JP5136876B2 - Reinforced fiber laminate and method for producing the same - Google Patents

Description

  The present invention relates to a reinforced fiber laminate used for molding a fiber reinforced resin and a method for producing the same, and in particular, by using a unidirectional reinforcing fiber base material in which reinforcing fibers are aligned in one direction, excellent handleability and shaping. The present invention relates to a reinforcing fiber laminate formed in a specific form capable of exhibiting properties and a method for producing the same.

  As a reinforcing fiber base material used for molding a fiber reinforced resin, a unidirectional reinforcing fiber base material itself is a base material in which reinforcing fibers are simply aligned in one direction. Cracks (gap between yarns) are likely to occur, and the handleability is poor as a dry substrate. Moreover, since it has the anisotropy peculiar to the base material arranged in one direction, it is difficult to form a complicated shape such as a curved surface shape or an uneven shape. Due to the rigidity in the orientation direction of the reinforcing fibers that are linearly oriented, cracking (gap between yarns) is likely to occur during shaping, and when cracking occurs, the part becomes resin-rich during molding and the resin cures In this case, it is easy to close. When such a shrinkage occurs particularly on the surface of the molded body, an undesirable feeling of unevenness is generated, and it becomes difficult to maintain the surface quality at a desired quality. Furthermore, in the case of a woven fabric base, the resin flows well through a gap formed by crimping the woven yarn. However, in the case of a unidirectional reinforcing fiber base, particularly in the case of a base material in which the reinforcing fibers are closely arranged, the resin flows. There is no gap, and the fluidity of the resin is poor, making it difficult to impregnate the resin.

  On the other hand, the unidirectional reinforcing fiber base material itself is a base material in which reinforcing fibers are simply aligned in one direction. Therefore, the unidirectional reinforcing fiber base material can be formed into a flat sheet-like base material without unevenness, and more or less uneven and textured fabrics are produced. Compared with the reinforcing fiber substrate of the form, when placed on the surface of the molded body, there is also an advantage that an excellent surface quality can be secured without causing a smooth and inconvenient pattern.

Various types of reinforcing fiber bases for molding fiber reinforced resins using unidirectional reinforcing fiber bases are known, and a thermoplastic resin material is disposed between a unidirectional reinforcing fiber base and another reinforcing fiber base. Although these are known to be heat-sealed (for example, Patent Documents 1 and 2), these are basically structures for forming a reinforced fiber laminate as a multilayer laminate. However, it is not necessarily configured to solve the problems unique to the unidirectional reinforcing fiber base as described above.
JP 2005-22396 A JP 2006-27091 A

  Therefore, the object of the present invention is to maintain the advantage of the unidirectional reinforcing fiber base material that can obtain an excellent surface quality when formed into a molded body, particularly focusing on the above-mentioned problems unique to the unidirectional reinforcing fiber base material. Provided is a reinforcing fiber laminate and a method for producing the same, which can greatly improve handling and shaping, and resin impregnation during molding, which were problems when using a unidirectional reinforcing fiber substrate. There is.

In order to solve the above-mentioned problems, the reinforcing fiber laminate according to the present invention has two layers of unidirectional reinforcing fiber bases in which reinforcing fibers are aligned in one direction, and the two layers of unidirectional reinforcing fiber bases are The unit reinforcing fiber laminate is formed by being bonded to each other with a binder made of a thermoplastic resin interposed between layers, and the unit reinforcing fiber laminate is laminated in plural layers, and the unit reinforcing fiber is used as an intermediate layer. A resin flow medium having a resin flow resistance lower than that of the laminate is disposed at a position between the unit reinforcing fiber laminates adjacent to each other in the laminating direction of the unit reinforcing fiber laminate, and another reinforcing fiber substrate is also laminated. It consists of what is characterized by.

That is, the two-layer unidirectional reinforcing fiber bases are fixed to each other and are handled integrally. Since the reinforcing fibers of the two-layer unidirectional reinforcing fiber base material are fixed and held together via the binder, the reinforcing fibers are more dispersed than in the case of the unidirectional reinforcing fiber base material having only one layer. Or the occurrence of cracks (gap between yarns) is prevented or suppressed, and handleability is greatly improved. In addition, cracks (gap between yarns) are less likely to occur during shaping, and the problem of shrinkage when the resin is rich or when the resin is cured is resolved. In particular, by disposing the reinforcing fiber laminate at the surface forming portion of the molded body, a good surface quality can be easily obtained without causing a smooth and undesirable pattern or the like. And the reinforced fiber laminated body which concerns on this invention is made into the structure which laminated | stacked it by making the reinforced fiber laminated body of the above structures into 1 unit. In such a laminated structure of unit reinforcing fiber laminates, the unit reinforcing fiber laminates are not fixed to each other while maintaining the above-described effects, so that the unit reinforcing fiber laminates are relatively fixed as necessary. Even when shaping along a curved surface or uneven surface, an appropriate deviation does not occur naturally between the unit reinforcing fiber laminates, and no cracks are generated. Shape becomes possible.

