JP5157391B2 - Reinforced fiber substrate, laminate and fiber reinforced resin - Google Patents

Description

  The present invention relates to a reinforced fiber substrate, a laminate, and a fiber reinforced resin comprising the same.

  More specifically, the present invention relates to a reinforcing fiber base material having excellent handling properties and excellent impregnation properties of a matrix resin. Moreover, this invention relates to the fiber reinforced resin excellent in the mechanical characteristics shape | molded from the reinforced fiber base material or laminated body which has the outstanding handleability.

  A fiber reinforced resin obtained by impregnating a reinforced fiber with a matrix resin has been used mainly for aviation, space, and sports applications because it satisfies the required characteristics such as excellent mechanical properties and light weight. As these typical production methods, an autoclave molding method is known. In such a molding method, a fiber reinforced resin is molded by laminating a prepreg in which a matrix resin is impregnated in advance into a group of reinforcing fiber bundles and laminating the prepreg on a mold and heating and pressing in an autoclave. The prepreg used here has an advantage that an extremely reliable fiber reinforced resin can be obtained when it is used, but there is a problem that the production costs are high.

  On the other hand, examples of the molding method excellent in the productivity of the fiber reinforced resin include injection molding such as a resin transfer molding method (RTM). Such an RTM is obtained by laminating a fabric composed of bundles of reinforcing fibers not pre-impregnated with a matrix resin (dry) on a mold and injecting a liquid low-viscosity matrix resin into the matrix later. A fiber reinforced resin is formed by impregnating and solidifying the resin. However, the injection molding method is excellent in the productivity of the fiber reinforced resin, but since the matrix resin needs to have a low viscosity, compared to the fiber reinforced resin molded from the high viscosity matrix resin used for the prepreg, There was a problem with inferior mechanical properties.

  In response to such a problem, by a technique of arranging a thermoplastic resin layer having a gap between layers of a preform laminated with a reinforcing fiber base material, or a technique of applying a resin blended with an epoxy resin and thermoplastic resin particles on a fabric Techniques have been proposed in which the mechanical properties (delamination resistance, delamination toughness, etc.) of the fiber reinforced resin obtained by injection molding are improved (see, for example, Patent Documents 1 to 4).

However, in the above proposal, the thermoplastic resin layer arranged to improve the mechanical properties, or a resin blended with an epoxy resin and thermoplastic resin particles causes a problem that the impregnation property of the matrix resin is significantly reduced. The problem of obtaining fiber reinforced resin with high productivity, which is the original purpose, could not be achieved. Alternatively, even if the impregnation property can be maintained, the mechanical properties of the fiber reinforced resin are not sufficiently improved. That is, in the prior art, regarding the resin material applied to the dry fabric, although the configuration in the thickness direction of the fabric is a particularly important factor for expressing high mechanical properties, there is no description relating thereto. The above proposal is not disclosed at all, and the reinforced fiber base material and laminate capable of achieving both the mechanical properties and the impregnation property of the matrix resin are not achieved by the above proposal. Yes.
JP 2002-249605 A International Publication No. 00/061363 Pamphlet Japanese Patent Laid-Open No. 2003-082117 JP 2005-022396 A

  The object of the present invention is to solve such problems of the prior art. Specifically, the fiber has good matrix resin impregnation properties and excellent mechanical properties (particularly, compressive strength after application of impact). It is intended to provide a reinforced fiber base material and laminate that are not only capable of obtaining a reinforced resin with high productivity but also excellent in handleability (particularly, shape stability, tackiness when laminated). Further, the present invention intends to provide a fiber reinforced resin obtained from such a reinforced fiber base material and laminate.

  The present invention employs the following means in order to solve such problems.

(1) In a form in which a resin material has a gap within a range of 2 to 20% by weight of the fabric at least on one side surface of the fabric composed of a group of reinforcing fiber yarns formed by arranging reinforcing fiber yarns in parallel. The reinforced fiber base material, wherein each of the resin materials is a buried portion having a thickness of 15 μm or more and 97 μm or less, in which a plurality of single yarns of the reinforcing fiber yarns penetrate the resin material. And the thickness of the embedded portion of the resin material is the thickness of the fabric constituting the reinforcing fiber base, and the thickness of the buried portion of the resin material is fixed in a form having a thickness on the surface of the fabric and an exposed portion having an average thickness of 10 to 250 μm. A reinforcing fiber substrate characterized in that it is thinner and 50 to 100% of the total projected area of the resin material is fixed to the surface of the fabric in the above form.

(2) the thickness of the fabric is 70～400Myuemu, and the thickness of the embedded portion of the resin material is in the range of 50% or less of the thickness of the fabric constituting the reinforcing fiber substrate, the (1) The reinforcing fiber substrate as described.

Strengthening (3) the resin material, is scattered on the surface of the fabric, and the average diameter of the resin material as seen from the surface of the fabric is Ru der less 1 mm, according to (1) or (2) Fiber substrate.

