WO2004018186A1 - 繊維強化複合材料成形品の製造方法と同製品 - Google Patents
繊維強化複合材料成形品の製造方法と同製品 Download PDFInfo
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- WO2004018186A1 WO2004018186A1 PCT/JP2003/010516 JP0310516W WO2004018186A1 WO 2004018186 A1 WO2004018186 A1 WO 2004018186A1 JP 0310516 W JP0310516 W JP 0310516W WO 2004018186 A1 WO2004018186 A1 WO 2004018186A1
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- composite material
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- molded article
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/68—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts by incorporating or moulding on preformed parts, e.g. inserts or layers, e.g. foam blocks
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
- B29C70/345—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using matched moulds
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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
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
- B29C70/543—Fixing the position or configuration of fibrous reinforcements before or during moulding
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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
- B29C2791/00—Shaping characteristics in general
- B29C2791/001—Shaping in several steps
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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
- B29C2791/00—Shaping characteristics in general
- B29C2791/002—Making articles of definite length, i.e. discrete articles
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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
- B29C2793/00—Shaping techniques involving a cutting or machining operation
- B29C2793/0009—Cutting out
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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
- B29C2793/00—Shaping techniques involving a cutting or machining operation
- B29C2793/0081—Shaping techniques involving a cutting or machining operation before shaping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/24—Condition, form or state of moulded material or of the material to be shaped crosslinked or vulcanised
- B29K2105/246—Uncured, e.g. green
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- 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
- B29L2025/00—Frameless domes
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- 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
-
- 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
- B29L2031/52—Sports equipment ; Games; Articles for amusement; Toys
- B29L2031/5227—Clubs
Definitions
- the present invention is a method for producing a fiber-reinforced composite material molded article having a three-dimensional shape, and is particularly suitable for efficiently producing a three-dimensional molded article having a good appearance and a large curvature using a plurality of pre-preda.
- the present invention relates to a method for producing a fiber-reinforced composite material molded article. Background art
- the three-dimensional shape has a gentle convex shape having a small curvature.
- the pre-preda was pressed and stretched from both sides by a press die having a desired shape, whereby the pre-preda could be easily formed.
- Patent Document 1 when a head portion of a three-dimensional golf club is preformed, a plurality of heads are formed. Although it is divided into parts, each part is made by press-molding a pre-predder cut into a predetermined shape by a press die. Each part of the preformed head and the preformed shaft are inserted into a hollow mold, and pressure is applied from the inside of the preformed article to form the heat.
- the golf club is manufactured by joining and integrating the shaft with each part of the golf club.
- the pre-preda is first cut into a circle, and a plurality of cuts 3b are formed at equal intervals radially except for the center 3a of the circular pre-preda.
- notches 4b are formed radially at equal intervals while leaving the center 4a of the circular pre-predder 4.
- the center portions 3a and 4a of the circular pre-preders 3 and 4 are aligned with the apexes of a press die (third press die described later) 20 having a hemispherical convex portion 20a shown in FIG.
- a press die (fourth press die described later) having a hemispherical concave portion 21a as shown is laminated on a hemispherical press die 20 or 21 in accordance with the center of the bottom. At this time, the adjacent edge portions of the notch 3b or the notch 4b are overlapped with each other. Next, the mold was covered with a press die of the other party and pressed to form a hemispherical molded product as a whole.
- the step of placing the pre-preda on a press die and overlapping the edges of the cuts or cuts is usually performed manually. Therefore, the above-mentioned method tends to lack the stability of the quality of the molded product, and is insufficient in terms of uniformity and productivity.
- the edges of the notches or notches do not overlap sufficiently or are unstable, a drawback due to being drawn into the edges may occur. It is said that it is difficult to adopt the above method for molded products that require high strength and appearance because they are easy to enter and disturb the arrangement of reinforcing fibers.
- the present invention has been made to solve this conventional problem, and its purpose is to stand up by applying pressure using a pre-predder cut into a predetermined shape.
- the fiber-reinforced composite enables stable and efficient production of a uniform-quality molded product without producing any shrinkage in the molded product.
- An object of the present invention is to provide a preformed product and a finished molded product obtained by a method for producing a material molded product and the same method. Disclosure of the invention
- the basic structure of the present invention is a method for producing a fiber-reinforced composite material molded article by simultaneously molding a plurality of pre-predas cut into a predetermined shape,
- the fiber-reinforced composite material molded article in the present invention refers not only to a final product that can itself be a product, but also to be molded by another method that is later joined and integrated with other parts. And preforms before they are formed into final products.
- a plurality of prepregs may be arranged in a stacked manner as long as a plurality of prepregs are arranged in a stacked manner when they are placed on a mold. Laminate multiple pre-preders before placing them on It also includes placing while.
- a method of forming at least one set of partially divided pieces and the remaining part for each pre-predator is to form a laminated body by laminating a plurality of pre-preders cut into a predetermined shape, and cut or cut the laminated body.
