JP2008307692A - Fiber-reinforced plastic and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber-reinforced plastic having excellent handleability, resin impregnation properties and shapability even in a complicated shape having a three-dimensional shape and the like and having excellent mechanical characteristics and quality, and to provide a manufacturing method capable of efficiently producing the fiber-reinforced plastic. <P>SOLUTION: At least two sheets, in which many continuous reinforcing fiber yarns are arrayed in parallel, are arranged so that the reinforcing fiber yarns may cross and a cloth consisting of a thermoplastic resin (A) may be interposed between the sheets, to form a laminate. A fiber-reinforced plastic formed by molding a multiaxial molding material in which the laminates are integrated by a stitching thread consisting of a thermoplastic resin (B) or by the thermoplastic resin (A) and a fiber-reinforced plastic prepared by molding a fiber-reinforced thermoplastic resin base material which has monofilament-like discontinuous reinforcing fibers dispersed at random in a thermoplastic resin (C) are integrated in the form of continuity of the thermoplastic resin (A) and the thermoplastic resin (C). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a fiber reinforced plastic capable of easily and efficiently obtaining a fiber reinforced plastic having excellent mechanical properties and quality even in a complicated shape having a three-dimensional shape and the like, and a method for producing the same. More specifically, the present invention relates to a fiber reinforced plastic obtained by compression molding a multiaxial molding material composed of continuous reinforcing fibers and a fiber reinforced thermoplastic resin base material composed of discontinuous reinforcing fibers, and a method for producing the same.

  Conventionally, fiber reinforced plastics (hereinafter abbreviated as FRP) using carbon fibers or glass fibers as reinforced fibers are excellent in specific strength and specific elastic modulus, and thus have been used in various applications.

  As a method of molding such FRP, a prepreg in which a reinforcing fiber base material is impregnated with a matrix resin in advance is used, this is set in a mold, covered with a bag film, heated and pressurized in an autoclave, and the thermosetting resin is cured. In general, there are widely used autoclave molding methods and vacuum injection molding methods in which a reinforced fiber base material in a dry state is set in a mold, and a liquid thermosetting resin is injected under a reduced pressure (vacuum state) in the mold Are known.

  However, in the autoclave molding method and the vacuum injection molding method, it is necessary to laminate the base materials, and it is necessary to cover with a bag film and reduce the pressure to a vacuum. In particular, in the vacuum injection molding, it is necessary to inject a thermosetting resin. Further, in these methods, the molding time (cycle time) per process including the above-described steps becomes too long, and it is difficult to adapt to, for example, automobile members having a large number of production. Furthermore, these methods are all suitable for simple shapes such as flat surfaces and quadratic surfaces, but in order to form complex shapes such as ribs and bosses, the base material is shaped into those shapes. However, it takes time and labor, and the molding time becomes longer.

  For the problem of molding time, for example, there is a method of omitting the lamination process when forming into FRP by using a multi-axis stitch base material that is laminated in advance and sewed with stitch yarn and integrated. It has been proposed (for example, Patent Document 1). However, such a technique requires a step of injecting a matrix resin (thermosetting resin) prepared separately and further curing it, so that the effect is not sufficient.

  On the other hand, as a means for omitting the resin injection / curing step, a molding material (for example, Patent Document 2) in which synthetic resin fibers serving as a matrix and reinforcing fibers are integrated in advance and used as the multiaxial stitch base, A molding material (for example, Patent Document 3) in which a film serving as a matrix is inserted between layers of a multiaxial stitch base has been proposed.

  However, the method described in Patent Document 2 is inferior in resin impregnation property because it is a molding material in which synthetic resin fibers serving as a matrix are arranged in a reinforcing fiber layer in a multiaxial stitch base, and impregnation with resin Has a problem that a high pressure is required, and in the method described in Patent Document 3, it is difficult for the sewing thread to penetrate the film, or the laminated sheet is formed into a complicated shape such as a quadratic curved surface. There has been a problem that the resin film cannot follow the shape when it is shaped and wrinkles are generated. Furthermore, since both of these are continuous fibers in the form of reinforcing fibers, it is very difficult to form complex shapes such as ribs and bosses.

That is, in the conventional techniques including Patent Documents 1 to 3, a molding material that has excellent handling properties, resin impregnation properties, and shapeability, and can obtain FRP with excellent mechanical properties and quality with high productivity. And no FRP derived from it has been found and such techniques are craved.
US Patent Application Publication No. 2005/0059309 Japanese Patent Application Laid-Open No. 2001-073241 JP 2004-346175 A

  An object of the present invention is to solve the above-mentioned problems of the prior art, and even if it is a complicated shape having a three-dimensional shape, etc., it has excellent handling properties, resin impregnation properties, and shaping properties, An object of the present invention is to provide a fiber reinforced plastic having excellent characteristics and quality and a production method capable of efficiently obtaining the fiber reinforced plastic.

In order to achieve the above object, the present invention employs the following configuration. That is,
(1) At least two sheets in which a large number of continuous reinforcing fiber yarns are arranged in parallel so that the reinforcing fiber yarns intersect and at least a fabric-like body made of the thermoplastic resin (A) Fiber reinforcement formed by molding a multiaxial molding material that is arranged between the sheets to constitute a laminate, and the laminate is integrated with a stitch yarn made of a thermoplastic resin (B) or a thermoplastic resin (A). A plastic resin and a fiber reinforced plastic formed by molding a fiber reinforced thermoplastic resin base material in which monofilamentous and discontinuous reinforcing fibers are randomly dispersed in the thermoplastic resin (C) are thermoplastic resin (A ) And the thermoplastic resin (C) are integrated in a continuous form.

  (2) At least two sheets in which a large number of continuous reinforcing fiber yarns are arranged in parallel so that the reinforcing fiber yarns intersect and at least a fabric-like body made of the thermoplastic resin (A) A multi-axial molding material which is disposed between the sheets to form a laminate, and the laminate is integrated with a stitch yarn made of the thermoplastic resin (B) or the thermoplastic resin (A); A method for producing a fiber-reinforced plastic, comprising simultaneously compressing and molding a fiber-reinforced thermoplastic resin base material in which discontinuous reinforcing fibers are randomly dispersed in a thermoplastic resin (C).

  (3) At least two sheets in which a large number of continuous reinforcing fiber yarns are arranged in parallel, and at least a fabric-like body made of the thermoplastic resin (A) so that the reinforcing fiber yarns intersect each other A multi-axis molding material in which a laminated body is disposed between the sheets to constitute a laminated body, and the laminated body is integrated with a stitch yarn made of a thermoplastic resin (B) or a thermoplastic resin (A), is compression-molded. A fiber-reinforced thermoplastic resin base material in which fibrous and discontinuous reinforcing fibers are randomly dispersed in the thermoplastic resin (C) is a continuous form of the thermoplastic resin (A) and the thermoplastic resin (C). A method for producing a fiber-reinforced plastic, characterized by molding so as to be integrated.