  (4) The reinforcing fiber substrate according to any one of (1) to (3), wherein the resin material is disposed on both surfaces of the fabric.

  (5) The main component of the resin material is one or a mixture of two or more thermoplastic resins selected from the group consisting of polyethersulfone, polyamide, polyvinyl formal, phenoxy resin and polycarbonate. The reinforcing fiber substrate according to any one of to (4).

  (6) Any of the above (1) to (4), wherein the main component of the resin material is one or a mixture of two or more thermosetting resins selected from epoxy, unsaturated polyester, vinyl ester and phenol A reinforcing fiber substrate according to any one of the above.

  (7) The reinforcing fiber substrate according to any one of (1) to (6), wherein the resin material has a melt viscosity at a shear rate of 1000 / s in a range of 100 to 1000 Pa · s.

  (8) The fabric extends in a direction intersecting with the reinforcing fiber yarns and the reinforcing fiber yarn group in which the reinforcing fiber yarns are aligned in parallel in one direction, and the fineness is the fineness of the reinforcing fiber yarns. The reinforcing fiber substrate according to any one of (1) to (7), which is a unidirectional woven fabric composed of an auxiliary fiber yarn group that is 1/5 or less.

  (9) The fabric is a bi-directional woven fabric composed of the reinforcing fiber yarn group arranged in one direction and the reinforcing fiber yarn group arranged in one direction in a different direction. )-Reinforcing fiber base material in any one of (7).

  (10) At least two layers of the reinforcing fiber yarns arranged in one direction and the reinforcing fiber yarn groups arranged in one direction in different directions are cross-laminated and the fineness is a reinforcing fiber yarn. The reinforcing fiber base material according to any one of (1) to (7), wherein the reinforcing fiber base material is a stitch base material that is stitched and integrated with an auxiliary fiber yarn group that is 1/5 or less of the length.

( 11 ) A fiber-reinforced resin comprising the reinforcing fiber substrate according to any one of (1) to (10) as a reinforcing fiber.

( 12 ) The reinforcing fiber volume content is in the range of 53 to 65%, and the normal temperature compressive strength after impact application described in SACMA-SRM-2R-94 is 240 MPa or more, as described in ( 11 ) above. Fiber reinforced resin.

According to the reinforcing fiber substrate or laminate of the present invention, the resin material attached to the fabric embeds the single yarn of the reinforcing fiber yarn and is physically and firmly bonded. A fiber reinforced resin excellent in mechanical properties of strength can be obtained. The strong bonding of the resin material also contributes to excellent handling properties such as form stability and tackiness when laminated.
In addition, according to the reinforcing fiber substrate or laminate of the present invention, the resin material attached between the layers of the fabric or laminate adheres in a form having a gap, and not only increases the area of the resin material in the plane, Since the height is also increased in the thickness direction, the impregnation property of the matrix resin is good, and the fiber reinforced resin can be obtained with high productivity.
By impregnating such a reinforcing fiber substrate or laminate with a matrix resin, a fiber reinforced resin having excellent mechanical properties can be obtained with high productivity.

  The reinforcing fiber base material of the present invention is a resin material in a range of 2 to 20% by weight of the fabric on the surface of at least one side surface of the fabric composed of reinforcing fiber yarns formed by arranging reinforcing fiber yarns in parallel. Is a reinforcing fiber base disposed in a form having a gap, and each of the resin materials includes an embedded portion in which a plurality of single yarns of the reinforcing fiber yarns penetrates the resin material; Fixed in a form having an exposed portion having a thickness on the surface of the fabric, the embedded portion thickness of the resin material being thinner than the thickness of the fabric constituting the reinforcing fiber substrate, and the total projected area of the resin material 50 to 100% is bonded to the surface of the fabric in the above-described manner.

  The fabric used for the reinforcing fiber base of the present invention includes a group of reinforcing fiber yarns formed by aligning reinforcing fiber yarns in parallel. Here, arranging in parallel means arranging adjacent reinforcing fiber yarns side by side so as not to substantially intersect or cross each other. Preferably, adjacent reinforcing fiber yarns are continuously arranged at a constant interval of 20 to 200% of the reinforcing fiber yarn width, or arranged so as to overlap with a certain width within a range not exceeding the reinforcing fiber yarn width. Refers to that. Here, “substantially not intersecting or crossing” means that even if there is a meandering fiber yarn and an overlapping portion in the width direction occurs, it exceeds the fiber yarn width of the narrower one of the adjacent fiber yarns. If they do not overlap, it is not included in this. The term “constant” here means that the width and interval are within a range of ± 50% from the average value. More preferably, when two adjacent reinforcing fiber yarns are approximated to a straight line within a length range of 100 mm, the angle formed by the approximated straight line is arranged to be 5 ° or less, more preferably It is arrange | positioning so that it may become 2 degrees or less. Here, approximating the yarn to a straight line means that a straight line is formed by connecting a starting point and an end point of 100 mm.