In such a reinforcing fiber laminate according to the present invention, the orientation directions of the reinforcing fibers of the two-layer unidirectional reinforcing fiber base (unit reinforcing fiber laminate) are preferably set to different directions. In particular, it is preferable that the orientation direction of the reinforcing fibers of the two-layer unidirectional reinforcing fiber base material is set in correspondence with the load direction of the molded body formed using the reinforcing fiber laminate. In this way, even when a highly anisotropic unidirectional reinforcing fiber substrate is used, the mechanical properties of the fiber reinforced resin to be molded can be maximized in the required direction. Is possible.

The unit in the laminated structure of reinforcing fiber laminate, further, other reinforcing fiber substrate, for example, unidirectional reinforcing fiber base material of the textile substrate and a single layer of reinforcing fibers that have been stacked. The unit reinforcing fiber laminate may be contained in any one of the layers, and is preferably contained as at least one surface layer.

Further, as the intermediate layer, a low resin flow medium of the resin flow resistance than the unit reinforcing fiber laminate are located. As described above, the unidirectional reinforcing fiber base has less gaps than the woven base, so that the resin does not flow easily. However, the difficulty of the resin flow is covered by a resin flow medium disposed in the middle. . As the resin flow medium, for example, a synthetic fiber network can be applied.

Further, in order to improve the fluidity of the resin, a needle shape penetrating in the thickness direction of the reinforcing fiber laminate composed of at least the two unidirectional reinforcing fiber base materials over substantially the entire area of the reinforcing fiber laminate. A configuration in which holes are perforated can be employed. This perforated structure of needle-like holes can be adopted for a single unit reinforcing fiber laminate, and can also be adopted for a reinforcing fiber laminate in which a plurality of layers are laminated. In particular, it is effective when the number of laminated layers is 8 or more and the basis weight is 2,000 g / m ² or more.

  The binder is preferably made of a thermoplastic resin compatible with the matrix resin impregnated in the reinforcing fiber laminate. As a result, this portion of the molded body after molding can be formed in a homogeneous layer, and local variations in mechanical properties are prevented from occurring.

  In the present invention, the type of reinforcing fiber of the unidirectional reinforcing fiber base is not particularly limited, but typically carbon fiber can be used.

The method for producing a reinforcing fiber laminate according to the present invention provides a binder made of a thermoplastic resin on a unidirectional reinforcing fiber substrate in which reinforcing fibers are aligned in one direction, and is separately provided on the binder. A unit reinforced fiber laminate is formed by stacking unidirectional reinforcing fiber bases and fixing two layers of unidirectional reinforcing fiber bases to each other via the binder. In addition to layer lamination , as an intermediate layer, a resin fluid medium having a resin flow resistance lower than that of the unit reinforcing fiber laminate is disposed at a position between unit reinforcing fiber laminates adjacent to each other in the laminating direction of the unit reinforcing fiber laminate. In addition, another reinforcing fiber base material is laminated . Since the two-layer unidirectional reinforcing fiber bases that are fixed and held to each other via the binder are fixed to each other and handled integrally, the handling is greatly improved as described above, and the shaping The characteristics are also greatly improved. And it is set as the laminated structure of the unit reinforcement fiber laminated body which consists of such a unidirectional reinforcement fiber base material of two layers adhering mutually.

More specifically, the reinforcing fiber laminate is, for example, once heated and melted after the binder is cooled and then fixed on one unidirectional reinforcing fiber substrate of the unit reinforcing fiber laminate. By stacking the other unidirectional reinforcing fiber substrate on the unidirectional reinforcing fiber substrate to which the bonding material is fixed, reheating and melting the binder, and then cooling the unidirectional reinforcing fiber substrates, Can be manufactured by fixing them together.

Moreover, in this manufacturing method, the orientation directions of the reinforcing fibers of the two-layer unidirectional reinforcing fiber base (unit reinforcing fiber laminate) can be set in different directions, and in that case, the two-layer unidirectional It can be set as the structure by which the orientation direction of the reinforced fiber of a reinforced fiber base material is set corresponding to the load direction of the molded object shape | molded using the said reinforced fiber laminated body.

Also, the same, as an intermediate layer, place the lower resin flow medium of the resin flow resistance than the unit reinforcing fiber laminate. As the resin flow medium, for example, a synthetic fiber network or a glass fiber nonwoven fabric can be used.

  The binder made of the thermoplastic resin can be applied, for example, in the form of a woven or non-woven fabric, or can be applied in the form of short fibers, granules, or powder. In a state where the two-layer unidirectional reinforcing fiber bases are fixed to each other, the binding material does not need to spread over the entire surface between the layers, and may be scattered to the extent necessary for fixing the two layers. .

  Similarly to the above, in order to improve the fluidity of the resin, a reinforcing fiber laminate comprising at least the two unidirectional reinforcing fiber bases in the thickness direction over substantially the entire area of the reinforcing fiber laminate. It is preferable to employ a method of drilling a needle-like hole that penetrates or a method of using a thermoplastic resin that is compatible with the matrix resin impregnated in the reinforcing fiber laminate as the binder.