  (4) The absolute value of the difference between the solubility parameter (SP value) δA of the thermoplastic resin (A) and the solubility parameter (SP value) δC of the thermoplastic resin (C) is 3 or less. The manufacturing method of the fiber reinforced plastic as described in said (2) or (3).

(5) The basis weight of the reinforcing fiber yarn in each sheet is in the range of 50 to 350 g / m ² , and the basis weight of the fabric-like body made of the thermoplastic resin (A) is in the range of 15 to 250 g / m ² . The fiber-reinforced plastic according to any one of (2) to (4), wherein the fiber-reinforced thermoplastic resin base material has a reinforcing fiber weight content of 25 to 80 wt%. Production method.

  (6) The absolute value of the difference between the solubility parameter (SP value) δA of the thermoplastic resin (A) and the solubility parameter (SP value) δB of the thermoplastic resin (B) is 3 or less ( The manufacturing method of the fiber reinforced plastic in any one of 2)-(5).

  (7) When the melting point of the thermoplastic resin (A) is TmA and the melting point of the thermoplastic resin (B) is TmB, TmA and TmB are expressed by the formula (TmB-150) ≦ TmA ≦ (TmB-20). The method for producing a fiber-reinforced plastic according to any one of (2) to (6), wherein the relationship is satisfied.

  (8) When the melting point of the thermoplastic resin (A) is TmA and the melting point of the thermoplastic resin (B) is TmB, TmA and TmB have the relationship of the formula (TmB-20) <TmA <(TmB + 20). The method for producing a fiber-reinforced plastic according to any one of (2) to (6), wherein the method is satisfied.

  (9) When the melting point of the thermoplastic resin (A) is TmA and the melting point of the thermoplastic resin (C) is TmC, the relationship of TmA and TmC is expressed by the following formula (TmC-20) <TmA <(TmC + 20). The method for producing a fiber-reinforced plastic according to any one of (2) to (8), wherein:

  According to the present invention, a fiber reinforced plastic having excellent handling properties, resin impregnation properties, and formability, and excellent mechanical properties and quality even in a complicated shape having a three-dimensional shape or the like at the time of molding. It can be obtained efficiently.

  The present invention can efficiently produce a fiber reinforced plastic (FRP) having excellent handling characteristics, resin impregnation properties, and formability, and having excellent mechanical properties and quality even in a complicated shape having a three-dimensional shape or the like. As a result of earnest study on the production method for obtaining, a fiber reinforced heat composed of a multiaxial molding material in which continuous reinforcing fibers and a cloth-like body are integrated by stitch yarn or thermoplastic resin (A), and discontinuous reinforcing fibers. When the plastic resin base material is integrated in a continuous form, it has been found that such problems can be solved all at once.

  Next, the present invention will be further described with reference to the drawings using examples.

  FIG. 1 is a schematic perspective view showing one embodiment of the multiaxial molding material in the present invention. FIG. 2 is a schematic perspective view showing one embodiment of the fiber-reinforced thermoplastic resin base material in the present invention. FIG. 3 is a schematic cross-sectional view of the multiaxial molding material and the fiber-reinforced thermoplastic resin base material in the present invention before compression molding. FIG. 4 is a schematic cross-sectional view showing one embodiment of the FRP of the present invention.

  As shown in FIG. 4, the FRP of the present invention comprises at least two sheets in which a large number of continuous reinforcing fiber yarns Y are arranged in parallel, such that the reinforcing fiber yarns intersect and is thermoplastic. A fabric-like body made of a resin (A) is disposed at least between the sheets to constitute a laminate, and the laminate is a stitch yarn 6 (or thermoplastic resin (A), made of a thermoplastic resin (B), not shown. A fiber reinforced plastic formed by molding the multiaxial molding material 8 integrated with the fiber, and a fiber reinforced thermoplastic in which monofilamentous and discontinuous reinforcing fibers are randomly dispersed in the thermoplastic resin (C). The fiber reinforced plastic formed by molding the resin base 12 is integrated in a continuous form of the thermoplastic resin (A) and the thermoplastic resin (C).

  Here, the continuation of the reinforcing fiber in the present invention represents an aspect in which the reinforcing fiber is continuous over the entire length in the fiber direction, and the discontinuity is a concept used in contrast to the continuity, and the fiber length is limited. However, about 1 to 15 mm is preferably used from the viewpoint of moldability. Next, the reinforcing fiber yarn represents a mode in which a large number of reinforcing fibers are bundled, and the number of reinforcing fibers per yarn may be in the range of 1000 to 50000. It is preferable from the viewpoint of handleability. On the other hand, the monofilament-like reinforcing fiber is an embodiment in which the reinforcing fibers are not bundled but one by one, but the reinforcing fibers may be fixed together by a sizing agent or entanglement. This represents an embodiment in which the number of reinforcing fibers per single fibrous reinforcing fiber is less than 100. The intersection of reinforcing fiber yarns in the present invention represents an aspect in which the reinforcing fiber yarns are oriented in different directions, and represents that the absolute value of the angle formed by these directions is 10 to 170 °. Also, the integration of the thermoplastic resin (A) and the thermoplastic resin (C) in a continuous form means that both resins are physically or chemically adsorbed at the resin interface. Physical adsorption refers to a state in which resins are mixed and entangled at the molecular level, a state in which they are adsorbed by intermolecular force, and a state in which they are adsorbed by an anchor effect. Indicates a covalent bond. Furthermore, the random dispersion in the present invention represents an embodiment in which the orientation of the reinforcing fiber is not biased, and the orientation parameter (fp) of the fiber-reinforced thermoplastic resin substrate is within the range of −0.25 to 0.25. Represents that.

The orientation parameter (fp) of the fiber reinforced thermoplastic resin substrate is measured by the following method. A part of the fiber reinforced thermoplastic resin substrate is cut out, and a cross section perpendicular to the thickness is polished to prepare an observation test piece. The test piece obtained by polishing a depth portion of 100 μm or less from the surface of the fiber-reinforced thermoplastic resin substrate is observed with an optical microscope, and 400 reinforcing fibers are selected at random. The reinforcing fibers are generally elliptical on the polished surface, and the major axis direction of the ellipse is taken as the fiber orientation direction. Next, a reference straight line as an angle reference is arbitrarily set, and all angles formed by the orientation direction of the selected reinforcing fibers with respect to the reference line (hereinafter, may be abbreviated as orientation angle α) are measured. The orientation angle α is measured by measuring the angle in the counterclockwise direction with respect to the reference line. Using this orientation angle α, an orientation parameter (fp) is calculated by the following equation.
Fp = 2 × Σ (cos ² αi × Ni / Ntotal) −1
Αi: measured orientation angle (unit: °) (i = 1, 2, 3,..., N)
Ni: Frequency of fibers with orientation angle αi (unit: book) (i = 1, 2, 3,..., N)
Ntotal: number of fibers whose orientation angle was measured (400)
The FRP production method of the present invention comprises at least two sheets in which a large number of continuous reinforcing fiber yarns Y are arranged in parallel as shown in FIG. 1 so that the reinforcing fiber yarns Y intersect each other, and , A fabric-like body 5 made of a thermoplastic resin (A) is arranged at least between the sheets to form a laminate, and the laminate is a stitch yarn 6 (or thermoplastic resin (A) made of a thermoplastic resin (B). ), A multiaxial molding material 8 integrated by (not shown), and a fiber in which single fiber-like and discontinuous reinforcing fibers 10 as shown in FIG. 2 are randomly dispersed in the thermoplastic resin (C) 11 The reinforced thermoplastic resin substrate 12 is compression-molded simultaneously.