  As a form of the cloth, any form can be applied as long as it can be handled as a cloth, and various forms such as a woven fabric, a knitted fabric, and a sheet can be used. For example, in a state where the reinforcing fiber yarns are aligned in parallel, the auxiliary fiber yarns may be a woven structure inserted so as to cross the reinforcing fiber yarns in a direction orthogonal or oblique to the arrangement direction of the reinforcing fiber yarns, or the auxiliary fiber yarns It may be a warp knitting (for example, 1/1 tricot knitting structure) or a knitting structure arranged in a weft knitting, or may be formed by a support (particle, mesh, non-woven fabric, woven fabric, knitted fabric, etc.) It may be a held non-woven structure or a combination thereof (details will be described later).

  The reinforced fiber base material of the present invention refers to a material in which a resin material is disposed in a range of 2 to 20% by weight on at least one surface of a fabric. A preferred range is 3 to 17% by weight, and a more preferred range is 4 to 14% by weight. By disposing the resin material in the above range, deformation of the reinforcing fiber yarn and the auxiliary fiber yarn is suppressed, and the form stability of the fabric is brought about. Furthermore, tackiness (adhesiveness) between them can be obtained at the time of heating when laminating reinforcing fiber bases to be described later. As a result, it is possible to obtain a reinforced fiber base material excellent in handleability. Such handleability cannot be obtained when the resin material is less than 2% by weight. On the other hand, when the resin material exceeds 20% by weight, there is a problem that the volume content of the reinforcing fiber becomes too low when the fiber reinforced resin is used, and the mechanical properties may be deteriorated. Further, when the resin material exceeds 20% by weight, there is a problem that when the reinforcing fiber base materials are bonded by heating, the resin material is deformed to block the flow path of the matrix resin and impede impregnation.

  Here, the resin material needs to be disposed on the surface of the fabric in a form having a gap. The resin material is disposed on the surface of the fabric in a form having a gap. The covering portion and the non-covering portion are made of the resin material so that the ratio of the projected area of the resin material to the reinforcing fiber base is 5 to 80%. Indicates that the resin material is disposed in a mixed manner. The projected area of the resin material refers to the area ratio covered by the resin material within the unit area of the reinforcing fiber substrate when viewed from a direction substantially perpendicular to the surface of the reinforcing fiber substrate. Here, “substantially perpendicular to the surface of the reinforcing fiber substrate” means a direction perpendicular to the plane of the reinforcing fiber substrate placed in a plane. As a method for measuring the projected area, for example, the image of the reinforcing fiber base imaged by a CCD camera or the like is calculated from the number of pixels by separating the image from the luminance distribution into a resin material and a cloth by image processing. Here, the imaging magnification is 50 times, an image in a measurement range described later is acquired with a resolution of 10 dots / 1 mm or more, and a material having a diameter of 0.5 mm or more is measured as a resin material on the image (or equivalent) The operation may be performed by data processing on a computer). When the boundary between the resin material and the fabric is unclear, it is preferable to use excitation light as a light source because the boundary can be emphasized by receiving fluorescence emitted from the resin material. In addition, if measurement from image processing is difficult, the image acquired with a scanner or digital camera may be enlarged, and the contour of the resin material visually traced may be measured manually or traced. A thing may be calculated by image processing. In any measurement method, an average value of values calculated within a range of 300 mm × 300 mm extracted from any 10 locations of the reinforcing fiber base is used as a projection area, and the measuring method is appropriately selected according to the reinforcing fiber base. To do.

  The ratio of the covering area where the resin material is arranged in such a form is preferably in the range of 5 to 50%, and it is preferable that the gaps (non-covering portions) are more uniformly dispersed. Examples of the resin material include a porous film, a short fiber nonwoven fabric, a cut fiber, and a granular material. Among these, a granular material is preferable. By taking this form, when the above amount of the resin material is arranged on the surface of the fabric, it functions as a so-called spacer that forms a space between layers of the reinforcing fiber bases adjacent to each other in the thickness direction. When the fiber reinforced resin is molded by molding, it acts as a matrix resin flow path, so that not only the matrix resin impregnation is facilitated, but also the impregnation speed is increased, and the fiber reinforced resin has excellent productivity. (This is called an interlayer flow path forming effect). When the resin material is arranged on the surface of the fabric in a form having no gap (that is, when the resin material is attached so as to cover the entire surface of the fabric), it also becomes a barricade that blocks the flow path of the matrix resin. There is a problem of impeding resin impregnation. In this case, not only the resin flow path between the layers is not formed, but also the flow of the resin in the thickness direction is blocked. As a result, an unimpregnated portion is formed in the fiber reinforced resin.