  Also in such a manufacturing method, although it does not specifically limit as a reinforced fiber of a unidirectional reinforcing fiber base material, A carbon fiber can be used typically.

  Thus, according to the reinforcing fiber laminate and the method for producing the same according to the present invention, while utilizing the property of the unidirectional reinforcing fiber substrate that an excellent surface quality of the molded body can be obtained, the unidirectional reinforcing fiber base The handling property and shapeability of the reinforcing fiber laminate using the material and the resin impregnation property at the time of molding can be greatly improved, and it becomes possible to produce a molded product having excellent surface quality. In addition, a molded body having good and uniform mechanical properties can be easily manufactured by good resin impregnation and selection of a specific binder.

Hereinafter, the present invention will be described in detail together with preferred embodiments.
The basic structure of the reinforcing fiber laminate according to the present invention will be described with reference to FIG. As shown in FIG. 1, a reinforcing fiber laminate (unit reinforcing fiber laminate) 1 is a unidirectional reinforcing fiber substrate (hereinafter abbreviated as a UD substrate) of reinforcing fibers having different orientations (L-axis and M-axis directions), for example. It has a structure in which two layers 2 and 4 are laminated, and the two layers are fixed to each other with a binder 3 (binder) 3 disposed between the two layers. The binder 3 is made of a thermoplastic resin, and FIG. 1 shows an example in which the binder 3 is composed of a heat-meltable woven fabric or nonwoven fabric.

  The material of the binder 3 is a thermoplastic resin. For example, the following types can be used. For example, polyester, polyolefin, styrene resin, polyoxymethylene, polyamide, polyurethane, polyurea, polydicyclopentadiene, polycarbonate, polymethylene methacrylate, polyvinyl chloride, polyphenylene sulfide, polyphenylene ether, polyether imide, polysulfone, polyarylate, polyether Fluorine resins such as sulfone, polyketone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyarylate, polyethernitrile, polyimide, polyamideimide, phenol, phenoxy, polytetrafluoroethylene, and elastomer (preferably butadiene)・ Acrylonitrile, its carboxylic acid or amine modification, fluoroelastomer, Xane elastomers), rubbers (butadiene, styrene / butadiene, styrene / butadiene / styrene, styrene / isoprene / styrene, natural rubber, etc.), RIM resins (eg polyamide 6, polyamide 12, polyurethane, polyurea, polydicyclopentadiene) Used), cyclic oligomers (including those that form polycarbonate resins, polybutylene terephthalate resins, etc.), copolymers, modified products, and blended resins of two or more types. can do. Among these, at least one selected from polyamide, polyester, polyolefin, and polyphenylene sulfide, which are easily available as a nonwoven fabric, is preferable.

  As the reinforcing fiber of the unidirectional reinforcing fiber base material in which the reinforcing fibers are aligned in one direction, it is preferable to use those that can be used as reinforcing fiber yarns for composite materials, such as carbon fiber, graphite fiber, glass fiber, etc. Inorganic fibers, and organic fibers such as aramid, paraphenylenebenzobisoxazole, polyvinyl alcohol, and polyimide, and one or more of these may be used in combination. Among these, carbon fibers are excellent in specific strength and specific elastic modulus and are preferably used.

  Reinforced fiber yarns have 0.2 to 2.5% by weight of a sizing agent attached to improve handling properties and scratch resistance during the manufacture of multiaxial molding materials or stitching. Preferably it is. In the fiber yarn to which the sizing agent within the above range is attached, the generation of fluff is efficiently suppressed.

  Reinforcing fiber yarns can be used either untwisted or twisted, but in terms of mechanical properties such as tensile strength and compressive strength, those with substantially no twist (less than 1 turn / m) can be used. preferable.

  The reinforcing fiber laminate as described above can be basically produced by, for example, the following method. That is, when producing a UD base material (base material 4 or 2) by pulling it out from the creel and aligning it, the sheet-like binder 3 is placed on the aligned UD base material (4 or 2). For example, the binder 3 is once melted by heating with a far infrared heater from above, and then cooled and fixed in a subsequent process. On top of that, a UD base material (2 or 4) oriented in another direction is placed, reheated and fused, and then cooled and fixed. Thereby, the UD base materials 2 and 4 are mutually fixed, and the target unit reinforcement fiber laminated body 1 is produced.

Other configurations can be employed for the binder. For example, it is not a form like the above-mentioned woven fabric or non-woven fabric, but an independent short fiber having a length of 3 mm or less, a particulate form having a diameter of about 1 mm, or a powder form having a particle size of 0.1 mm or less. , Spread on the UD base material moderately (1 g / m ² or more, 30 g / m ² or less) and almost uniformly, fix the resin on the UD base material, and stack the other UD base material on it. As shown in FIG. 2, the reinforcing fiber laminate 10 in which both the UD bases 2 and 4 are fixed to each other via the binder 5 can be obtained. FIG. 3 is an enlarged view of a part of FIG. That is, the state is shown in which the thermoplastic resin (tacky fire) 5 of the above-described form is fixed to the aligned UD base material 2 across a plurality of adjacent reinforcing fiber bundles and the form is maintained.