- a notch By forming a notch, at least one set of partially separated pieces and the remaining part is formed for each pre-predder, or by forming a notch or notch for each pre-predder, at least one piece for each pre-predder Either of the methods of forming the partially separated pieces and the rest of the set may be used.
- a separation piece and a remaining part can be respectively formed on a plurality of pre-predaders at the same time, thereby improving production efficiency.
- notches or cutouts are made one by one, but the shape of the partially separated piece for each pre-predder is reduced to a preferable shape as described later.
- a part of the separated pieces separated by the cuts or cutouts is pressed to form a three-dimensional shape, and thereafter, the remaining part is partially formed on the part of the separated pieces.
- the additional pressing is applied separately, which facilitates the molding operation.
- the arrangement of the reinforcing fibers is disturbed due to the notch or the notch edge being pulled in. Nor.
- the cuts or cutouts of the plurality of pre-predas to be superimposed are formed so as to be at least two different positions.
- the pre-predas are formed into a three-dimensional shape and then superimposed, even if a gap is formed between the cuts or cut-outs of a single pre-preda, the whole is obtained as a closed state. Since the overlapping part of the separation pieces does not concentrate due to bias between each pre-predator, it does not become locally thick, greatly contributing to the improvement of appearance and strength be able to.
- a plurality of pre-predaders have a configuration in which the shape of a partially separated piece of each pre-preder is formed to be substantially similar to or congruent with another pre-predder. It is preferable to form a notch or a notch so as to increase the width of the partially separated piece on the layer side which becomes concave due to the application of pressure to the partially separated piece.
- the edges of the cuts or cutouts forming the respective partially separated pieces of the pre-preda be narrowed substantially in parallel or toward the outer peripheral portion.
- the center of the notch or the notch of each pre-preder is spaced apart by 2 mm or more from each other.
- the remaining part is partially overlapped with the separation piece, but when the cut or cut ends match in a state where a plurality of pre-predas are overlapped, the plurality of pre-predas are mutually attached at the end position. Because of the interference, it is difficult to partially overlap the remaining part with the separation piece, so that when forming, an opening may be formed at the end position.
- each notch or notch is spaced apart by 2 mm or more between the plurality of pre-preders, and when it approaches less than 2 mm, the end of the notch or notch in each pre-predder is reduced. It concentrates almost at one point, so-called aperture after molding is concentrated 6
- Such openings can significantly reduce product strength.
- the openings formed in one prepreg can be covered with another prepreg, and molding A molded product with a clean appearance and strength as a whole is obtained.
- the distance between the above-mentioned ends can be determined as appropriate according to the curvature of the molded product, and it is sufficient that the ends of the cuts or notches do not substantially touch each other between substantially different pre-predaders. In such a case, the above-mentioned problems are unlikely to occur even in a molded product having a large curvature.
- the reinforcing fiber in the present invention it is preferable to use any reinforcing fiber selected from the group consisting of carbon fiber, glass fiber and organic fiber (including aramide fiber and PBO fiber) for the pre-preda. Furthermore, it is preferable to use a pre-preda made of a unidirectional material or a woven fabric in which reinforcing fibers are aligned in one direction.
- the material of the reinforcing fiber and its pre-preda structure can be appropriately selected according to the use of the fiber-reinforced composite material molded article, required strength, and the like, and the fiber directions can be appropriately combined and laminated.
- an epoxy resin having excellent bonding strength with the reinforcing fiber as the matrix resin since the final product has excellent strength.
- an epoxy resin composition comprising the following components A, B, C, and D.
- Component B an amine compound having at least one sulfur atom in the molecule (component B-1) and / or a reaction product of an epoxy resin with an amine compound having at least one sulfur atom in the molecule (B-2) Ingredient)
- D component Dicyandiamide T JP2003 / 010516
- the content of each of the sulfur atom and the component c in the epoxy resin composition was 0.2 to 7 mass 0 /. And preferably 1 to 15% by mass, and more preferably the C component is a granular material having an average particle size of 150 m or less.
- the fiber-reinforced composite material molded article according to the present invention having excellent appearance can be obtained in a very short time.
- the fiber-reinforced composite material molded product in the present invention also includes a preformed product before the thermosetting resin (epoxy resin composition) is completely cured.
- a preform of a fiber-reinforced composite material formed of a pre-preda can be manufactured.
- a finished product having an excellent appearance can be manufactured in a short time.
- it is preferable to employ compression molding in this step because molding can be performed at a high pressure and curing can be performed in a short time.
- FIG. 1 is a plan view in which a cut is made in one circular pre-preda to form four sets of partially separated pieces and the rest.
- FIG. 2 is a plan view in which a cutout is made in one circular pre-preda to form four sets of partially separated pieces and a remainder.
- FIG. 3 is a plan view when three circular pre-predas are stacked.
- FIG. 4 is a schematic view showing a typical example of the first press die.
- FIG. 5 is a schematic view showing a representative example of the second press die.
- FIG. 6 is a schematic view showing a typical example of the third press die.
- FIG. 7 is a schematic view showing a typical example of a fourth press die.