  In addition, when the resin material of the above amount and form is disposed on at least one surface, when an impact or the like is applied to the fiber reinforced resin obtained by laminating and molding the reinforcing fiber base, the resin material However, by inhibiting the development of cracks in the fiber reinforced resin, particularly in the laminated interlayer, it also exhibits a function as a so-called crack stopper that keeps the fiber reinforced resin from being damaged to a minimum when subjected to an impact. In particular, in a fiber reinforced resin obtained by laminating and molding a reinforced fiber base material, a significant decrease in residual compressive strength after impact is a problem, and in this problem, the resin material is at least on one surface. A high effect is expressed by being arranged. In other words, when the fiber reinforced resin is subjected to an impact, by suppressing the expansion of damage, the fiber reinforced resin after the impact is also less effective in reducing the mechanical properties (particularly the compressive strength) (this) Is called the interlayer reinforcement effect).

  Further, in the aspect of fixing the resin material in the reinforcing fiber base of the present invention, each of the resin materials is a buried portion in which a plurality of single yarns of the reinforcing fiber yarns penetrates at least the resin material, It is necessary to be fixed in a manner having an exposed portion having a thickness on the surface of the fabric. Although the form of the embedded part and the exposed part will be described later, by fixing in this manner, the interlayer reinforcing effect of the resin material in the fiber reinforced resin can be expressed with extremely high efficiency. On the other hand, outside this mode (when only the exposed part and only the buried part are formed), the resin material cannot function effectively in the fiber reinforced resin, and the function as a crack stopper is fully expressed in the fiber reinforced resin. Can not.

  Moreover, the thickness of the embedding part of the resin material in the reinforcing fiber base of the present invention needs to be thinner than the thickness of the fabric constituting the reinforcing fiber base. By having such a thickness of the embedded portion, the excellent handling property and the resin impregnation property of the reinforcing fiber base material are compatible without impairing the interlayer reinforcing effect of the resin material. On the other hand, when the thickness of the embedded portion is the same as the thickness of the fabric constituting the reinforcing fiber base, the embedded portion penetrates the reinforcing fiber yarn in the thickness direction, so that the matrix resin is impregnated when molding the fiber reinforced resin. It inhibits and the resin impregnation property of a reinforced fiber base material will be reduced.

  In the reinforced fiber base material of the present invention, it is necessary that 50 to 100% of the total projected area of the resin material is fixed to the surface of the fabric in the above-described manner. By fixing 50 to 100% of the total projected area of the resin material in the above-described manner, the effect of the resin material (particularly the interlayer reinforcement effect) can be more reliably and widely applied over the entire surface of the reinforcing fiber base. Yes (details on the effect of this requirement will be described later). On the other hand, when the resin material fixed in the above mode is less than 50% of the total projected area of the resin material, the effect of the resin material (particularly, the interlayer strengthening effect) works only locally and the variation becomes large. .

  Hereinafter, the reinforcing fiber substrate of the present invention will be described with reference to the drawings.

  FIG. 1 is a perspective view schematically showing one embodiment of the reinforcing fiber base of the present invention.

  In FIG. 1, the reinforcing fiber base 1 is composed of a fabric 2 and a resin material 3 fixed to the fabric 2. The fabric 2 is composed of reinforcing fiber yarns 4 and auxiliary fiber yarns 5, and the reinforcing fiber yarns 4 and auxiliary fiber yarns 5 form the fabric 2 with a non-woven structure. The fabric 2 is mainly a reinforcing fiber yarn 4 and is a kind of fabric called a so-called unidirectional nonwoven fabric. In this example, the resin material 3 takes the form of a short fiber nonwoven fabric, is arranged with a gap on the surface of the fabric 2, and fixes the reinforcing fiber yarns 4 and the auxiliary fiber yarns 5. Although not shown, a resin material is also disposed on the back surface of the fabric 2 with a gap, and the auxiliary fiber yarns are similarly fixed to the reinforcing fiber yarns.

  FIG. 2 is a schematic cross-sectional view schematically showing an aspect in which the resin material is fixed to the reinforcing fiber yarn in the fabric in the reinforcing fiber base of the present invention.

  FIG. 9 is a schematic cross-sectional view schematically showing an aspect in which the resin material is fixed to the reinforcing fiber yarns in the fabric in the reinforcing fiber substrate outside the scope of the present invention.

  FIG. 2 shows an aspect of fixing the resin material 8 to the reinforcing fiber yarn 7 in the fabric constituting the reinforcing fiber base 6. In FIG. 2, the resin material 8 is an embedded portion in which a plurality of single yarns 9 constituting the reinforcing fiber yarn 7 penetrate the resin material 8 (the region between the broken lines 13 and 14 in the resin material 8. ) And an exposed portion (a region between the broken lines 12 and 13 of the resin material 8) having a thickness on the surface of the reinforcing fiber yarn 7 and being fixed to the surface of the fabric. Yes. Here, the position (boundary of each region) indicated by each broken line will be described in detail. A broken line 12 shown in FIG. 2 indicates a position where the resin material protrudes most from the cloth in a cross section including an axis substantially perpendicular to the cloth surface of the resin material 8, and a broken line 13 penetrates the resin material 8. Among the plurality of single yarns 9 constituting the reinforcing fiber yarn 7, one showing the position of the single yarn forming the fabric surface described later, the broken line 14 is an axis substantially perpendicular to the fabric surface of the resin material 8 It shows the position where the resin material penetrates most into the fabric in the included cross section.