  As this thermoplastic resin, a resin similar to the resin applicable to the woven fabric and the nonwoven fabric described above can be applied, but at least one selected from polyamide, polyester, polyolefin, and polyphenylene sulfide is preferable.

  The UD base material in the form shown in FIG. 3 can be produced, for example, as shown in FIG. In the method shown in FIG. 4, the reinforcing fiber bundle drawn out and supplied from the creel stand group 31 is stretched in the form of a sheet as the UD base material 33 while traveling through the speed regulating roll 32, and the hopper 34 is further formed thereon. The tacky fire 5 made of the thermoplastic resin stored in the sprayer is sprayed from slits extending in the width direction of the UD base material 33 of the tacky fire coating head 35, and the thermoplastic resin is fixed by the fixing heater 36 made of an infrared heater or the like from above. Is heated and melted to flatten the tacky fire 5, and then cooled with cold air from the cold air blowing means 37 to fix the thermoplastic resin to the upper surface of the UD base material 33. Then, the surface side to which the resin is fixed is covered with a cover film 38 (for example, polyethylene (PE) film) supplied separately, and wound as a winding roll 39. And at the time of lamination | stacking of the UD base materials mentioned above, what is necessary is just to use for the above lamination | stacking in the state which unwinded from the winding roll 39 and removed the cover film 38. FIG. For example, a thermoplastic resin is reheated by means such as hot pressing while disposing a UD base material oriented in another direction, and the UD base materials are fixed to each other with the thermoplastic resin and laminated.

  For example, the resin flow impregnation is improved as follows. As described above, one of the disadvantages of the UD base material is that there is no gap due to crimping like a woven fabric, and therefore the resin fluidity may be much worse than that of the woven fabric. In particular, because there is a thermoplastic resin disposed between the two layers of the UD base material, that is, a state in which a torn film is stuck between the layers, the resin in the thickness direction of the base material is further increased. Poor fluidity. Therefore, as the number of layers increases, the flow resistance of the resin in the thickness direction increases and the resin flow and impregnation become extremely difficult. As a result, unimpregnated (voids) or air bubbles cannot be completely removed and pinholes frequently occur.

  In order to improve the resin flow and impregnation in the thickness direction of the base material, as shown in FIG. 5, for example, “Kenyama” used for flower arrangement, a needle 7 (3 mm or less in diameter) on a metal plate. A perforated jig 6 in which the tip is thin and sharply embedded and fixed at a predetermined pitch (for example, 3 mm to 30 mm), and a perforated plate 8 having holes having the same pitch as the pitch of the needle 7 of the perforated jig 6 ( The reinforcing fiber laminate 1 of the UD base material is disposed between the center line pitch in the drawing and the thermoplasticity in the reinforcing fiber laminate 1 is received from the preheated porous plate 8. The reinforcing fiber laminate 1 is perforated by pressing in a state where the resin is softened (state of FIG. 6), and cooled in that state to maintain the perforated state. If it does in this way, resin will flow from the perforated part in the thickness direction of a substrate, and will come to be impregnated. Of course, the perforation operation may be performed after a desired number of unit reinforcing fiber laminates 1 are laminated. However, depending on the number of laminated units, a thin needle may not be able to penetrate, so one unit reinforcing fiber laminate 1 It is preferable to operate every time.

Moreover, the following method can also be employ | adopted as another measure of resin fluidity | liquidity improvement.
(1) As shown in FIG. 7, when the unit reinforcing fiber laminate 1 is laminated and an FRP product requiring a desired plate thickness is formed by an RTM molding method or the like, the resin flows from the outer peripheral end of the laminated base material 11. However, since there is no gap caused by crimping like a woven fabric in the surface direction (longitudinal direction) of the laminated base material 11, the thermoplastic resin is fixed to the base material layer between the unit reinforcing fiber laminates 1. Therefore, the resin flow resistance is very large, and the resin does not flow easily in that direction.
(2) As a measure for improving the fluidity of the resin in the surface direction, the resin flow medium 12 whose resin flow resistance is extremely lower than that of the unit reinforcing fiber laminate 1 is disposed in the middle part of the laminate substrate, and the laminate substrate First, the resin injected from the end portion is caused to flow through the resin fluidized medium 12 to fill the resin fluidic medium 12 in the entire surface direction (of the laminated substrate 11) (or after filling), and The resin is flowed and impregnated in the thickness direction of the material 11. In particular, in the thickness direction, the resin penetrates almost by capillary action.
(3) It goes without saying that the use of a base material with perforations as described above has a much faster and more reliable impregnation rate than simple permeation by capillary action.
(4) The resin flow medium 12 has a resin flow characteristic lower than the resin flow resistance in the surface direction of the laminated base material 11 made of reinforcing fibers (for example, a flow of 1/2 to 1/20 with respect to the laminated base material 11). However, it is necessary to select the material so that the adhesiveness and wettability with the matrix resin of the fiber reinforced resin molded product does not fall below a predetermined characteristic. Resin-made ones are desirable from the viewpoint of clearing such properties and economical efficiency, but inorganic fiber reinforcing fibers may also be used. As the resin, a thermoplastic resin capable of forming a woven fabric or a non-woven fabric that can be easily configured to have a low flow resistance is optimal. In particular, a mat form composed of short fibers or continuous fibers, or a mesh-like (net-like) woven fabric or the like is preferable.