- Figure 8 shows the partial separation of the three pre-preders on the first press die.
- FIG. 3 is a schematic diagram when only a hemisphere is formed.
- FIG. 9 is a schematic diagram showing a case where all the remaining portions of the three pre-predaers are partially overlapped on a third press die and are all formed into a hemispherical shape.
- FIG. 10 is a plan view showing an example of a cut shape of a circular pre-preda as a molding material of a conventional hemispherical molded body.
- FIG. 11 is a plan view showing an example of a notch shape of a circular pre-preda as a molding material of a conventional hemispherical molded body.
- the pre-preda is first cut into a circle. Then, as shown in FIG. 1, four sets of two sets of parallel linear cuts 1b are formed while leaving the center 1a of the circular pre-predder 1, and the center 1a is formed between the cuts 1b.
- the four partial separation pieces 1c are formed in a cross shape around the central part 1a, and four fan-shaped remaining parts 1d are formed between the partial separation pieces 1c.
- the cut shape of the pre-preda does not necessarily have to be a circle, and when the pre-preda is formed into a shape other than a hemisphere, it can be cut into a suitable shape such as an ellipse, a sector, or a rectangle as needed. .
- the cuts 1b are not necessarily parallel, and it is preferable that each of the partial separation pieces 1c be formed so as to become narrower toward the outer periphery, but as described later, the first press die is used. To ensure that there is no risk of interference between the parting piece and the mold during molding, at least It is preferable not to widen.
- each cut edge of d may be further cut in a triangular shape to form a cut 2b.
- the notch edges of the partial separation piece 2c are not necessarily parallel to each other, and may be narrower toward the outer periphery, but are preferably not wider.
- the partially separated pieces and the remaining part formed by the cuts or notches can be formed into a desired three-dimensional shape if one set is used. It is preferable to form four or more sets.
- FIG. 3 shows a state in which three pre-predaers 31 to 33 cut into a circle are stacked.
- These circular pre-predas 31 to 33 may be cut out from one large pre-preg, or may be prepared by preparing different types of pre-predas individually manufactured into the same shape.
- the three pre-predeers 3 1, 3 2, 3 3 have the same shape at the central part, but a partial separation piece 3 1, in order from the upper-layer prepreg 31 to the lower-most prepreg 33.
- the partially separated pieces 31c to 33c do not necessarily need to be formed in this way, but the layer on which the concave surface is formed by pressing a certain separated piece 31c to 33c is formed. It is preferable that the width of the partial separation piece in the above is not narrower than the width of the partial separation piece on the layer side forming the convex surface. If the width of the partial separation piece on the layer side forming the concave surface is wider than the width of the partial separation piece on the layer side forming the convex surface, there is a possibility that the partial separation piece may be caught in the mold.
- the shapes of the partially separated pieces are substantially similar or congruent. If the shapes of the partially separated pieces are significantly different, there is a possibility that the partially separated pieces may be caught in the mold, When the remaining part is overlapped, there is a possibility that a thick part is formed in the molded product.
- a method of forming a plurality of circular pre-preders 31 1, 32, 33 by superposing them on each other First, only the partially separated pieces 31c, 32c, and 33c are formed into a hemispherical shape using a press die, and then the remaining portions 31d, 32d, and 33d are formed into a hemispherical shape. It is formed by bending and partially overlapping the partially separated pieces 31c, 32c and 33c.
- the pre-predas 3 1 to 3 3 are overlapped and their partially separated pieces 3 1 c
- a first press mold 10 shown in FIG. 4 and a second press mold 11 shown in FIG. 5 are used.
- the first press die 10 forms the concave surface side of the molded product hemispherical shape, that is, the inner side surface, has a concave groove portion 10a composed of a cross-shaped hemispherical surface, and has the other portion, that is, Circular prepredder 3 1 ⁇ 3 3 rest 3 1 c!
- a fan-shaped projection 10 b having a flat upper surface is provided at the term It protrudes to almost the same height as.
- the three pre-predeers 31 to 33 may be set one by one on the first press die 10 and laminated, but as shown in FIG. It may be set in the press die 10.
- the second press die 11 has a shape that fits into the hemispherical concave groove portion 10a, and fits with the first press die 10 at a predetermined interval.
- the second press die 11 has a circular opening 11b formed in the center of a frame 11a, and fits into the circular opening 11 between the fan-shaped projections 10b.
- a cross-shaped hemispherical projection 11c that fits on the surface of the cross-shaped groove 10a is formed.
- the three circular pre-predeers 3 1, 3 2, 3 3 are placed on the first press mold 10. .
- the central portions 3 la, 32 a, and 33 a of each circular pre-predder 1 were placed on the top of the hemisphere 10 a of the first press die 10, and placed.
- Partially separated pieces 31c, 32c and 33c are arranged along the cross-shaped hemispherical concave groove 10a of the press die 10 and the adjacent remaining parts 3ld, 32d, 33 d is arranged on the flat surface of the sector-shaped protrusion 10 b of the press die 10.