  As shown in FIG. 1, the multiaxial molding material 8 comprises a laminate in which at least two sheets of reinforcing fiber yarns Y arranged in parallel are laminated so that the reinforcing fiber yarns Y intersect. Yes. Sheet 1 is a layer in which reinforcing fiber yarns Y are arranged in parallel in the longitudinal direction of the multiaxial molding material, and sheet 2 is a layer in which reinforcing fiber yarns Y are parallel to the longitudinal direction of the multiaxial molding material at + 45 °. The sheet 3 is a layer in which the reinforcing fiber yarns Y are arranged in parallel to the longitudinal direction of the multiaxial molding material at 90 °, and the sheet 4 is composed of the reinforcing fiber yarns Y in the multiaxial direction. It is a layer arranged in parallel at −45 ° with respect to the longitudinal direction of the molding material. Here, the longitudinal direction of the multiaxial molding material refers to a direction in which the multiaxial molding material is taken up by a winding device or a direction in which the multiaxial molding material is taken up by a take-up device.

  In the multiaxial molding material 8 shown in FIG. 1, the number of sheets of reinforcing fiber yarns is four, but these are examples of the multiaxial molding material of the present invention. Is not limited to this. A preferred laminated structure in the present invention is a mirror-symmetric laminated so as not to warp when formed into FRP, and the preferred laminated number is 3 to 12 from the balance between handleability and resin impregnation. Within range.

  As the form of the cloth-like body 5 in the multiaxial molding material 8 used in the present invention, the form is not particularly limited as long as it can be handled as one sheet, and the nonwoven fabric, film, mat, mesh, woven fabric, Various forms such as a knitted fabric can be selected. Especially when it is in the form of non-woven fabric, it is inexpensive as a material, has moderate deformability, has excellent handleability in the manufacturing process of multi-axis molding material, can reduce the load on the needle during stitching, etc. To preferred. As a nonwoven fabric, what was manufactured by the card | curd method, the melt blow method, the spun bond method, the papermaking method etc. is mentioned, for example. Such a non-woven fabric may be formed on a support such as a release paper or a film, or may be handled alone, but those that can be handled independently are available at a lower cost. Since the nonwoven fabric produced by the above method is a combination of discontinuous thermoplastic fibers, it has excellent formability when applied to multiaxial molding materials and smooth needle penetration in stitches (continuous stitching). Sex). In addition, a fabric in which continuous fibers are aligned to form a non-woven structure can be given as an example, and one or a combination of two or more of these can also be used. Among these, it is preferable to use those manufactured by the melt blow method or the spunbond method from the viewpoint of material cost, and those manufactured by the card method from the viewpoint of formability.

  A laminated body is integrated by the stitch thread | yarn which consists of a thermoplastic resin (B), or a thermoplastic resin (A). In the case where it is desired to promote the impregnation of the thermoplastic resin (A) into the sheet, the former embodiment using a stitch yarn forming a resin impregnation flow path is preferable. On the other hand, when it is desired to express extremely high mechanical properties, the latter embodiment in which the damage of the reinforcing fiber yarn can be minimized by using the stitch yarn is preferable.

  Examples of the thermoplastic resin (A) constituting the fabric body 5 of the multiaxial molding material 8 used in the present invention include “polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT)”. , Polyethylene naphthalate (PENp), polyester such as liquid crystal polyester, polyolefin such as polyethylene (PE), polypropylene (PP), polybutylene, polyoxymethylene (POM), polyamide (PA), polyphenylene sulfide (PPS), polyketone Fluoropolymers such as (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyethernitrile (PEN), polytetrafluoroethylene, and liquid crystal polymers (LCP) ”and other crystalline resins,“ in addition to styrene resins, polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene ether (PPE), polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), polyethersulfone, polyarylate (PAR) "and other amorphous resins, phenolic resins, phenoxy resins, polystyrenes, polyolefins, Examples thereof include thermoplastic elastomers such as polyurethane, polyester, polyamide, polybutadiene, polyisoprene, fluorine, and acrylonitrile, and thermoplastic resins selected from copolymers and modified products thereof. In the present invention, at least one of these can be employed as a preferred thermoplastic resin (A). More preferably, from the viewpoint of impregnating the thermoplastic resin between the carbon fibers, a crystalline resin is used, and the mechanical properties of FRP can be enhanced.

  The form of the stitch yarn 6 in the multiaxial molding material 8 used in the present invention may be any of a filament and a spun yarn, but is preferably a multifilament yarn in order to obtain the smoothness of the substrate surface. In the case of a multifilament yarn, by pressing the multiaxial molding material at the time of shaping or molding, the arrangement position of the filaments can be moved, and the thickness of the multifilament yarn can be reduced. Examples of the thermoplastic resin (B) constituting the stitch yarn 6 include “polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PENp), liquid crystal polyester and the like. Polyolefins such as polyester, polyethylene (PE), polypropylene (PP), polybutylene, polyoxymethylene (POM), polyamide (PA), polyphenylene sulfide (PPS), polyketone (PK), polyetherketone (PEK), poly Fluorine resins such as ether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether nitrile (PEN), polytetrafluoroethylene, and crystalline resins such as liquid crystal polymer (LCP), Enol resins, phenoxy resins, thermoplastic elastomers such as polystyrenes, polyolefins, polyurethanes, polyesters, polyamides, polybutadienes, polyisoprenes, fluorines, and acrylonitriles, copolymers thereof, Examples thereof include thermoplastic resins selected from modified products.