As the basis weight of the resin flow medium 12 in terms of the resin filling amount is preferably in the range of 10~1500g / m ^2. Specific materials include the following.
(1) Flame-resistant non-woven fabric, carbon felt 50CF manufactured by TRUSCO NAKAYAMA Co., Ltd. (form of fabric: felt-like non-woven fabric, basis weight: 680 g / m ² ).
(2) Continuous strand mat, manufactured by Nippon Sheet Glass Co., Ltd. (form of fabric: glass continuous fiber nonwoven fabric, basis weight: 300 to 600 g / m ² ).
(3) Mesh fabric, NBC nylon mesh NB20 (form of fabric: nylon plain fabric, thickness: 520 μm).

  Moreover, the said resin fluidization medium 12 is not limited to one place around the intermediate | middle of the laminated base material 11, You may increase suitably according to lamination | stacking thickness. In particular, it is more effective if it is arranged at a position close to the surface layer so that voids and pinholes do not occur on the design surface side.

  Further, the resin flow medium 12 is longer than at least the laminated base material 11 and extends as much as possible to the burr forming portion, so that the injected resin can smoothly flow to the resin flow medium 12. From the viewpoint of ease of removal of burrs after molding. In the burr forming part, it is more preferable that the resin fluidized medium 12 covers at least a part of the laminated base material 11 in order to maintain the continuity of the appearance. The length extending to the burr portion is preferably 3 to 100 mm from the viewpoint of material efficiency, and more preferably 5 to 30 mm.

Next, the laminated structure in the present invention and the laminated structure of the prior art will be compared by Examples and Comparative Examples.
Example 1
The structure shown in FIG. 7 is an example of the laminated structure of the present invention. A multilayer laminated body 11 in which three layers of reinforcing fiber laminated bodies 1 are laminated on the upper part of the resin flow medium 12 of the intermediate layer and two layers are laminated on the lower part. It is shown.
(1) Reinforced fiber laminate 1: Unidirectional orientation in which carbon fiber “Torayca” T700 × 12K yarn manufactured by Toray Industries, Inc. is aligned to a width of 1 m so that the basis weight of the reinforcing fiber laminate 1 is 300 g / m ^2. The base material was arrange | positioned at upper and lower two layers. As for the orientation angle of the upper and lower layers, the crossing angle of each other is 90 degrees.
(2) A polyamide 6 nonwoven fabric having a basis weight of 80 g / m ² , a melting point of 220 ° C., and a melt viscosity of 90 Pa · s (270 ° C., shear rate 1000 / s) was used as an interlayer binder.
(3) As a method of laminating the reinforcing fiber laminate 1, first, carbon fiber “Torayca” T700 × 12K yarns are pulled out from a number of creels, aligned and arranged (the basis weight is 150 g / m ² ) at the same time. A polyamide 6 non-woven fabric as a binder is disposed on the arranged carbon fiber sheets and wound around a roll. In the meantime, they are pressed with a hot roll heated to about 200 ° C., and then cooled by blowing cold air (normal temperature) from above. Thereafter, the carbon fiber sheet to which the wound binding material is attached is cut into a length of 1 m, and is arranged on the carbon fiber sheet to which the binding material is not cut so that the crossing angle is 90 degrees. At that time, the surfaces to which the binder is attached are combined, pressed again with the hot roll, and then cooled to form a UD laminate.
(4) As the resin flow medium of the intermediate layer, a continuous strand mat (fabric form: glass continuous fiber nonwoven fabric, basis weight: 350 g / m ² ) manufactured by Nippon Sheet Glass Co., Ltd. was used.
(5) Among the upper and lower five-layer reinforcing fiber laminate 1 formed by the above laminating method, in order to improve the resin flow impregnation property except for the outermost layer of the upper three layers as the design surface, a diameter of 1.5 mm × (Protrusion) A through hole is formed in each of the reinforcing fiber laminates 1 using a perforation jig having a length of 6 mm, a pitch of 18 mm, and needles arranged in a grid pattern and a perforated plate heated to about 200 ° C. (As shown in FIGS. 5 and 6).