- the shape of the hemispherical concave groove portion 10a and the sector-shaped protrusion portion 10b does not necessarily have to completely match the cut shape of the pre-preda, and may be bent or curved into a predetermined cubic shape or overlapped. It is enough if it is possible.
- each circular prepreg 3 1, 3 2, 3 3 is always accurately positioned at a fixed position with respect to the press mold 10. Can be positioned and positioned.
- each circular pre-predder 3 1, 3 2, 3 3 has a pair of cuts 3 1 b, 3 2 b, 33 b formed parallel or narrow toward the outer periphery, while the first press die Since the width of the concave groove portion 10a of 10 is equal to or greater than the width of the partially separated piece 3c, each partially separated piece between the two cuts 1b 3 1c, 3 2c and 33c do not interfere with the sector-shaped protrusion 10b on which the remaining portions 31d, 32d and 33d of the adjacent sectors are located.
- the cuts 31b, 32b, and 33b are formed so as to be substantially parallel to each other or to narrow toward the outer periphery as described above.
- the second press die 11 is fitted to the first press die 10, and the central portions 31a, 32a., 33a of the circular pre-predeers 31, 32, 33 are fitted.
- the partially separated pieces 3 1 c, 3 2 c, and 33 c are connected to the cross-shaped concave grooves 10 a of the first press die 10 and the cross-shaped hemispherical protrusions 1 1 c of the second press die 11. And press-molding.
- the width of the cross-shaped hemispherical projection 11c is set to be equal to or less than the width of the partially separated piece 33c on the concave side (that is, the lowermost layer). There is no interference between c and the rest of the fan shape 31d, 32d, 33d.
- the partially separated pieces 3 1 c, 3 2 c, and 3 3 c formed by stacking are fan-shaped
- the third press die 20 having a hemispherical convex portion 20a shown in FIG.
- a fourth press die 21 having a hemispherical concave portion 21a is used.
- the center of the central portions 31a, 32a and 33a is placed on the center of the protrusion 20a of the third press die 20 and placed, and has a hemispherical concave portion 21a.
- the fourth press die 21 is fitted into the third press die 20 and pressed. At this time, as shown in Figure 9
- the edge portions of the remaining portions 31d, 32d, and 33d partially overlap the surfaces of the edge portions of the separation pieces 31c, 32c, and 33c.
- the center portions 3 la, 32 a, 33 a of the circular pre-predas 31, 32, 33 and the partially separated pieces 31 c, 32 c, 33 c are previously hemispherical.
- the remaining portions 31 d, 32 d, and 33 d are edged to the partially separated pieces 31 c, 32 c, and 33 c without forming a seal or the like. It can be easily overlapped on the surface, and no shrinkage occurs in the remaining portions 31 d, 32 d, and 33 d due to being pulled in during mold clamping.
- the edges of the remaining portions 31d, 32d, and 33d are overlapped and formed into a hemispherical shape, and then heat-cured to form a fiber-reinforced composite material molded product.
- the molding of the present invention after forming a notch or a notch in each of the plurality of pre-preders, and laminating them, the remaining part is partially overlapped with the separating piece, and the molding is performed. If the cut end (end) on the center side of each notch or notch is located at the same position, it is often difficult for a plurality of pre-predas to interfere with each other at the end position, and to partially overlap the rest with the separation piece.
- the openings may occur after molding. Particularly, when the ends of the cuts or cutouts in each pre-preda are smaller than 2 mm, the cutouts or cutouts are concentrated at almost one point, and the openings tend to concentrate there. The result As a result, as a product, the strength often decreases at the openings.
- a plurality of pre-preders to be stacked are formed such that the ends of the centers of the notches or notches of each pre-preder are separated by at least 2 mm.
- the j formed apart means that the end position of the center of the notch or notch between each pre-predder is shifted, and the shift between the ends at this time is shifted toward the center. In this case, it includes the case where it shifts along the outer edge of the pre-predder and the case where it shifts diagonally toward the center.
- 3 3 are cut into 3 lb, 3 2 b, 3 3b to make the press mold accurate , It is possible to manufacture molded products of uniform quality. Also, in the second molding step, almost half of the finished product is formed into a hemispherical shape in the first molding step, so the remaining part is integrated with the previously molded half without forming any shear. Is done.
- the above-described two molding steps are performed using separate press dies.
- the sector-shaped protrusion 10 b of the first press die 10 is a movable piece member.
- a movable piece into the circular opening 1 1b of the second press die 11, it is possible to perform two-stage molding with one set of press dies, regardless of the vertical positional relationship. It becomes.
- a part of the plurality of pre-predeers 31, 32, and 33 may be overlapped with partially separated pieces 31 c, 32 c, and 33 c while the second press die 11 is first placed. It is also possible to dispose it on the inner surface of the hemispherical projection 11c, and then press the first press mold 10 to form.
- the manufacture of such a molded product other than a circular shape should be similarly performed.