  As shown in FIG. 2, the fiber reinforced thermoplastic resin base material 12 is a single fiber and discontinuous reinforcing fibers 10 are randomly dispersed in the thermoplastic resin 11. Examples of the form of the thermoplastic resin 11 include a particulate form and a fibrous form, or they may be melted and aggregated. The multiaxial molding material 8 and the fiber reinforced thermoplastic resin base material 12 are overlapped as shown in FIG. 3 and simultaneously compression molded. As a form of superposition, the multiaxial molding material 8 and the fiber reinforced thermoplastic resin base material 12 may be the same size, or the fiber reinforced thermoplastic resin base material 12 is partially formed with respect to the multiaxial molding material 8. An arranged form may be used. The compression molding means is not particularly limited, but press molding is preferred because of the fast molding time.

  Examples of the thermoplastic resin (C) 11 in the fiber reinforced thermoplastic resin substrate 12 used in the present invention include “polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate”. Polyester such as phthalate (PENp), liquid crystal polyester, polyolefin such as polyethylene (PE), polypropylene (PP), polybutylene, polyoxymethylene (POM), polyamide (PA), polyphenylene sulfide (PPS), polyketone (PK) , Fluorinated resins such as polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether nitrile (PEN), polytetrafluoroethylene, Crystalline resins such as MER (LCP), “in addition to styrene resins, polycarbonate (PC), polymethyl methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene ether (PPE), polyimide (PI), polyamide Amorphous resin such as imide (PAI), polyetherimide (PEI), polysulfone (PSU), polyethersulfone, polyarylate (PAR), etc., phenolic resin, phenoxy resin, polystyrene, polyolefin , Polyurethane-based, polyester-based, polyamide-based, polybutadiene-based, polyisoprene-based, fluorine-based, and acrylonitrile-based thermoplastic elastomers, and thermoplastic resins selected from copolymers and modified materials thereof. In the present invention, at least one of these can be employed as the preferred thermoplastic resin (C) 11. More preferably, from the viewpoint of impregnating the thermoplastic resin between the carbon fibers, a crystalline resin is used, and the mechanical properties of FRP can be enhanced.

  From another viewpoint, the method for producing FRP of the present invention includes at least two sheets in which a large number of continuous reinforcing fiber yarns Y are arranged in parallel as shown in FIG. And a fabric-like body 5 made of a thermoplastic resin (A) is arranged at least between the sheets to form a laminate, and the laminate 6 is a stitch yarn 6 made of a thermoplastic resin (B). (Or thermoplastic resin (A), not shown), after compression molding of the multiaxial molding material 8, single fiber-like and discontinuous reinforcing fibers as shown in FIG. C) A fiber-reinforced thermoplastic resin base material 12 randomly dispersed in 11 is molded so that the thermoplastic resin (A) and the thermoplastic resin (C) are integrated in a continuous form. That is, it is divided into two steps, a pre-process for forming a multiaxial molding material and a post-process for forming a fiber-reinforced thermoplastic resin substrate. Although the molding process is divided into two stages, the productivity is somewhat inferior, but when, for example, an FRP partially made of a fiber reinforced thermoplastic resin base material is arranged, the fiber reinforced thermoplastic resin group is only formed in the part. It becomes easy to mold the material, that is, the amount of the fiber-reinforced thermoplastic resin substrate used is small, and the cost is excellent. The means for compression-molding the multiaxial molding material in the previous step is not particularly limited, but press molding is preferred because of the fast molding time. As a method of forming the fiber-reinforced thermoplastic resin substrate later, press molding may be used as in the case of the multiaxial molding material, but other molding methods can be appropriately selected according to circumstances. To obtain more easily and efficiently, FRP made of multi-axial molding material molded in the previous process is placed in an injection molding machine and molded to be integrated by injection molding a fiber reinforced thermoplastic resin substrate. May be performed. In addition, FRP made of a fiber reinforced thermoplastic resin base material previously molded into a shape corresponding to a rib or the like is multiaxial by vibration fusion, ultrasonic fusion, high frequency fusion, hot plate fusion, laser fusion, etc. Examples of the method include fixing to an FRP made of a molding material, and these methods may be used as appropriate.

  In the FRP production method of the present invention, the absolute value of the difference between the solubility parameter (SP value) δA of the thermoplastic resin (A) and the solubility parameter (SP value) δC of the thermoplastic resin (C) is 3 or less. Preferably there is. When the absolute value of the difference in SP value is greater than 3, the compatibility of both components is low, the adhesiveness at the interface between the thermoplastic resin (A) and the thermoplastic resin (C) is low, and peeling occurs at the interface. May occur. A more preferable range of the absolute value is 2.5 or less, and more preferably 2 or less. The SP value in the present invention is determined by the value of the repeating unit of the polymer at a temperature of 25 ° C. determined by the method of Fedors. The method is described in F.A. Fedors, Polym. Eng. Sci. 14 (2), 147 (1974).

In the manufacturing method of FRP of this invention, it is preferable that the fabric weight of the reinforcing fiber yarn in each sheet | seat of a multiaxial molding material exists in the range of 50-350 g / m < ² >. More preferably, it is in the range of 90 to 190 g / m ² . When the basis weight of the reinforcing fiber yarns in each sheet is less than 50 g / m ² , not only the quality when the gap between the reinforcing fiber yarns adjacent to each other is made FRP but also becomes inferior, The gap causes a decrease in mechanical properties. In addition, when the basis weight of the reinforcing fiber yarns in each sheet exceeds 350 g / m ² , a portion where adjacent reinforcing fiber yarns overlap with each other is formed, so that the surface of the multiaxial molding material is uneven and the layer is thick. Therefore, the formability becomes inferior. Furthermore, when the layer becomes thick, it is necessary to apply an excessive external pressure when the cloth-like body composed of the thermoplastic resin is melted and completely impregnated, and the excessive external pressure causes the reinforcing fiber yarn to bend. Will arise.

Moreover, it is preferable that the fabric weight of the thermoplastic resin (A) is in the range of 15 to 250 g / m ² . More preferably, it exists in the range of 40-100 g / m < ² >. When the fabric weight is less than 15 g / m ² , the amount of the thermoplastic resin is relatively insufficient with respect to the amount of the reinforcing fiber yarn, and it becomes difficult to sufficiently impregnate. In order to avoid this problem, if the basis weight of the reinforcing fiber yarn is lowered beyond the above range, a gap is formed between the reinforcing fiber yarns, so that the strength when the FRP is used is not only lowered, but also the quality. May get worse. On the other hand, when the basis weight of the fabric-like body exceeds 250 g / m ² , the content of the reinforcing fiber yarn is relatively reduced, and sufficient strength cannot be expressed when FRP is used. In order to avoid this problem, if the basis weight of the reinforcing fiber yarn sheet is increased beyond the range of the present invention, the reinforcing fiber yarns overlap each other, resulting in unevenness on the surface, and inferior formability and quality. In addition, an excessive external pressure is required when the resin is impregnated, and the reinforcing fiber yarn may be bent. In addition, the basis weight of the reinforcing fiber yarn and the fabric-like body of each sheet is cut out in accordance with JIS R7602 (1989), paragraph 5.5, the local fusion is released, and the multiaxial molding material is disassembled. The values measured for the reinforcing fiber yarns and fabrics of each sheet.