Comparative Example 1
FIG. 8 shows a multilayer laminate 13 having a conventional laminate configuration.
(1) All layers are carbon fiber “Trekka” T700 × 12K yarn unidirectional base sheet (width 1 m) (2) The unidirectional base sheets 20 and 22 are in the 0 degree direction, and the unidirectional base sheet 21 is 90 The unidirectional base sheet 40, 42 is oriented in the +45 degree direction, and the unidirectional base sheet 41 is oriented in the -45 degree direction.
(3) The layers are bonded to each other with a binder mainly composed of a thermoplastic resin. The same polyamide 6 nonwoven fabric as in Example 1 was used as the binder.
(4) The laminating method is a state of a unidirectional woven fabric in which a carbon fiber sheet is woven in advance as a weft yarn of polyamide 6 yarns at a pitch of 50 to 100 mm, and the binder is sandwiched between layers in a predetermined direction. Then, after laminating, each layer is fixed by hot pressing at about 200 ° C.

In the present invention, another laminated structure may be used. That is,
(1) One of the objects of the present invention is to improve the design surface. In particular, the object is to reduce the unevenness of the surface (design surface) due to the cured sink marks of the matrix resin caused by crimping of the reinforcing fiber fabric. Therefore, the objective is to dispose at least the outermost layer on the design surface side, not a woven fabric, but a unidirectional reinforcing fiber base layer without crimps, and is characterized in that it can be disposed without any inconvenience.
(2) As shown in FIG. 7, it is not necessary to make all the reinforcing fiber bases unidirectional reinforcing fiber bases. As shown in FIG. 9, at least only the outermost layer on the design side is unidirectional reinforcing fibers. A unit reinforcing fiber laminate 1 is used as the base material (the unit reinforcing fiber laminate 1 is disposed on the opposite side for balance), and most of the other parts are non-unidirectional reinforcing fiber base materials such as woven fabrics. A (fabric) 14 may be arranged. Of course, there is no problem with non-woven fabrics.

Example 2
(1) Both side surface layers use carbon fiber “Torayca” T700 × 12K yarn manufactured by Toray Industries, Ltd. as in Example 1, so that the basis weight of the unit reinforcing fiber laminate 1 is 300 g / m ^2. Unidirectionally oriented base materials that were aligned to a width of 1 m were arranged in two upper and lower layers. As for the orientation angle of the upper and lower layers, the crossing angle of each other is 90 degrees.
(2) However, the binder between the layers is a non-woven fabric made of polyphenylene sulfide, having a basis weight of 54 g / m ² , a melting point of 280 ° C., and a melt viscosity of 60 Pa · s (330 ° C., shear rate of 1000 / s).
(3) As reinforcing fibers other than the unit reinforcing fiber laminate 1, two layers of upper layer and one layer reinforcing fiber fabric were stacked on the lower part via the resin fluid medium 12 of the intermediate layer. The reinforcing fiber fabric is carbon fiber “TORAYCA” T300 × 6K yarn cloth [product number CO6644] manufactured by Toray Industries, Inc. (weight is about 300 g / m ² ).
(4) Moreover, the nylon 6 plain fabric [NB-20] made from NBC was used for the resin fluidized medium 12 of the intermediate layer.

Molding and Evaluation of Carbon Fiber Reinforced Plastic (CFRP) (1) The results of trial production of a CFRP molded body by the RTM molding method using the laminated base material (FIGS. 7 to 9) formed by the present invention and the prior art are shown. .

(2) Molding conditions and procedures are as follows.
(A) Shape and dimension of prototype The shape is a rectangular dish having a stepped section as shown in FIGS.
The dimensions are about 70cm square on the outer circumference and the maximum depth is 15cm. The plate thickness is 1.2-1.5mm.
(B) Molding procedure
1) The laminated base materials (11, 13, 15) shown in FIGS.
2) The planar laminated base materials (11, 13, 15) are shaped in advance into the shape of the molded body shown in FIG.
The method is not shown, but the laminated base material (11, 13, 15) is placed on an AL shaping die equivalent to the lower die 19 in FIGS. 10 and 11, and a bagging film is placed thereon. Cover the film and seal the film and mold surface, and slowly depressurize the film. At that time, the shaping mold is heated to the softening temperature of the thermoplastic resin used as the fixing material of the UD laminate by a heater built in the mold. The laminated base material (11, 13, 15) formed under reduced pressure and vacuum pressure is fixed to a shape (the shape of the molded body) formed by cooling the mold or cooling the laminated base material with cold air.
3) Trim the outer peripheral edge of the reinforcing fiber portion of the shaped laminated base material (11, 13, 15) to the size of the molded product. On the other hand, the resin fluidized medium disposed in the intermediate layer is trimmed to be slightly larger (about 5 to 20 mm) than the outer peripheral end of the reinforcing fiber portion.
4) Lay-up the laminated base material (11, 13, 15) whose outer peripheral edge has been trimmed after shaping on the lower mold 19 of the RTM mold in which a release agent is previously applied on the molding surface.
5) After laying up, the upper die 18 is lowered and pressed to bring the laminated base material (11, 13, 15) into close contact with the lower die 19.
6) After the upper and lower molds are in close contact and fastened, the inside of the mold is depressurized to eliminate the air in the mold.
7) The mold is heated from the beginning (about 100 ° C.), and immediately after the pressure reduction in the mold is completed, the epoxy resin is immediately injected into the mold with a resin pressure of about 0.5 MPa.
8) After injecting the resin and completing the impregnation of the laminated base material (11, 13, 15), heat and hold for about 20 minutes.
9) Thereafter, the upper mold 18 is raised and opened, and the molded products (16, 17) are removed from the lower mold 19.