- the pre-predator include a sheet in which reinforcing fibers are aligned in one direction and impregnated with a matrix resin, and a sheet in which at least one of a warp and a weft is impregnated with a matrix resin in a woven fabric using the reinforcing fibers. It is preferably used.
- a prepreg consisting of a sheet in which reinforcing fibers are aligned in one direction is laminated in a plurality of layers so that the fibers are arranged in two directions of a 0 ° direction and a 90 ° direction, and further, in a ⁇ 45 ° direction. It can also be molded using a laminate of oriented ones, or a laminate of these repeatedly. Furthermore, even in a pre-predator made of a woven fabric, a plurality of layers can be laminated by changing the orientation angle of the fibers.
- the fiber-reinforced composite material molded article can be applied not only to a hemispherical shape but also to a variety of three-dimensional shapes such as a rectangular box shape, a spindle shape, and an elliptical spherical shape. Further, the present invention can be applied to the production of a substantially flat molded article having projections and recesses.
- the reinforced fiber composite material molded product obtained by the production method of the present invention is not limited to the final product.
- a container-shaped preformed product is molded by the method of the present invention, and thereafter, is formed in a molding die. It is also possible to combine pre-formed products and make the final product by internal molding, vacuum bag molding, auto creep molding, compression molding, etc.
- the preform at this time is also a part of the reinforced fiber composite material molded product of the present invention.
- the type of the above matrix resin is not particularly limited, and any of thermosetting resins such as epoxy resin, bismuth amide resin, phenol resin, and thermoplastic resin such as polyolefin and polyvinyl acetal may be used. Although it is possible, it is preferable to use a thermosetting resin because the strength of the molded article is improved. Among them, epoxy resins are particularly preferable because of their excellent adhesive strength with reinforcing fibers. When a final product is manufactured from a pre-formed product using a pre-prepared resin whose thermosetting resin is a thermosetting resin, the pre-formed product is manufactured by the above-described manufacturing method of the present invention while maintaining the thermosetting resin in an uncured state.
- thermosetting resins such as epoxy resin, bismuth amide resin, phenol resin, and thermoplastic resin such as polyolefin and polyvinyl acetal
- thermosetting resins because the strength of the molded article is improved.
- epoxy resins are particularly preferable because of their excellent adhesive strength with reinforcing fibers
- the preform After forming the preform, the preform is further heated and pressurized to form a hardened product, thereby obtaining a final product.
- the optimal conditions at the time of curing molding depend on the type of the thermosetting resin, but if not sufficiently cured, the flow of the uncured resin may lead to surface disorder and generation of pinholes. On the other hand, if molding is carried out under too severe conditions, molding irregularities and deterioration of appearance become severe.
- an epoxy resin composition comprising the following components A, B, C and D.
- Component B an amine compound having at least one sulfur atom in the molecule (component B-1) and a reaction product of Z or an epoxy resin with an amine compound having at least one sulfur atom in the molecule (B-2 Ingredient)
- D component Dicyandiamide
- the component A in the present invention is an epoxy resin.
- examples of this are bifunctional epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, dicyclopentadiene epoxy resin, fluorene epoxy resin, or these. And the like.
- 3 or more Examples of the above multifunctional epoxy resin include glycidylamines such as phenol novolak type epoxy resin, tarezole type epoxy resin, tetraglycidyl diamino diphenyl methane, triglycidyl diaminophenol, and tetraglycidyl diamine.
- glycidyl ether-type epoxy resin such as tetrakis (dalicydyloxyphenyl) ethanetris (glycidyloxymethane), epoxy resin modified from these, and brominated epoxy resin Examples include, but are not limited to, brominated epoxy resins. Also, as the component A, one or more of these epoxy resins may be used in combination.
- the component B of the present invention comprises an amine compound having at least one sulfur atom in the molecule (B-1 component) and an amine compound having at least one sulfur atom in the molecule with an amino or epoxy resin.
- the reaction product (B—two components) is determined.
- the B-11 component is not particularly limited as long as it is an amine compound having at least one sulfur atom in the molecule.
- examples thereof include 4,4′-diaminodiphenylsulfone and 3,3′diaminodiphene.
- Ninolesulfone, 4,4,1-diaminodidiphenyl sulfide, bis (4- (4-aminophenyl) phenyl) sulfone, bis (4- (3-aminophenyl) phenyl) sulfone, 4 "4-diaminodiphenyls Rufide, o-trian sulfone, and derivatives thereof are preferably used.
- the B-2 component is a reaction product obtained by reacting the above-mentioned epoxy resin with an amine compound having at least one sulfur atom in the molecule.
- a mixture containing the B-2 component is obtained by mixing and reacting the A component and the B-1 component, from which the B-2 component is isolated. There is no particular need to use it.
- the component A Part or all of the components added as the B-1 component may be changed to the B-2 component.
- one or both of the A component and the B-1 component may be completely consumed and changed to the B-2 component.
- the component C in the present invention is a urea compound.