  Furthermore, it is preferable that the weight content of the reinforcing fiber of the fiber-reinforced thermoplastic resin base material is 25 to 80 wt%. More preferably, it is in the range of 35 to 75 wt%. If the weight content of the discontinuous reinforcing fibers is less than 25 wt%, the reinforcing effect of the reinforcing fibers is reduced, and there are cases where sufficient strength cannot be achieved when the FRP is used. On the other hand, if the weight content of the discontinuous reinforcing fibers exceeds 80 wt%, the impregnation of the thermoplastic resin between the reinforcing fibers becomes insufficient, and the mechanical properties may be extremely reduced. Since the properties are lowered, an unfilled portion may occur, which is not preferable.

  When stitch yarn is used in the FRP manufacturing method of the present invention, the difference between the solubility parameter (SP value) δA of the thermoplastic resin (A) and the solubility parameter (SP value) δB of the thermoplastic resin (B) The absolute value is preferably 3 or less. Similar to the relationship between the thermoplastic resin (A) and the thermoplastic resin (C) described above, when the absolute value of the difference in SP value is larger than 3, the compatibility of both components is low, and the thermoplastic resin (A) And the adhesiveness at the interface between the thermoplastic resin (B) is lowered. When a load is applied to the FRP, the adhesion at the interface is low, so that slight peeling occurs at the interface, and the repeated loading causes the peeling to become a starting point, which is not preferable. A more preferable range of the absolute value is 2.5 or less, and more preferably 2 or less.

  Moreover, it is preferable that the melting point TmA of the thermoplastic resin (A) and the melting point TmB of the thermoplastic resin (B) satisfy the relationship of (TmB-150) ≦ TmA ≦ (TmB-20) (hereinafter referred to as aspect A). Called). The melting point refers to a value measured by DSC (Differential Scanning Calorimeter) according to JIS K7121 (1987) at a heating rate of 20 ° C./min in an absolutely dry state. In the present invention, the glass transition temperature + 100 ° C. obtained by the above measuring method is simply regarded as the melting point for those that do not exhibit a melting point (for example, an amorphous polymer).

  When the stitch yarn is used, when the melting points of the thermoplastic resin (A) and the thermoplastic resin (B) are in the relationship of the aspect A, the fabric-like body can be melted first when the FRP is formed. Thus, while the cloth-like body is melted and the thermoplastic resin (A) is impregnated in the layers of the reinforcing fiber yarns, each layer composed of the reinforcing fiber yarns is not melted. In addition to preventing the disorder of the orientation of the reinforcing fiber yarns, the through holes in the sheet thickness direction of the reinforcing fiber yarns formed by the stitch yarns serve as resin impregnation channels, and the molten thermoplastic resin ( There is an unexpected effect that the impregnation of A) is remarkably improved. Furthermore, since the cloth-like body is melted first and the resin is impregnated in each layer, the interlayer thickness in which the cloth-like body is inserted is thinned, the constraint by the stitch yarn is loosened, and each layer is easily sheared and deformed. Generation can be suppressed. For this reason, it is possible to obtain a high-quality FRP in which the orientation of the reinforcing fiber yarn is aligned and excellent mechanical properties can be expressed.

  In addition, when the fabric-like body composed of the thermoplastic resin (A) is also arranged in at least one of the outermost layers of the multiaxial molding material, the stitch yarn is used for laminating the plurality of multiaxial molding materials. It can be said that this is a preferred embodiment in the present invention, because the multi-axial molding material can be integrated (for example, a form of a preform) by partially melting the fabric-like body without melting it.

  As a specific combination of the embodiment A satisfying this relationship, for example, the thermoplastic resin (A) is polyamide 11, polyamide 12, or copolymer polyamide (for example, polyamide 6/66/12, polyamide 610/12, polyamide 6 / 66/610/12, etc.), and the thermoplastic resin (B) is polyamide 6 or polyamide 66, or the thermoplastic resin (A) is polyamide 6 and the thermoplastic resin (B) is polyamide 66. In some combinations, the thermoplastic resin (A) is a copolymerized polyester, the thermoplastic resin (B) is a polyester, the thermoplastic resin (A) is a copolymerized polyolefin, and the thermoplastic resin (B) is polyethylene or The combination that is polypropylene, the thermoplastic resin (A) is polyethylene, and the thermoplastic resin (B) is polypropylene. Combinations pyrene and the like. In the case of the above combination, when a resin similar to the thermoplastic resin (A) and the thermoplastic resin (B) is used, the adhesiveness between the two is excellent, and thus excellent mechanical properties can be expressed.

  Further, when the thermoplastic resin (A) is a polyolefin and the thermoplastic resin (B) is a combination of polyester, the difference in melting point between the thermoplastic resin (A) and the thermoplastic resin (B) can be increased. Since it can be easily impregnated, there is an advantage of excellent moldability.

  From another viewpoint, the melting point TmA of the thermoplastic resin (A) and the melting point TmB of the thermoplastic resin (B) satisfy the relationship of (TmB-20) <TmA <(TmB + 20), that is, thermoplasticity. It is preferable to use those in which the melting point TmA of the resin (A) and the melting point TmB of the thermoplastic resin (B) are substantially the same (hereinafter referred to as Aspect B).

  Further, the melting point TmA of the thermoplastic resin (A) and the melting point TmC of the thermoplastic resin (C) satisfy the relationship of (TmC-20) <TmA <(TmC + 20), that is, the thermoplastic resin (A) It is preferable to use those having a melting point TmA substantially equal to the melting point TmC of the thermoplastic resin (C). When the melting points of the thermoplastic resin (A) and the thermoplastic resin (C) are substantially the same, the two resins are easily integrated in a continuous form. When the melting point is out of the above range, when the multiaxial molding material and the fiber reinforced thermoplastic resin base material are compression molded at the same time, the resin on one side may melt first and the molding may not be successful. In the case where molding is performed in two stages, that is, a pre-process for molding the molding material and a post-process for molding the fiber-reinforced thermoplastic resin base material, the resins may not be compatible with each other, which is not preferable.

  Examples of continuous and discontinuous reinforcing fibers used in the present invention include carbon fibers, graphite fibers, glass fibers, and organic fibers such as aramid, paraphenylenebenzobisoxazole, polyvinyl alcohol, polyethylene, polyarylate, and polyimide. It is possible to use one or a combination of two or more of these. Among these, carbon fibers are excellent in specific strength and specific elastic modulus and are preferably used. The carbon fiber has a tensile strength of 4 GPa or more and 7 GPa or less, preferably 4.5 GPa or more and 6.5 GPa or less, and a tensile elastic modulus of 200 GPa or more and 500 GPa or less, particularly suitable for a structural material.

