Aと突起部とを一体として成形する方法、繊維強化樹脂成形体Aと突起部とを別々に製造しておき、当該突起部を当該繊維強化樹脂成形体Aに熱溶着したり、接着剤を用いて接合する方法が挙げられる。前記したように、突起部の内部に含まれる複数の強化繊維の一部または全部が、当該突起部以外の繊維強化樹脂成形体A中に含まれていると、突起部の根元における強度が向上し、突起部の座屈強度を高めることができるので、繊維強化樹脂成形体Aと突起部とを一体成形するのが好ましい方法である。
本発明に用いる部材Bは、少なくとも1つの貫通孔を有する。貫通孔の大きさおよび形状は、前記繊維強化樹脂成形体Aの突起部が完全に挿入でき、そしてかしめられる程度に貫通孔から突き出すことができればよい。貫通孔の形状としては、上記突起部の形状に対応して選択すればよく、繊維強化樹脂成形体Aの形状よりも大きく設計するのが好ましい。
貫通孔を得る方法としては、特に制限はないが、例えば、ドリル、エンドミル、ウォータージェット、レーザーなどにより穴あけ加工する方法、金型にあらかじめ貫通孔にあたる部分を打ち抜き刃を用いて前記基材をプレス成形する方法などが挙げられる。
本発明の繊維強化樹脂接合体は、その形状に特に制限はなく、例えば、面状や棒状の繊維強化樹脂成形体Aと、同形状の繊維強化樹脂成形体Bとから構成されていてもよい。また、繊維強化樹脂成形体Aが2以上の突起部を有し、それらの突起部全てを繊維強化樹脂成形体Bの2以上の貫通部にすべて挿入されてかしめられてもよい。さらには、1以上の突起部を有する繊維強化樹脂成形体Aの一つの突起部が、1つ以上の突起部と1つ以上の貫通部とを有する繊維強化樹脂成形体Bにおける、1つの貫通部に挿入してかしめられ、繊維強化樹脂成形体Bの1以上の突起部が、第三の成形体の貫通部に挿入されかしめられていてもよい。
0 < L1/L2 < 0.6
L1とL2の関係が上記の範囲にあると、優れた接合強度が得られる傾向にあるため、好ましく使用できる。上記溶け残り部の長さを制御する手法として特に限定はないが、具体的には前記突起部の座屈応力を上述の範囲に制御したり、かしめ条件を制御する方法がある。かしめ条件として、突起部の加熱温度、突起部にかける圧力、かしめ時間などがあるが、突起部にかける圧力を高めるなどしてかしめ時間を短縮化する程、溶け残り部の長さが大きくなる傾向にある。かしめ部における上記関係は、より好ましくは、下記式を満たす。
0 < L1/L2 <0.5
なお、上記かしめ部のL1とL2は、かしめ部を破壊してノギスなどによって求めることができる。
本発明の繊維強化樹脂接合体は、上記の如くかしめられているので、優れた接合強度を有するものであるが、用途によっては、他の接合方法、例えば、接着剤等によってかしめ部をさらに補強してもよい。
かしめ部は、部材Bの表面と接触していることが好ましいが、接合強度が保てるのであれば接触していなくてもよい。また、突起部は、部材Bの貫通孔内面とは接触していても接触していなくてもよい。
本発明の繊維強化樹脂接合体は、繊維強化樹脂成形体Aと部材Bとから基本的に構成される。一方の繊維強化樹脂成形体Aは、強化繊維とマトリクスとして熱可塑性樹脂とを含んでなり、少なくとも1つの突起部を有するものである。部材Bは、少なくとも1つの貫通孔を有するものであり、好ましくは、強化繊維とマトリクスとして熱可塑性樹脂とを含んでなるものである。繊維強化樹脂成形体Aの突起部は、部材Bの貫通孔に挿入され、突き出した部分(突出部)はかしめられている。かしめる際には、突出部を加熱しつつ加圧することが好ましく、変形が完了した後に冷却、固化することによって製造することができる。
本発明の繊維強化樹脂接合体は、かしめ部分が1つでもよいが、2つ以上あってもよい。
なお、本実施例における各値は、以下の方法に従って求めた。
(1)繊維強化樹脂接合体の十字引張強度は、自動車技術会1987年 No.406-87に従って測定した。具体的に、十字引張強度は、試験片のサイズが25mm×75mm×2.5mm、引張速度5mm/sで行った。
(2)突起部の座屈応力は、JIS K7181:2011に従って圧縮試験にて測定した。
(3)繊維強化樹脂成形体Aの引張弾性率は、JIS K7161:1994に従って引張試験にて測定した。
(4)かしめ部内部での突出部の未変形部(溶け残り部)の長さ(L1)とかしめ部の高さ(L2)は、上記(1)記載の試験後の破壊されたサンプルをノギスによって測定し、かしめ部内部での突出部の溶け残り部の割合(L1/L2)を算出した。
炭素繊維として、平均繊維長20mmにカットした東邦テナックス社製の炭素繊維“テナックス”(登録商標)STS40-24KS(平均繊維径7μm)を使用し、マトリクスとして、ユニチカ社製のナイロン6樹脂A1030を用いて、WO2012/105080パンフレットに記載された方法に基づき、炭素繊維目付け1800g/m2、ナイロン6樹脂目付け1500g/m2である等方的に炭素繊維が配向した、ナイロン6樹脂を含有する強化繊維マットを作成した。
具体的には、炭素繊維の分繊装置には、超硬合金を用いて円盤状の刃を作成し、0.5mm間隔に配置したスリッターを用いた。カット装置には、超硬合金を用いて螺旋状ナイフを表面に配置したロータリーカッターを用いた。このとき、刃のピッチを20mmとし、炭素繊維を繊維長20mmにカットするようにした。
カッターを通過したストランドをロータリーカッターの直下に配置したフレキシブルな輸送配管に導入し、引き続き、これを開繊装置に導入した。開繊装置としては、径の異なるSUS304製のニップルを溶接し、二重管を製作して使用した。二重管の内側の管に小孔を設け、外側の管との間にコンプレッサーを用いて圧縮空気を送気した。この時、小孔からの風速は、100m/secであった。この管の下部には下方に向けて径が拡大するテーパ管を溶接した。