(3) Comparison of molding time The resin flow impregnation time during RTM molding using the laminated base material 11 of the present invention was about 5 minutes. The resin flow impregnation time in the case of using another laminated substrate 15 of the present invention is shortened due to the use of a woven fabric in which the resin easily flows and the fact that there are few fixing materials between the layers that cause flow resistance. Minutes.

  On the other hand, when the laminated base material 13 of the prior art was used, 18.5 minutes were required for resin flow impregnation. The reason why the time required for the resin impregnation in the case of the prior art several times as long as that of the present invention is that (1) the resin flow medium that reduces the resin flow resistance in the surface direction of the substrate is not applied, (2 ) Adhesive material with high resin flow resistance is used for each UD base material, and (3) The gap between the stepped corners is large, the resin flow quickly flows into such a gap, and the resin flow balance is poor. And so on.

(4) Comparison of molded products Among the laminated base materials 11, 13, and 15, the one using the laminated base materials 11 and 15 configured in the present invention is an RTM-molded compact (see FIG. 10). 16) can be molded almost according to the shape of the mold. That is, the reinforcing fiber is firmly filled in the corner portion of the stepped portion. On the other hand, as shown in FIG. 11, the RTM molded body (17) using the laminated base material 13 constituted by the prior art has rounded reinforcing fibers at the corners of the stepped portion. Resin excess portions (not shown) are formed at the corners, thereby forming a mold shape. Since the excessive resin portion is not filled with reinforcing fibers, the strength is low and cracks are likely to occur.

(5) Comparison Consideration The reason why the excessive resin portion is generated in the laminated base material 13 of the prior art is fixed by the fixing material for each UD base material, and therefore it is difficult to deform from the stage of shaping by the reduced pressure (adhesion) The material is softened by heating, but its deformation resistance is large), but it is difficult to follow a shape with a small curvature, so that the reinforcing fiber substrate can be completely adhered to the stepped corner even in the RTM mold. The cause is not. On the other hand, the laminated base materials 11 and 15 constituted by the present invention are extremely flexible with respect to deformation because the UD base material fixed with a binder is at most two layers, and can follow a considerably small radius of curvature. The reinforcing fiber was able to reach the stepped corner of the mold completely.

The effects of the present invention including the results of the examples and comparative examples are summarized as follows.
(1) Improving the quality of the design surface Compared with the case of using a woven or non-woven fabric as the surface layer of the reinforcing fiber, the surface unevenness (roughness) was greatly reduced, and the smoothness was greatly improved. Specifically, the surface roughness of the FRP molded product is 0.8 to 3.5 μm for fabric use, although it differs considerably depending on the type of woven fabric base material for reinforcing fibers and the denier of the UD base material. In use, it is greatly improved to 0.3 to 1.2 μm.
(2) Improvement of formability Since the conventional UD base material laminate fixes each layer with a fixing material, even if it is heated at the time of shaping to soften the fixing material, the present invention (the binding material has two layers) The unit UD laminates do not generate deformation force with each other as in the case of a unit), so that the deformation resistance is large, that is, the present invention has a great advantage in shaping.
(3) Improvement of moldability
1) In the present invention, by arranging a resin fluidized layer having a low resin flow resistance around the middle of the laminated base material, the resin fluidity in the surface direction of the molded body is high, and the resin fluid impregnation is significant compared to the prior art. Time can be shortened. Furthermore, by providing a small-diameter through-hole in the base material, the resin flow impregnation can be further improved, and molding can be performed in a short time with almost no defects.
2) Due to the above effects, not only the impregnation time is shortened, but also when the resin containing the bubbles flows from the substrate surface direction to the thickness direction, the bubbles stay between the laminated substrates (so-called filtration function works). ) Since bubbles do not flow to the design surface, surface defects such as voids and pinholes are eliminated.
3) Since the deformation resistance of the laminated base material is small, the shapeability and the followability to the mold shape are high, and it becomes possible to easily form a complicated shape with a small curvature radius.

As an application field of the FRP molded object shape | molded by applying this invention, the following fields can be mentioned, for example.
(1) Transportation fields such as aircraft members, railway vehicle members, automobile members, motorcycle members, etc. (2) Sports equipment fields such as tennis rackets, golf shafts, skis, snowboards, boats, etc. (3) Windmill blades, robot arms, medical care Among general industrial fields such as equipment (X-ray heaven plate, etc.) and rolls, the required strength is high, and it is suitable for applications where surface design is required.