- dichlorodimethinoleurea, phenyldimethinoleurea, 0—trizintholefone, bis (4- (3-aminophenoxy) phenyl) sulfone, mesooxali norreurea, vanolebituric acid, hydroxybarbituric acid, zirili Tulic acid, boluric acid, and the like are preferably used.
- a compound having no halogen in the molecule as the component C for example, phenyldimethylperyl, etc., is particularly suitable because it has high reactivity and low toxicity.
- the content of the C component in the epoxy resin composition is 1 to 15 mass. /. It is particularly preferred that It is more preferably at least 3% by mass, more preferably at most 12% by mass. If the amount is less than 1% by mass, the curing reaction may not be completed sufficiently in a short time. If the amount exceeds 15% by mass, it may not be able to be stored for a long time at around room temperature, which is not preferable in terms of resin storage. Les ,.
- the average particle size is preferably 15 ⁇ m ⁇ or less, more preferably 50 ⁇ m or less. If the average particle size exceeds 150 ⁇ m or less, the dispersion speed of the particles decreases, and as a result, the speed of the curing reaction decreases, and one of the important effects of the present invention is that the curing time is short. May not be achieved.
- the D component in the present invention is dicyandiamide.
- This dicyandiamide acts as a curing agent for the epoxy resin, and can be cured at a relatively low temperature in a short time by using it in combination with other components in the present invention.
- the content of the D component in the epoxy resin composition is preferably from 0.1 to 10% by mass.
- the average particle diameter of the component D is preferably 150 ⁇ or less, particularly preferably 50 ⁇ or less, because the dispersibility is improved and the reaction rate is increased.
- the epoxy resin of the present invention further includes inorganic fine particles such as finely divided silica, pigments, elastomers, defoamers, aluminum hydroxide as a flame retardant, magnesium oxide, a bromine-containing compound or a phosphorus-based compound. , Poly-Burf Olmar, Polyvinyl Acetal, Poly-Butyl Butyral, Poly-Hydroxy-Poly-Poly-Polyether, etc. An appropriate amount of a complex salt or a tertiary amine compound may be added.
- inorganic fine particles such as finely divided silica, pigments, elastomers, defoamers, aluminum hydroxide as a flame retardant, magnesium oxide, a bromine-containing compound or a phosphorus-based compound.
- Poly-Burf Olmar Polyvinyl Acetal, Poly-Butyl Butyral, Poly-Hydroxy-Poly-Poly-Polyether, etc.
- the epoxy resin composition of the present invention has a sulfur atom content of 0.2 to 7 mass in the epoxy resin composition. / 0 is preferred. If it is less than 0.2% by mass, it is difficult to complete the curing molding in a short time, and if it exceeds 7% by mass, it may not be able to be stored for a long time at around room temperature, which is not preferable in terms of resin storage. .
- the temperature condition is not particularly limited as long as the thermosetting resin is cured, but is preferably from 130 ° C to 220 ° C, more preferably from 140 ° C to 180 ° C.
- the content be C or less, because good appearance is maintained while shortening the molding time.
- this compression molding it is possible to obtain a integrally cured product by laminating a plurality of pre-predas. For example, when a preformed product in which the reinforcing fiber is a woven fabric is formed by superimposing a plurality of preformed products in which the reinforcing fiber is a directional material, and at least a part of the surface of the preformed product is further formed. It is also possible to paste SMC and integrally mold. In particular, by attaching SMC, it is possible to manufacture molded products with complicated curved shapes. ,
- the following components of the matrix resin were used. If the content of the sulfur atom is not described below, the molecule does not contain a sulfur atom.
- YPDN701 Cresole novolak type resin (YDPN-701, manufactured by Toto Kasei Co., Ltd.)
- Ep 828 Bisphenol A type liquid epoxy resin (Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.)
- Ep807 Bisphenol F type liquid epoxy resin (Epicoat 807 manufactured by Japan Epoxy Resin Co., Ltd.)
- E p l O O l Bisphenol A type solid epoxy resin (Epicoat 1001 manufactured by Japan Epoxy Resin Co., Ltd.)
- Ep604 Glycidylamine type epoxy resin (Epikoto 604, manufactured by Japan Epoxy Resin Co., Ltd.)
- N-740 phenolic novolak epoxy resin (EPICLON N-740, manufactured by Dainippon Ink & Chemicals, Inc.)
- DD S diaminodiphenylsulfone (Wakayama Seika Co., Ltd.) (Manufactured by Seika Cure-S, sulfur atom content, 12.9 mass%)
- BAPS 4, 4 'diaminodifuyeldisulphide (Wakayama Seika Co., Ltd., BAPS, sulfur atom content, 7.4% by mass)
- P DMU 3-Phenyl-1, 1-Dimethinoleurea
- the prepredder used in this example is a unidirectional material in which carbon fiber “TR50S” manufactured by Mitsubishi Rayon Co., Ltd. is aligned in one direction, and YD PN701 is 35 weight parts, Ep8 28 is 59 parts by weight, DI CY is 4 parts by weight, and DCMU is 2 parts by weight.