  Each of these positions is prepared by preparing an embedded sample so that the reinforcing fiber base cut out in a direction perpendicular to the reinforcing fiber yarns is cut out and located on the subsequent observation surface, and after polishing the sample, the polished surface (observation surface) ), The aspect of the resin material can be confirmed by observing with an optical microscope. The position of the single yarn forming the fabric surface in the cross section cut in the direction orthogonal to the reinforcing fiber yarn is the exposed portion side of the resin material among the plural single yarns constituting the reinforcing fiber yarn penetrating through the resin material The center of gravity of the cross section of the single yarn located at the outermost part of the yarn is plotted at intervals of 10 and the plot is defined as the position of a straight line obtained by linear approximation. The broken lines 12 and 14 are drawn parallel to the broken line 13. The thickness direction of the fabric is a direction orthogonal to the broken line 13.

  On the other hand, in FIG. 9, each of the broken lines 21, 22, and 23 corresponds to each of FIG. That is, the broken line 21 in FIG. 9 corresponds to the broken line 12 in FIG. 2, similarly, the broken line 22 corresponds to the broken line 13, and the broken line 23 corresponds to the broken line 14. In the reinforcing fiber base 16 shown in FIG. 9, the resin material 17 is bonded only to the surfaces of a plurality of single yarns 19 constituting the reinforcing fiber yarn 18. That is, the single yarn 19 constituting the reinforcing fiber yarn 18 has no single yarn corresponding to the single yarn 9 of FIG.

  In the reinforced fiber base material of the present invention, the resin material imparts an interlayer reinforcing effect to the fiber reinforced resin as described above. This interlaminar reinforcement effect improves the interlaminar fracture toughness of fiber reinforced resin obtained by laminating reinforced fiber base materials and injection molding such as resin transfer molding method (RTM), etc. The effect which suppresses the progress of the crack of the lamination | stacking interlayer part which arises in this is expressed. As a result, the residual compressive strength after impact of the fiber reinforced resin obtained by injection molding such as resin transfer molding (RTM) is dramatically improved. In the fiber reinforced resin obtained by injection molding such as resin transfer molding method (RTM), the effect of interlayer reinforcement by this resin material is shown in FIG. 2 of the present invention and in FIG. 9 outside the scope of the present invention. The feature of the present invention is that the improvement effect is greatly different from that of the aspect. As described in the background art, regarding the interlayer reinforcement effect, a technique for arranging a thermoplastic resin material such as thermoplastic particles between layers in a molding material called a prepreg in which a reinforcing fiber is impregnated with a thermosetting resin in advance. However, the present invention can be obtained by a conventional resin injection molding method by examining the form of a reinforcing fiber base applied to a resin injection molding method such as a resin transfer molding method (RTM). It is clarified that a fiber reinforced resin having an interlayer reinforcing effect much higher than the obtained fiber reinforced resin can be obtained. That is, the reinforcing fiber base material of the present invention has an adhesive property between the resin material and the reinforcing fiber yarn by forming a buried portion in which a plurality of single yarns constituting the reinforcing fiber yarn penetrate at least the resin material. -The impact resistance is remarkably improved, and the interlaminar fracture toughness that is remarkably excellent, and the effect of suppressing the decrease in the residual compressive strength after receiving the impact is exhibited.

  Since the embedded portion of the resin material 8 in the reinforcing fiber base material of the present invention shown in FIG. 2 is a portion through which a plurality of single yarns of the reinforcing fiber yarn penetrates the resin material, the embedded portion is The region is a mixture of resin material and reinforcing fiber single yarn. In a fiber reinforced resin obtained by laminating and molding a reinforcing fiber base material having such a buried portion on the surface of the fabric, it is possible to more efficiently act the interlayer reinforcing effect by the resin material. Specifically, in the fiber reinforced resin obtained by laminating and molding the reinforced fiber base material of the present invention, not only the laminated layers but also the surface region of the reinforced fiber base material (from the surface on the interlayer side of the fabric to the embedded portion of the resin material 8). The progress of cracks in the depth region corresponding to the thickness (the region between the broken lines 13 and 14 in FIG. 2) can be suppressed. In particular, when the adhesiveness between the reinforcing fiber yarn and the matrix resin of the fiber reinforced resin is low, the crack at the time of applying the impact proceeds near the boundary between the reinforcing fiber substrate and the matrix resin between the layers. Moreover, in the fiber reinforced resin using the reinforced fiber base material in which the embedded portion is not formed, the crack progresses easily because the path where the crack progresses becomes the adhesive surface between the resin material and the reinforced fiber base material. Therefore, a sufficient interlayer strengthening effect is not exhibited. On the other hand, in the case of the reinforcing fiber base material of the present invention, since it has an embedded part, when cracks develop near the boundary between the reinforcing fiber base material and the matrix resin between layers, it always becomes a path across the resin material, and the resin The effect of fixing the material to the surface of the reinforcing fiber substrate can be maximized. Even if a path that does not cross the resin material is taken, the inside of the buried part can be advanced or advanced so as to avoid the buried part, so in any case, the resistance for crack development should be increased. Can do. That is, the function as a crack stopper of the resin material can be expressed to the maximum. Furthermore, the buried portion functions effectively even with respect to cracks (transverse cracks) that progress in the thickness direction of the reinforcing fiber base.