この等方性基材を、上部に凹部を有する金型を用いて260℃に加熱したプレス装置にて、2.0MPaにて5分間加熱し、厚さ2.3mmの平板の成形板(I)を得た。この成形板(I)中の炭素繊維は、単糸状のものと一部が開繊された繊維束状のものとが混在していた。炭素繊維は、成形板(I)中の平面方向に等方的に分散していた。臨界単糸数86であり、平均繊維数は420であった。
炭素繊維の供給量を340g/min、ナイロン6樹脂の供給量を530g/minとし、炭素繊維目付け1200g/m2、ナイロン6樹脂目付け1500g/m2とした以外は製造例1と同様にして繊維強化樹脂成形板を製造した。
炭素繊維の供給量を170g/min、ナイロン6樹脂の供給量を530g/minとし、炭素繊維目付け600g/m2、ナイロン6樹脂目付け1500g/m2とした以外は製造例1と同様にして繊維強化樹脂成形板を製造した。
ナイロン6樹脂の代わりに、ポリカーボネート樹脂(帝人(株)製、「パンライト」(登録商標))を用いた以外は製造例1と同様にして繊維強化樹脂成形板を製造した。
炭素繊維の供給量を90g/min、ナイロン6樹脂の供給量を530g/minとし、炭素繊維目付け300g/m2、ナイロン6樹脂目付け1500g/m2とした以外は製造例1と同様にして繊維強化樹脂成形板を製造した。
炭素繊維の供給量を45g/min、ナイロン6樹脂の供給量を530g/minとし、炭素繊維目付け150g/m2、ナイロン6樹脂目付け1500g/m2とした以外は製造例1と同様にして繊維強化樹脂成形板を製造した。
炭素繊維の供給量を0g/min、ナイロン6樹脂の供給量を530g/minとし、炭素繊維目付け0g/m2、ナイロン6樹脂目付け1500g/m2とした以外は製造例1と同様にして繊維強化樹脂成形板を製造した。
製造例1で得られた成形板(I)を200mm×100mmの大きさに切り出し、120℃の熱風乾燥機で4時間乾燥した後、赤外線加熱機により成形板(I)の温度を280℃まで昇温した。外周が200mm×100mm、Φ(直径)6mm、深さ10mmの孔(凹部)が8個付いた金型を140℃に設定し、上記加熱した成形板(I)を同金型内に導入した。ついで、プレス圧力5MPaで1分間加圧し、Φ6mm、高さ10mmの8個の突起部を持つ成形板(I’)を得た。これを、突起部が中央に来るように25mm×75mmにカットした。この成形板(I’)の引張弾性率は26GPaであった。突起部の座屈応力は120MPaであった。
上述と同様に、外周が200mm×100mmの平板用金型を用いて200mm×100mmの成形板(I’’)を得た。これを、25mm×75mmにカットし、中央にΦ6mmの貫通孔を加工した。
製造例2で得られた成形板を用いた以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は22GPaであった。突起部の座屈応力は100MPaであった。繊維強化樹脂接合体の十字引張強度は2.1kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.35であった。
製造例3で得られた成形板を用いた以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は18GPaであった。突起部の座屈応力は85MPaであった。繊維強化樹脂接合体の十字引張強度は1.8kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.30であった。
突起部の形状がΦ8mm、高さ8mmである事、貫通孔の形状がΦ8mmである以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は26GPaであった。突起部の座屈応力は160MPaであった。繊維強化樹脂接合体の十字引張強度は3.0kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.4であった。
突起部の形状がΦ10mm、高さ6mmである事、貫通孔の形状がΦ10mmである以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は26GPaであった。突起部の座屈応力は200MPaであった。繊維強化樹脂接合体の十字引張強度は3.5kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.50であった。
突起部の形状が上辺10mm、下辺22mm、厚み5mm、高さ10mmの台形状である事、貫通孔の形状が22mm×5mmである事以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は26GPaであった。突起部の座屈応力は250MPaであった。繊維強化樹脂接合体の十字引張強度は3.5kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合はで0.20であった。
加圧力を2500Nにしたこと以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は26GPaであった。突起部の座屈応力は120MPaであった。繊維強化樹脂接合体の十字引張強度は1.7kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.65であった。