The tensile strength of the yarn can be determined according to a tensile test method specified in JIS R-7601 after impregnating a carbon fiber yarn with a resin having the following composition and curing at 130 ° C. for 35 minutes.
(Resin composition)
-Alicyclic epoxy resin (3,4-epoxycyclohexylmethyl-3,4-epoxy-cyclohexyl-carboxylate) 100 parts by weight-3 parts by weight of boron trifluoride monoethylamine-4 parts by weight of acetone The tensile modulus can be obtained from the slope of the load-elongation curve by performing a tensile test in the same manner as the above-described tensile strength measurement method.

The reinforcing fiber yarn used for the multiaxial molding material can be either untwisted or twisted. However, in terms of mechanical properties such as tensile strength and compressive strength, it is substantially untwisted (1 turn / m Less). From this point of view, in the production of the multiaxial molding material in the present invention, the reinforcing fiber yarns may be longitudinally unwound and mixed with unwinding twist, but the horizontal unwinding will not cause unwinding twisting. Thus, it is preferable that the reinforcing fiber yarn is present in the multiaxial molding material in a substantially non-twisted state (less than 1 turn / m). By laterally unraveling, not only is it easy to reliably obtain a high-quality FRP even in the basis weight within the scope of the present invention, but also the reinforcing fiber volume fraction Vf and mechanical characteristics can be enhanced. In particular, if the basis weight of the reinforcing fiber yarn in each sheet is 190 g / m ² or less, a gap (gap) between the reinforcing fiber yarns is easily formed in the sheet, and the quality of the FRP may be inferior. Spider is preferred. The above effect is remarkably exhibited when the fineness of the reinforcing fiber yarn is within the following range. The fineness of the reinforcing fiber yarn is preferably 500 to 7,000 tex, more preferably 1,000 to 2,000 tex. When the fineness is too small, there is almost no problem that the fiber yarn is twisted, and the effect of the present invention may not be exhibited. Further, since the fiber yarn is expensive and many fiber yarns having such a fineness are used, the multiaxial molding material itself is also expensive. On the other hand, if the fineness is too large, for example, when obtaining a multi-axis molding material having a low basis weight of reinforcing fiber yarns per layer of 100 g / m ² or less, the yarn width is likely to fluctuate with a slight force and stable. It may be difficult to maintain the finished yarn width.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not particularly limited thereto.

The raw materials in Examples and Comparative Examples, and intermediate materials composed of these raw materials are as follows.
<Multi-axis molding material>
Reinforcing fiber yarn / PAN-based carbon fiber yarn: 12,000 filaments, fineness 800 tex, tensile strength 4,900 MPa, tensile elastic modulus 240 GPa, 0 turns / m, sizing agent 0.5% by weight.
Stitch yarn / stitch yarn A: polyamide 66, 10 filament, fineness 33 dtex, melting point 255 ° C., SP value 13.6.
-Stitch yarn B: polytetrafluoroethylene, 10 filaments, fineness 56 dtex, melting point 327 ° C., SP value 6.2
Fabric-like / nonwoven fabric A: Polyamide 6, basis weight 80 g / m ² , melting point 220 ° C., SP value 13.5.
Non-woven fabric B: Polyamide 12, basis weight 80 g / m ² , melting point 178 ° C., SP value 13.0.
Film C: Polyamide 6, basis weight 80 g / m ² , melting point 220 ° C., SP value 13.5.

A multiaxial molding material having a width of 1.3 m was prepared by the following procedure. That is, the laminated body which has the nonwoven fabric A in each of between each sheet | seat comprised with the reinforced fiber yarn and outermost layer was formed.
(1) The nonwoven fabric A arranged in the outermost layer was continuously arranged on the belt conveyor so that the longitudinal directions of the nonwoven fabric A and the belt conveyor were parallel. Such a belt conveyor continues to move in the longitudinal direction (0 ° direction) at a constant speed (1 m / min in the present embodiment) while laminating the subsequent layers of reinforcing fiber yarns and the nonwoven fabric. It was intended to be transported continuously.
(2) On the nonwoven fabric A, the reinforcing fiber yarns that have been laterally unwound so as not to mix the untwisted twist are set to −45 ° with respect to the longitudinal direction (the direction in which the belt conveyor conveys, 0 ° direction). A -45 ° sheet was formed in parallel and arranged to be 150 g / m ² . The arrangement of the reinforcing fiber yarns of the −45 ° sheet was performed by a carriage device. The carriage device in this step reciprocates in the -45 ° direction, and is a device that arranges reinforcing fiber yarns on the belt conveyor during the forward movement (or backward movement), and the belt conveyor moves in the longitudinal direction. Control was performed so that the reinforcing fiber yarns do not overlap each other and are arranged next to each other in order in synchronization with the conveying speed.
(3) The second nonwoven fabric A is placed on the −45 ° sheet, and the reinforcing fiber yarns are parallel to the longitudinal direction at + 90 ° with respect to the longitudinal direction in the same manner as in the −45 ° sheet formation. And a + 90 ° sheet was formed so as to be 150 g / m ² .
(4) A third non-woven fabric A is placed on the + 90 ° sheet, and the reinforcing fiber yarns are parallel to the longitudinal direction at + 45 ° in the same manner as in the −45 ° sheet formation. And it arranged so that it might become 150 g / m < ² >, and the +45 degree sheet | seat was formed.
(5) The fourth nonwoven fabric A is arranged on the + 45 ° sheet layer, and the reinforcing fiber yarns are parallel to the longitudinal direction at 0 ° in the same manner as in the −45 ° sheet formation. And a 0 ° sheet was formed by arranging so as to be 150 g / m ² .
(6) The 5th nonwoven fabric A was arrange | positioned on the said 0 degree sheet | seat, and the laminated body was formed.

Subsequently, the laminate on the belt conveyor formed as described above was stitched together with the stitch yarn A and integrated. In such stitches, the stitch yarn A was unwound by an unwinding device and knitted while allowing the needle to penetrate the laminate. The knitting structure of the stitch yarn was an irregular 1/1 tricot knitting combining a chain knitting and a 1/1 tricot knitting. Nonwoven fabric A was excellent in needle penetrability, and the fibers of the nonwoven fabric were not entangled with the needle.
<Fiber-reinforced thermoplastic resin substrate>
Reinforcing fiber yarn / PAN-based carbon fiber yarn, 12,000 filaments, fineness 800 tex, tensile strength 4,200 MPa, tensile elastic modulus 230 GPa, sizing agent 1.5% by weight.
Thermoplastic resin / resin A: Polyamide 6, melting point 220 ° C., SP value 13.5.
Resin B: polypropylene, melting point 165 ° C., SP value 8.0.