- a unidirectional material pre-preda carbon fiber content of 56% by volume
- a fiber weight of 175 g / m 2 and a resin content of 35% was obtained.
- the unidirectional material was used as a pre-predder of one set of constituent units, in which a laminated body in which the fibers were alternately arranged in the directions of 0 ° and 90 ° was alternately used.
- one set of pre-preda was cut into a circle, and as shown in Fig. 3, three sets of pre-preda were constructed. From the upper layer to the lower layer of each of the pre-predeers 3 1, 3 2, 3 3, the cuts 3 1 b, 3 2 b, 3 are made so that the widths of the respective partially separated pieces 3 1 c, 32 c, 33 c become wider in order. 3b formed.
- the central part 31a, 32a, 33a of each pre-predeer 31, 32, 33 is placed on the top of the cross-shaped hemisphere 10a of the first press die 10 shown in Fig. 4.
- the partially separated pieces 3 1 c, 32 c, and 33 c are combined with the hemispherical concave grooves 10 a
- the remaining portions 31 d, 32 d, and 33 d were placed on the flat surface on the fan-shaped projection 10 b of the same press die 10 while being placed along the groove surface.
- alignment was performed by setting the width of the partially separated piece 33 c of the lowermost layer and the interval between the sector-shaped protrusions 10 b of the first press die 10 to be the same. .
- the prepredder was heated at 80 ° C. for 10 seconds using an infrared heater in order to soften it.
- the second press mold 11 shown in FIG. 5 is fitted to the first press mold 10 to form a cross-shaped partial separation piece 3 1 including the central portions 31 a, 32 a, and 33 a.
- c, 32c, and 33c were pressed into a hemispherical shape and shaped into the shape shown in FIG.
- the shape of the pre-preda was fixed and the mold was removed.
- the prepreg fixed in the shape when the mold was removed was placed on the hemispherical convex portion 20a of the third press mold 20 shown in FIG. 6, and the top of the convex portion 20a and the central portion of the prepreg. 3 la, 32 a, and 33 a were placed together with each other and heated with an infrared heater at 80 ° C for 10 seconds to soften it. And the fan-shaped remaining parts 3 1 d, 32 d, and 33 d are curved in a hemispherical shape, and are superimposed on and adhered to the edges of the partially separated pieces 31 c, 32 c, and 33 c. As shown in FIG. After that, the inside of the press mold was cooled to 20 ° C. by air blow, and then the shape of the pre-preda was fixed and the mold was released to obtain a preform 41.
- This final molded product has a gap at the cut position, which partially disperses the separated pieces and the remaining laminated part, alleviates uneven thickness, provides excellent lamination strength and appearance, and has excellent production stability. I was able to get the product.
- a unidirectional material fiber basis: 125 g / m 2
- unidirectional carbon fiber TR50S manufactured by Mitsubishi Rayon Co., Ltd.
- a preformed product 41 was obtained in the same manner as in Example 1 except that a resin impregnated with the epoxy resin composition obtained by kneading (resin content 30%) was used.
- the sulfur atom content of this epoxy resin composition is 0.777%.
- This preformed product is set in a lower die (not shown) for compression molding having a shear edge structure, and subjected to a hardening molding at 140 ° C for 5 minutes under a load of pressure SO kgf Z cm 2.
- the final molded product was obtained.
- the gap at the cut position was closed, and a part of the separated piece and the remaining laminated portion were dispersed to reduce uneven thickness.
- a final product with good appearance and excellent production stability was obtained.
- an excellent molded product was obtained in the same manner as in Example 1, but the molding was completed in a particularly short time of 5 minutes.
- an epoxy resin composition having the composition shown in Table 1 was used, and a pre-molded product and a final product were obtained in the same manner as in Example 2 except that the components A and B were pre-reacted as necessary. Was. All are preformed products In this case, the pre-molded product was obtained without any disorder of the fiber, and the final product was also a molded product with good appearance.
- a preform and a final product were obtained in the same manner as in Example 2, except that the epoxy resin composition having the composition shown in Table 2 was used as the epoxy resin.
- the preforms did not cause turbulence in the fiber, and clean preforms were obtained.
- the final product was smooth at first glance, but had an appearance such that when exposed to light, the surface was slightly blue.