  Further, when the embedded portion is a fiber reinforced resin, a plurality of single yarns constituting the reinforcing fiber yarn penetrate at least the resin material to form the embedded portion. Improves adhesion with matrix resin. The formation of a strong bond between the matrix resin layer (interlayer) and the reinforcing fiber layer (inside the layer) by having such a buried portion is called an anchor effect.

  In the reinforcing fiber base material of the present invention, it is necessary that 50 to 100% of the total projected area of the resin material is fixed to the surface of the fabric in the above-described manner. Here, the total projected area of the resin material is the total sum of the areas of the covering portions of the resin material when the reinforcing fiber base is captured from a direction substantially perpendicular to the reinforcing fiber base, 50% to 100% are fixed in the above-described manner, thereby providing excellent handling property in the reinforced fiber base material or the laminate, and more effective in the interlayer reinforcement effect and anchor effect of the resin material described above in the fiber reinforced resin. Can be activated. The ratio of the area fixed according to the above aspect to the total projected area is preferably 70 to 100%, more preferably 90 to 100%. That is, as the buried portion is formed in a wider area, the above-described effect is also exerted in a wider area. If it is less than 50%, not only is the handling property of the reinforcing fiber base material or laminated body inferior, but also damage selectively progresses in the unformed portion of the embedded portion in the fiber reinforced resin, and the interlayer reinforcing effect is efficient. Does not express. In other words, when there are not enough buried parts to suppress the expansion of cracks (damage) in the fiber reinforced resin, the fiber reinforced resin provides excellent mechanical properties (especially compressive strength after application of impact) (interlayer reinforcement). (Effect) cannot be obtained.

  Here, in the reinforcing fiber base material of the present invention, examples of the means for forming the embedded portion include a treatment in which a resin material is disposed on at least the surface of the fabric and fixed using heat or heat and pressure in combination. Such treatment can be carried out using known equipment such as a far-infrared heater, hot press roll, autoclave, press machine, etc., among them, if it is a far-infrared heater, hot press roll, by continuously treating, It is preferable because the reinforcing fiber substrate can be produced efficiently. For the reasons described above, the treatment is preferably performed over a wider area and more preferably over the entire surface of the fabric having the resin material disposed on the surface. Thus, the reinforced fiber base material of a desired aspect can be acquired with the process area which performs the said process.

In the present invention, and essential and that the thickness of the embedded portion is 15μm or more 97μm or less, wherein a thickness of 70~400μm of the fabric, and, within the range of 50% or less of the thickness of the fabric constituting the reinforcing fiber substrate It is preferable that More preferred thickness of the embedded portion is less than 40% of the thickness of the fabric constituting the reinforcing fiber substrate, further preferably embedded portion of the thickness is in the range of less than 30% of the thickness of the fabric constituting the reinforcing fiber substrate. Here, the thickness of the fabric constituting the reinforcing fiber base means that the fabric surface of the back surface is formed from the position of the single yarn forming the fabric surface of the front surface at an arbitrary position of the reinforcing fiber base. It refers to the distance to the position of the single yarn, and specifically refers to the distance between the positions of the broken line 13 in FIG. 2 on both the front and back surfaces.

The thickness of the fabric is preferably 87 to 290 μm, and more preferably 94 to 220 μm. Generally, the thickness of the fabric tends to increase as the fabric weight (weight per unit area: g / m ² ) increases. When the thickness of the fabric is large, in obtaining a fiber reinforced resin by laminating a plurality of reinforcing fiber base materials, when satisfying a predetermined laminated structure, since the basis weight per single layer is increased, the effect of reducing the weight of FRP is obtained. In some cases, the degree of freedom of design is limited. For example, when the layers are stacked to have a predetermined thickness, the layers may not have a predetermined stacked configuration. On the other hand, if the thickness of the fabric is small, when the predetermined thickness is satisfied, the number of the reinforcing fiber bases is inevitably increased, so the productivity in the laminating process is lowered and the cost is increased.
The measurement of the thickness of the fabric constituting the reinforcing fiber base is carried out by cutting the reinforcing fiber base cut out in the direction perpendicular to the reinforcing fiber yarns from any 10 locations in the reinforcing fiber base, and the cut surface becomes the subsequent observation surface. An embedded sample is prepared so as to be positioned, and after polishing the sample, the state of the resin material on the polished surface (observation surface) can be confirmed by observing with an optical microscope at a magnification of 500 times or more. From such an observation surface, the thickness of three places is measured according to the above definition so that the observation visual fields do not overlap, and this is performed for each cross section, and all averages are calculated as the thickness of the fabric constituting the reinforcing fiber substrate of the present invention. To do. The same measurement method is applied to the thickness of the buried portion of the resin material and the average thickness of the exposed portion.