参考例1で得られた成形板を用いた以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は13GPaであった。突起部の座屈応力は70MPaであった。繊維強化樹脂接合体の十字引張強度は1.4kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.45であった。
参考例2で得られた成形板を用いた以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は11GPaであった。突起部の座屈応力は50MPaであった。繊維強化樹脂接合体の十字引張強度は1.3kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.40であった。
参考例3で得られた成形板を用いた以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は8GPaであった。突起部の座屈応力は30MPaであった。繊維強化樹脂接合体の十字引張強度は1.0kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.40であった。
突起部の形状がΦ4mm、高さ12mmであること、貫通孔の形状がΦ4mmであること以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は26GPaであった。突起部の座屈応力は60MPaであった。繊維強化樹脂接合体の十字引張強度は1.2kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.70であった。
製造例4で得られた成形板を用いた以外は、実施例1と同様にして繊維強化樹脂接合体を得た。
突起部を有する成形板の引張弾性率は24GPaであった。突起部の座屈応力は110MPaであった。繊維強化樹脂接合体の十字引張強度は2.3kNであった。また、試験後のサンプルのかしめ部の高さに対する、かしめ部内部の突出部における溶け残り部の割合は0.45であった。
本出願は、2014年3月25日出願の日本特許出願(特願2014-061711)に基づくものであり、その内容はここに参照として取り込まれる。
Claims (13)
- 強化繊維と熱可塑性樹脂とを含有し、かつ、座屈応力が80~450MPaの範囲にある少なくとも1つの突起部を有する繊維強化樹脂成形体Aと、少なくとも1つの貫通孔を有する部材Bとを含んで構成された繊維強化樹脂接合体であって、前記繊維強化樹脂成形体Aの突起部は前記部材Bの貫通孔内を貫通しており、かつ前記貫通孔から突き出した部分にかしめ部を有することを特徴とする、繊維強化樹脂接合体。
- 前記繊維強化樹脂成形体Aの引張弾性率が15~35GPaの範囲にある、請求項1に記載の繊維強化樹脂接合体。
- 前記強化繊維のうち少なくとも1つの強化繊維が、前記繊維強化樹脂成形体Aの突起部と当該突起部以外の部分とに渡って存在する、請求項1または2に記載の繊維強化樹脂接合体。
- 前記かしめ部が、内部に未変形部を有し、
前記未変形部の長さL1と、前記かしめ部の高さL2とが、下記式を満たす、請求項1~3のいずれか1項に記載の繊維強化樹脂接合体。
0 < L1/L2 < 0.6 - 前記部材Bが、金属、樹脂、および強化繊維を含有する樹脂からなる群から選ばれる少なくとも一種の部材である、請求項1~4のいずれか1項に記載の繊維強化樹脂接合体。
- 前記部材Bにおける前記強化繊維を含有する樹脂が熱可塑性樹脂である、請求項5に記載の繊維強化樹脂接合体。
- 前記部材Bにおける前記熱可塑性樹脂が、前記繊維強化樹脂成形体Aに含有されている熱可塑性樹脂と同種の熱可塑性樹脂である、請求項6に記載の繊維強化樹脂接合体。
- 前記かしめ部は、前記部材Bの表面と接触している、請求項1~7のいずれか1項に記載の繊維強化樹脂接合体。
- 前記繊維強化樹脂成形体Aに含有されている前記強化繊維は不連続の繊維である、請求項1~8のいずれか1項に記載の繊維強化樹脂接合体。
- 強化繊維と熱可塑性樹脂とを含有し、かつ、座屈応力が80~450MPaの範囲にある少なくとも1つの突起部を有する繊維強化樹脂成形体Aの前記突起部を、少なくとも1つの貫通孔を有する部材Bの前記貫通孔に挿入し、前記突起部の先端部を前記貫通孔から突き出す工程、および当該突き出した先端部をかしめる工程、を含む、繊維強化樹脂接合体の製造方法。
- 前記かしめる工程は、前記先端部を加熱しつつ加圧する工程を含む、請求項10に記載の繊維強化樹脂接合体の製造方法。
- 前記加熱は、赤外線または超音波による加熱である、請求項11に記載の繊維強化樹脂接合体の製造方法。
- 前記突起部の先端部に由来する未変形部の長さ(L1)とかしめ部の高さ(L2)との関係が下記式を満たすようにかしめる、請求項10~12のいずれか1項に記載の繊維強化樹脂接合体の製造方法。
0 < L1/L2 < 0.6
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JPWO2015146846A1 (ja) | 2017-04-13 |
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US20160096340A1 (en) | 2016-04-07 |
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