Two types of fiber reinforced thermoplastic resin base materials were prepared by the following procedure.
(1) A PAN-based carbon fiber yarn was cut with a cartridge cutter to obtain a chopped yarn having a fiber length of 6.4 mm.
(2) The pellet-like polyamide 6 resin was immersed in liquid nitrogen for 3 minutes, and freeze-pulverized with a pulverizer. The obtained pulverized particles were classified with a 14 mesh (opening diameter 1.18 mm) sieve, and the pulverized particles that passed through the 14 mesh sieve were further classified with a 60 mesh (opening diameter 0.25 mm) sieve and remained on the 60 mesh sieve. The pulverized particles were collected to obtain 14 to 60 mesh particles A.
(3) 10 l of a 1.5 wt% aqueous solution of a surfactant (manufactured by Wako Pure Chemical Industries, Ltd., “sodium n-dodecylbenzenesulfonate” (product name)) is stirred to prepare a previously foamed dispersion. did.
(4) Into this dispersion, 430 g of the chopped yarn and 630 g of particles A were added and stirred for 10 minutes, and then poured into a paper machine having a paper surface of length 1000 mm × width 1000 mm, sucked and degassed. A fiber reinforced thermoplastic resin web was obtained.
(5) After drying this fiber reinforced thermoplastic resin web at a temperature of 100 ° C. for 2 hours, the entire fiber reinforced thermoplastic resin web is preheated to a temperature of 280 ° C. And pressed at 1 MPa.
(6) It arrange | positioned between the cooling boards temperature-controlled at the temperature of 30 degreeC, and it cold-pressed at 1 Mpa, and obtained the fiber reinforced thermoplastic resin base material P of length 1000mm, width 1000mm, and thickness 1mm. The weight content of carbon fibers was 40 wt%, and the orientation parameter (fp) was 0.05.
(1) PAN-based carbon fiber yarn is fed into the crosshead die while extruding the pellet-shaped resin A in a crosshead die attached to the tip of the resin A in a single-screw extruder while being sufficiently melted and kneaded. Then, the resin A was sufficiently impregnated in the carbon fiber yarn. Here, the crosshead die refers to a device that impregnates a molten resin or the like into a continuous fiber bundle in the die while opening the fiber bundle.
(2) The continuous fibrous strand thus obtained was cooled and then cut into 7 mm with a cutter to obtain a fiber reinforced thermoplastic resin substrate Q. The weight content of the carbon fibers was 20 wt%, and the orientation parameter (fp) was 0.19.

Example 1
Multiaxial molding material: 4 sheets are mirror-symmetrically laminated so that the 0 ° sheet is in the center, and fiber reinforced thermoplastic resin base material A1: 2 sheets are overlapped, and a hemispherical quadratic curved surface as shown in FIG. The multi-axis molding material was arranged on the outer side of the spherical surface with respect to the mold 13 having The convex mold has a rib groove 14 having the shape shown in FIG. 6 at the position shown by the dotted line in FIG. The wrinkles generated while melting the resin in the nonwoven fabric and the fiber-reinforced thermoplastic resin base material were stretched while following the mold while being heated to 230 ° C., and pressed (pressed) at 25 MPa for 240 seconds. While pressurizing, the mold temperature was cooled to 50 ° C. and then the pressure was released and demolded to obtain FRP having ribs.
The absolute value of the difference between the SP value of the multiaxial molding material fabric and the SP value of the fiber reinforced thermoplastic resin base material is 0, and the SP value of the multiaxial molding material fabric and the stitch yarn The absolute value of the difference from the SP value is 0.1.
The obtained FRP was filled with fibers and resin up to the end of the rib, and the cross section was observed with an optical microscope. As a result, the resin was impregnated into the inside of the reinforcing fiber yarn, and voids were hardly generated. Further, regarding the surface quality, the fiber orientation disorder and the surface unevenness were slightly generated, but the generation of wrinkles was not observed, and the surface quality was generally good.

(Example 2)
Multiaxial molding material: After six sheets are mirror-symmetrically laminated so that the 0 ° sheet is in the center, and placed in a mold having the same shape as the mold used in Example 1 and not having a rib groove, FRP was obtained under the same conditions as in Example 1. Subsequently, the obtained FRP was placed in a mold having rib grooves similar to the mold used in Example 1, and then a fiber reinforced thermoplastic resin substrate at a barrel temperature of 260 ° C. and a mold temperature of 80 ° C. FRP having a rib was obtained by injection molding A2.
The absolute value of the difference between the SP value of the multiaxial molding material fabric and the SP value of the fiber reinforced thermoplastic resin base material is 0, and the SP value of the multiaxial molding material fabric and the stitch yarn The absolute value of the difference from the SP value is 0.1.
The obtained FRP was filled with fibers and resin up to the end of the rib, and the cross section was observed with an optical microscope. As a result, the resin was impregnated into the inside of the reinforcing fiber yarn, and voids were hardly generated. Further, regarding the surface quality, the fiber orientation disorder and the surface unevenness were slightly generated, but the generation of wrinkles was not observed, and the surface quality was generally good.

(Example 3)
FRP having ribs in the same manner as in Example 1 except that the multi-axial molding material is nonwoven fabric B, the fiber reinforced thermoplastic resin base material is resin B, and the mold temperature is 200 ° C. Got. The weight content of carbon fibers in the fiber-reinforced thermoplastic resin substrate was 40 wt%, and the orientation parameter (fp) was -0.06.
The absolute value of the difference between the SP value of the cloth-like body of the multiaxial molding material and the SP value of the resin of the fiber-reinforced thermoplastic resin base material is 5, and the SP value of the cloth-like body of the multiaxial molding material and the stitch yarn The absolute value of the difference from the SP value is 0.6.
The obtained FRP was filled with fibers and resin up to the end of the rib, and the cross section was observed with an optical microscope. As a result, the resin was impregnated into the inside of the reinforcing fiber yarn, and voids were hardly generated. Further, regarding the surface quality, the fiber orientation disorder and the surface unevenness were slightly generated, but the generation of wrinkles was not observed, and the surface quality was generally good. However, when a load was applied to the obtained FRP, partial peeling was confirmed at the interface between the FRP made of a multiaxial molding material and the FRP made of a fiber-reinforced thermoplastic resin substrate.

Example 4
An FRP having ribs was obtained in the same manner as in Example 1 except that the stitch yarn of the multiaxial molding material was changed to the stitch yarn B.
The absolute value of the difference between the SP value of the multiaxial molding material fabric and the SP value of the fiber reinforced thermoplastic resin base material is 0, and the SP value of the multiaxial molding material fabric and the stitch yarn The absolute value of the difference from the SP value is 7.3.
The obtained FRP was filled with fibers and resin up to the tip of the rib, and when the cross section was observed with an optical microscope, the resin was impregnated into the inside of the reinforcing fiber yarn and there was almost no void, but the stitch yarn Peeling was observed at the interface between the resin and the resin. Further, regarding the surface quality, the fiber orientation disorder and the surface unevenness were slightly generated, but the generation of wrinkles was not observed, and the surface quality was generally good.