  In the reinforcing fiber substrate of the present invention, the exposed portion of the resin material functions as a spacer when the reinforcing fiber substrate is laminated, but the thickness of the embedded portion of the resin material is 50% of the thickness of the reinforcing fiber substrate. If it exceeds, the resin material of the exposed part that functions as a spacer or crack stopper is relatively insufficient, so that the function may not be sufficiently exhibited. That is, the resin material fixed to the fabric is distributed to the inside and outside of the reinforcing fiber yarn, but as described above, because the amount thereof is limited, the thickness of the embedded portion of the resin material becomes deep. This leads to a decrease in the amount of the resin material in the exposed portion, and accordingly, the thickness of the exposed portion decreases. As a result of the reduced thickness of the exposed part, the resin material does not function sufficiently as a spacer or crack stopper, and sufficient space cannot be secured between the layers laminated with the reinforcing fiber base, resulting in insufficient formation of the resin flow path. There is a case.

On the other hand, if the thickness of the embedded portion of the resin material is less than 15 μm, contrary to the above, since the resin material protruding outside the reinforcing fiber yarn is relatively large, the function of the resin material as a spacer is Although it becomes high, there is a concern that the thickness of the exposed portion of the resin material or the projected area becomes large and the reinforcing fiber content of the fiber reinforced resin is lowered. Adhesion and between the resin material and the reinforcing fiber yarns, in order to express the most of such anchor effect of the matrix resin, it is preferable is 15 [mu] m or more. From this point of view, in terms of the thickness of the embedded portion of the resin material was 15 [mu] m or more and within a range of 50% or less of the thickness of the reinforcing fiber substrate, interlayer reinforcing effect and the interlayer flow path shape effect of the resin material Can be expressed more efficiently.

In addition, when laminating a plurality of reinforcing fiber substrates, if the unevenness in the vertical direction is too large on the fabric surface of the resin material adhered to the surface of the fabric, the reinforcing fiber substrate or reinforcing fiber yarn adjacent to it is bent. there's a possibility that. That is, the smaller the unevenness on the surface of the reinforcing fiber base, the smaller the bending of the yarn and the higher the physical properties of the fiber-reinforced resin. From this viewpoint, in the present invention, the average thickness of the exposed portion of the resin material is in the range of 10 to 250 μm . Preferably, it is 10-100 micrometers, More preferably, it is the range of 15-60 micrometers.

Such a resin material needs to be in the form having the gaps described above, but in particular, it is excellent in the impregnation of the matrix resin into the laminated reinforcing fiber base (particularly in the vertical direction of the laminated surface), molding Resin in the form of a dot from the point that the reinforcing fiber volume content of the fiber reinforced resin can be increased, and that the molded fiber reinforced resin can minimize the diffusion of moisture in the resin material even under high temperature and high humidity heat Are preferably dispersed.
Here, the dot shape means a resin material having an average diameter of 1 mm or less as viewed from the surface of the fabric. For example, the average diameter of a perfect circle, an ellipse and an irregular shape (amoeba shape) is 1 mm or less. Are included in the form of dots in the present invention. Note that the average diameter in a point shape other than a perfect circle is the average minor axis in the case of an ellipse, and the diameter of the circumscribed circle in the case of an irregular shape. In addition, the point-shaped resin is dispersedly arranged in a point-like form so that 10 points in a range of 100 mm × 100 mm are taken at an arbitrary position from the fabric and the resin weight does not vary by 10% or more. This means that the resin is distributed in a dense and discrete manner.

  Since the resin material can be uniformly dispersed on the surface of the fabric as the dot-shaped resin material has a smaller average diameter, the resin material preferably has an average diameter of 1 mm or less, more preferably 500 μm or less, and 250 μm. The following is more preferable. When the average diameter of the resin material is 30 μm or more, the resin material is disposed straddling the reinforcing fiber yarns and the auxiliary fiber yarns on the surface of the reinforcing fiber base material. It can be a reinforcing fiber substrate.

  Such a resin material may be disposed on one side of the fabric or may be disposed on both sides of the fabric. The former is preferred when producing a reinforcing fiber substrate at a lower cost. The latter is preferable when it is desired to improve the handleability of the reinforcing fiber base, or when it is not desired to use the front and back of the reinforcing fiber base properly, and the latter can be used depending on the purpose.