  The reinforcing fiber laminate and the manufacturing method thereof according to the present invention can be applied to molding of all reinforcing fiber plastics, and are particularly suitable for fields requiring high surface quality.

It is a disassembled perspective view of the reinforcing fiber laminated body (unit reinforcing fiber laminated body) which concerns on one embodiment of this invention. It is a disassembled perspective view of the reinforcing fiber laminated body (unit reinforcing fiber laminated body) which concerns on another embodiment of this invention. It is a fragmentary perspective view of the reinforcing fiber laminated body of FIG. It is a schematic block diagram which shows an example of the binder provision method. It is a schematic sectional drawing which shows an example of the drilling method. It is a schematic sectional drawing which shows the next step of FIG. It is sectional drawing of the reinforced fiber laminated body which concerns on another embodiment of this invention. It is sectional drawing of the conventional reinforcing fiber laminated body. It is sectional drawing of the reinforced fiber laminated body which concerns on another embodiment of this invention. It is a schematic block diagram which shows an example of shaping | molding using the reinforced fiber laminated body which concerns on this invention. It is a schematic block diagram which shows an example of shaping | molding using the conventional reinforcing fiber laminated body.

Explanation of symbols

1, 10 Reinforced fiber laminate (unit reinforcing fiber laminate)
2,4 Unidirectional reinforcing fiber base 3, 5 Binder 11, 15 Reinforcing fiber laminate (unit reinforcing fiber laminate in which a plurality of layers are laminated)
12 Resin fluid medium 14 Woven fabric
16 Molded body 18 Upper mold 19 Lower mold 31 Creel stand group 32 Speed regulation roll 33 UD base material 34 Hopper 35 Tacky fire coating head 36 Adhering heater 37 Cold air blowing means 38 Cover film 39 Winding roll

Claims (12)

Two layers of unidirectional reinforcing fiber base materials in which reinforcing fibers are aligned in one direction are stacked, and the two layers of unidirectional reinforcing fiber base materials are fixed to each other with a binder made of a thermoplastic resin interposed between layers. The unit reinforcing fiber laminate is formed , and a plurality of the unit reinforcing fiber laminates are laminated, and as the intermediate layer, a resin fluid medium having a resin flow resistance lower than that of the unit reinforcing fiber laminate is a unit reinforcing fiber laminate. A reinforcing fiber laminate, which is disposed at a position between unit reinforcing fiber laminates adjacent to each other in the laminating direction of the body, and in which another reinforcing fiber substrate is further laminated. The reinforcing fiber laminate according to claim 1 , wherein the resin fluid medium is made of a synthetic fiber network. Wherein over substantially the entire area of the reinforcing fiber laminate, needle hole penetrating at least the consisting unidirectional reinforcing fiber base material of the two-layer reinforced fiber laminate in the thickness direction is perforated claim 1 or 2 Reinforced fiber laminate as described in 1. The reinforcing fiber laminate according to any one of claims 1 to 3 , wherein the binder is made of a thermoplastic resin compatible with a matrix resin impregnated in the reinforcing fiber laminate. The reinforcing fiber laminate according to any one of claims 1 to 4 , wherein the reinforcing fibers of the unidirectional reinforcing fiber base are made of carbon fibers. A binder made of a thermoplastic resin is applied on a unidirectional reinforcing fiber base material in which reinforcing fibers are aligned in one direction, and another unidirectional reinforcing fiber base material is stacked on the binding material. A unit reinforcing fiber laminate is formed by fixing two layers of unidirectional reinforcing fiber bases to each other through a material, and a plurality of the unit reinforcing fiber laminates are laminated, and the unit reinforcing fiber is used as an intermediate layer. A resin flow medium having a resin flow resistance lower than that of the laminate is disposed at a position between the unit reinforcing fiber laminates adjacent to each other in the laminating direction of the unit reinforcing fiber laminate, and another reinforcing fiber base is also laminated. The manufacturing method of a reinforced fiber laminated body characterized by the above-mentioned. The method for producing a reinforcing fiber laminate according to claim 6 , wherein a synthetic fiber network is used as the resin fluid medium. The manufacturing method of the reinforced fiber laminated body of Claim 6 or 7 which provides the said binder in the form of a woven fabric or a nonwoven fabric. The manufacturing method of the reinforced fiber laminated body in any one of Claims 6-8 which provides the said binder in the form of a short fiber, a granule, or powder. Over substantially the entire area of the reinforcing fiber layer, perforating the needle hole penetrating at least the consisting unidirectional reinforcing fiber base material of the two-layer reinforced fiber laminate in the thickness direction, any claim 6-9 A method for producing a reinforcing fiber laminate according to claim 1. The method for producing a reinforced fiber laminate according to any one of claims 6 to 10 , wherein a thermoplastic resin that is compatible with a matrix resin impregnated in the reinforced fiber laminate is used as the binder. The manufacturing method of the reinforced fiber laminated body in any one of Claims 6-11 using carbon fiber as a reinforced fiber of the said unidirectional reinforcing fiber base material.

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