(Example 5)
An FRP having ribs was obtained in the same manner as in Example 1 except that the film C was used as the multiaxial molding material.
The absolute value of the difference between the SP value of the multiaxial molding material fabric and the SP value of the fiber reinforced thermoplastic resin base material is 0, and the SP value of the multiaxial molding material fabric and the stitch yarn The absolute value of the difference from the SP value is 0.1.
The obtained FRP was filled with fibers and resin up to the end of the rib, and the cross section was observed with an optical microscope. As a result, the resin was impregnated into the inside of the reinforcing fiber yarn, and voids were hardly generated. Further, the surface quality was generally good, but the fiber orientation was disordered and the surface was slightly uneven, and the wrinkles that were not seen in Example 1 were slightly generated.

(Comparative Example 1)
An FRP having ribs was obtained in the same manner as in Example 1 except that a fiber reinforced thermoplastic resin base material was not used and only 6 sheets of multiaxial molding material were mirror-symmetrically laminated so that the 0 ° sheet was in the center.
The obtained FRP was filled with fibers and resin only about 20% of the ribs.

  Applications of the FRP obtained by the manufacturing method of the present invention are required for strength, rigidity and light weight, such as bicycle parts, sports members such as golf heads, automobile members such as doors and seat frames, robot arms, etc. There are mechanical parts. In particular, the present invention can be preferably applied to automobile parts such as seat panels and seat frames that require molding followability of complicated shapes in addition to strength and light weight.

It is a schematic perspective view which shows one embodiment of the multiaxial molding material in this invention. It is a schematic perspective view which shows one embodiment of the fiber reinforced thermoplastic resin base material in this invention. It is a schematic sectional drawing which shows one embodiment of the multiaxial molding material and the fiber reinforced thermoplastic resin base material before the compression molding in this invention. It is a schematic sectional drawing which shows one embodiment of the fiber reinforced composite material of this invention. It is the schematic which shows an example of a metal mold | die shape, (A) is a side view, (B) is a top view. It is sectional drawing which shows an example of the groove shape with which the metal mold | die was equipped in order to form a rib.

Explanation of symbols

Y: Reinforcing fiber yarn 1: Sheet with reinforcing fiber yarns arranged in parallel in the longitudinal direction 2: Sheet with reinforcing fiber yarns arranged in parallel at + 45 ° with respect to the longitudinal direction 3: Reinforcing fiber yarns Sheets arranged in parallel at 90 ° to the longitudinal direction 4: Sheets of reinforcing fiber yarns arranged in parallel at −45 ° to the longitudinal direction 5: Fabric-like material between layers 6: Stitch yarn 7: Needle 8: Multiaxial molding material 9: Outer fabric layer 10: Monofilamentous and discontinuous reinforcing fiber 11: Thermoplastic resin 12: Fiber reinforced thermoplastic resin base material 13: Mold 14: Rib groove

Claims (9)

At least two sheets in which a large number of continuous reinforcing fiber yarns are arranged in parallel, and a fabric-like body made of the thermoplastic resin (A) is at least between the sheets so that the reinforcing fiber yarns intersect. And a fiber reinforced plastic formed by molding a multiaxial molding material in which the laminate is integrated with a stitch yarn made of the thermoplastic resin (B) or the thermoplastic resin (A). A fiber reinforced plastic formed by molding a fiber reinforced thermoplastic resin base material in which monofilamentous and discontinuous reinforcing fibers are randomly dispersed in the thermoplastic resin (C) is formed of the thermoplastic resin (A) and the heat. A fiber-reinforced plastic, characterized in that the plastic resin (C) is integrated in a continuous form. At least two sheets in which a large number of continuous reinforcing fiber yarns are arranged in parallel, and a fabric-like body made of the thermoplastic resin (A) is at least between the sheets so that the reinforcing fiber yarns intersect. And a multiaxial molding material in which the laminate is integrated with a stitch yarn made of the thermoplastic resin (B) or the thermoplastic resin (A), and a single fiber and discontinuous A method for producing a fiber-reinforced plastic, comprising simultaneously compression-molding a fiber-reinforced thermoplastic resin base material in which reinforcing fibers are randomly dispersed in a thermoplastic resin (C). At least two sheets in which a large number of continuous reinforcing fiber yarns are arranged in parallel, and a fabric-like body made of the thermoplastic resin (A) is at least between the sheets so that the reinforcing fiber yarns intersect. A multi-axial molding material in which the laminated body is integrated with a stitch yarn made of the thermoplastic resin (B) or the thermoplastic resin (A). A fiber reinforced thermoplastic resin base material in which discontinuous reinforcing fibers are randomly dispersed in the thermoplastic resin (C) is integrated in a continuous form of the thermoplastic resin (A) and the thermoplastic resin (C). A method for producing a fiber-reinforced plastic, characterized by being molded as described above. The absolute value of the difference between the solubility parameter (SP value) δA of the thermoplastic resin (A) and the solubility parameter (SP value) δC of the thermoplastic resin (C) is 3 or less. Or the manufacturing method of the fiber reinforced plastic of 3. The basis weight of the reinforcing fiber yarns in each sheet is in the range of 50 to 350 g / m ² , and the basis weight of the fabric-like body made of the thermoplastic resin (A) is in the range of 15 to 250 g / m ² , And the weight content rate of the reinforced fiber of the said fiber reinforced thermoplastic resin base material is 25-80 wt%, The manufacturing method of the fiber reinforced plastic in any one of Claims 2-4 characterized by the above-mentioned. 6. The absolute value of the difference between the solubility parameter (SP value) δA of the thermoplastic resin (A) and the solubility parameter (SP value) δB of the thermoplastic resin (B) is 3 or less. The manufacturing method of the fiber reinforced plastic in any one of. When the melting point of the thermoplastic resin (A) is TmA and the melting point of the thermoplastic resin (B) is TmB, TmA and TmB satisfy the relationship of the formula (TmB-150) ≦ TmA ≦ (TmB-20). A method for producing a fiber-reinforced plastic according to any one of claims 2 to 6. When the melting point of the thermoplastic resin (A) is TmA and the melting point of the thermoplastic resin (B) is TmB, TmA and TmB satisfy the relationship of the formula (TmB-20) <TmA <(TmB + 20). The method for producing a fiber-reinforced plastic according to any one of claims 2 to 6. When the melting point of the thermoplastic resin (A) is TmA and the melting point of the thermoplastic resin (C) is TmC, TmA and TmC satisfy the relationship of the formula (TmC-20) <TmA <(TmC + 20). The method for producing a fiber-reinforced plastic according to any one of claims 2 to 8.

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