- the fiber-reinforced composite material molded product of the present invention can be used as a final product as a golf club, a hermet, an outer panel of a motorcycle, a car, a high-speed vehicle, an aircraft, or the like, or a housing of an electronic device such as a personal computer or a mobile phone. Etc. can also be suitably used. '
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Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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AT03792742T ATE447478T1 (de) | 2002-08-20 | 2003-08-20 | Verfahren zur herstellung eines geformten produkts aus faserverstürktem verbundmaterial |
CA002495748A CA2495748C (en) | 2002-08-20 | 2003-08-20 | Method of producing molded article of fiber-reinforced composite material and the molded article |
JP2004530580A JP4022222B2 (ja) | 2002-08-20 | 2003-08-20 | 繊維強化複合材料成形品の製造方法 |
US10/525,677 US8790563B2 (en) | 2002-08-20 | 2003-08-20 | Method of producing molded article of fiber-reinforced composite material and the molded article |
EP03792742A EP1535726B1 (en) | 2002-08-20 | 2003-08-20 | Method of producing formed product of fiber-reinforced composite material |
DE60329920T DE60329920D1 (de) | 2002-08-20 | 2003-08-20 | Verfahren zur herstellung eines geformten produkts aus faserverstürktem verbundmaterial |
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JP2002239625 | 2002-08-20 | ||
JP2002/239625 | 2002-08-20 | ||
JP2003/86132 | 2003-03-26 | ||
JP2003086132 | 2003-03-26 |
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US (1) | US8790563B2 (ja) |
EP (1) | EP1535726B1 (ja) |
JP (1) | JP4022222B2 (ja) |
KR (1) | KR100643103B1 (ja) |
CN (1) | CN100540279C (ja) |
AT (1) | ATE447478T1 (ja) |
CA (1) | CA2495748C (ja) |
DE (1) | DE60329920D1 (ja) |
ES (1) | ES2335492T3 (ja) |
WO (1) | WO2004018186A1 (ja) |
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- 2003-08-20 CN CNB038196298A patent/CN100540279C/zh not_active Expired - Lifetime
- 2003-08-20 AT AT03792742T patent/ATE447478T1/de not_active IP Right Cessation
- 2003-08-20 EP EP03792742A patent/EP1535726B1/en not_active Expired - Lifetime
- 2003-08-20 KR KR1020057002818A patent/KR100643103B1/ko active IP Right Grant
- 2003-08-20 WO PCT/JP2003/010516 patent/WO2004018186A1/ja active Application Filing
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JP2009530140A (ja) * | 2006-03-21 | 2009-08-27 | ディーエスエム アイピー アセッツ ビー.ブイ. | 造形部品の製造方法および前記方法で得られる造形部品 |
US8911580B2 (en) | 2007-03-30 | 2014-12-16 | Airbus Operations Gmbh | Method for producing a structural component |
JP2010523357A (ja) * | 2007-03-30 | 2010-07-15 | エアバス・オペレーションズ・ゲーエムベーハー | 構造部品の製造方法 |
WO2010022651A1 (en) * | 2008-08-25 | 2010-03-04 | Byd Company Limited | Shell for electronic device and method of forming the same |
KR20150038250A (ko) * | 2012-09-10 | 2015-04-08 | 미쯔비시 레이온 가부시끼가이샤 | 섬유 강화 복합 재료 성형품의 제조 방법 및 섬유 강화 복합 재료 성형품 |
KR101630584B1 (ko) | 2012-09-10 | 2016-06-14 | 미쯔비시 레이온 가부시끼가이샤 | 섬유 강화 복합 재료 성형품의 제조 방법 및 섬유 강화 복합 재료 성형품 |
WO2014038710A1 (ja) * | 2012-09-10 | 2014-03-13 | 三菱レイヨン株式会社 | 繊維強化複合材料成形品の製造方法及び繊維強化複合材料成形品 |
US10315343B2 (en) | 2012-09-10 | 2019-06-11 | Mitsubishi Chemical Corporation | Manufacturing method for molded article of fiber-reinforced composite material and molded article of fiber-reinforced composite materials |
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US10300632B2 (en) | 2012-10-30 | 2019-05-28 | Mitsubishi Chemical Corporation | Method of producing preform |
JP6134822B1 (ja) * | 2016-01-13 | 2017-05-24 | レノボ・シンガポール・プライベート・リミテッド | 繊維強化樹脂材の加工方法および繊維強化樹脂材 |
JP2017124530A (ja) * | 2016-01-13 | 2017-07-20 | レノボ・シンガポール・プライベート・リミテッド | 繊維強化樹脂材の加工方法および繊維強化樹脂材 |
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WO2019244994A1 (ja) | 2018-06-20 | 2019-12-26 | 三菱ケミカル株式会社 | プリプレグシートおよびその製造方法、繊維強化複合材料成形品およびその製造方法、ならびにプリフォームの製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
JPWO2004018186A1 (ja) | 2005-12-08 |
CA2495748A1 (en) | 2004-03-04 |
US8790563B2 (en) | 2014-07-29 |
EP1535726A4 (en) | 2007-02-28 |
EP1535726B1 (en) | 2009-11-04 |
KR20050058368A (ko) | 2005-06-16 |
EP1535726A1 (en) | 2005-06-01 |
JP4022222B2 (ja) | 2007-12-12 |
ATE447478T1 (de) | 2009-11-15 |
US20050253294A1 (en) | 2005-11-17 |
CA2495748C (en) | 2008-07-29 |
CN100540279C (zh) | 2009-09-16 |
ES2335492T3 (es) | 2010-03-29 |
KR100643103B1 (ko) | 2006-11-10 |
DE60329920D1 (de) | 2009-12-17 |
CN1675051A (zh) | 2005-09-28 |
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