  The preferable form of the fabric used for the reinforcing fiber substrate of the present invention will be described below.

  FIG. 3 is a perspective view showing one embodiment of a fabric used for the reinforcing fiber base of the present invention.

  In FIG. 3, the fabric 26 is composed of warp yarns (or weft yarns) that are reinforcing fiber yarns 27 and weft yarns (or warp yarns) that are auxiliary fiber yarns 28, and the reinforcing fiber yarns 27 and auxiliary fiber yarns. The strips 28 intersect with each other in a plain weave structure to form a fabric 26. The fabric 26 is mainly composed of reinforcing fiber yarns 27. In this way, the woven fabric in which the reinforcing fiber yarns are arranged in only one direction is called a unidirectional woven fabric, and such a unidirectional woven fabric is not limited to the one shown in FIG. Any woven structure such as plain weave, satin weave, twill weave, etc. can be applied. Among them, a preferred woven structure is a unidirectional non-crimp fabric. Non-crimp woven fabric means that auxiliary fiber yarns are arranged between reinforcing fiber yarns, and they are arranged parallel to each other and in a sheet form to form a warp sheet, and the auxiliary fiber yarns in the warp direction. This is a kind of unidirectional woven fabric in which the strip and the auxiliary yarn group in the weft direction form a woven structure and integrally hold the reinforcing fiber yarn group. In the case of a unidirectional woven fabric, particularly a unidirectional non-crimp woven fabric, not only the handleability of the reinforcing fiber substrate but also the straightness of the reinforcing fiber yarn and the impregnation property of the matrix resin are expressed more highly. It can be said that it is the most preferable form as a fabric.

  The following forms may be sufficient as the fabric used for the reinforcement fiber base material of this invention besides the form mentioned above.

  4 and 5 are perspective views showing another embodiment of the fabric used for the reinforcing fiber substrate of the present invention.

  In FIG. 4, the fabric 29 is composed of warp yarns in which reinforcing fiber yarns 30 are arranged in one direction and weft yarns in which reinforcing fiber yarns 31 are arranged in one direction in a direction different from the warp yarns. The warp yarn and the weft yarn intersect with each other in a plain weave structure to form the fabric 29. Thus, the woven fabric in which the reinforcing fiber yarns are oriented in two directions is called a bi-directional woven fabric, and any woven structure such as satin weave or twill weave can be applied in addition to the plain weave structure shown in FIG. Can do.

  Such bi-directional woven fabric has a structure formed by reinforcing fiber yarns crossing each other, so that not only is excellent in handleability as a fabric, but also when a fiber reinforced resin is molded by injection molding described later, This intersection point becomes a flow path of the matrix resin and exhibits excellent impregnation properties. As for crimping, the reinforcing fiber yarns are intertwined with each other, so it is inferior to the unidirectional fabric described above, but by making the cross section of the reinforcing fiber yarns used smoother, the formation of crimps is kept to a minimum. Can do. For example, before forming the structure, refraction / oscillation treatment by air / jet injection or roll may be performed, and the reinforcing fiber yarns may be spread thinly. It may be.

  In FIG. 5, a fabric 32 includes a first layer 33 in which reinforcing fiber yarn groups are arranged in one direction, and a second layer 34 in which reinforcing fiber yarn groups are arranged in one direction in a direction different from the first layer. And the two layers are integrated by warp knitting made of auxiliary fiber yarns (stitch yarns) 35 to form a fabric 32. A fabric in which the two layers are integrated by warp knitting composed of auxiliary fiber yarns (stitch yarns) 35 in which reinforcing fiber yarns oriented in two directions are cross-laminated in this way is called a biaxial stitch base material, Such a biaxial stitch base material can be applied to the present invention without being limited to the one shown in FIG.

  The fabric applied to the present invention is not limited to the biaxial stitch base material, and at least two or more layers of reinforcing fiber yarns arranged in one direction are cross-laminated in different directions, and auxiliary fiber yarns (stitch yarns). A so-called multiaxial stitch base material integrated by warp knitting made of 35 can also be applied. As the multi-axis stitch base material, for example, “−45 ° / 0 ° / + 45 ° / 90 °...” May be laminated in four or more layers so as to be pseudo-isotropic. Further, it may be laminated in multiple directions. In the case of multilayer lamination, from the viewpoint of interlayer reinforcement, it is preferable to dispose a resin material at least every two layers, and it is more preferable to dispose a resin material between the respective layers. When the resin material is disposed between the respective layers, the effect of the resin material (particularly, the interlayer strengthening effect) can be maximized.

  The above-mentioned biaxial stitch base material and multi-axis stitch base material are generically referred to as a stitch base material, and the stitch base material refers to a stitch integrated with auxiliary fiber yarn groups. Here, the stitching integration is not particularly limited as long as a constraint sufficient to maintain the fabric form is obtained, and examples thereof include warp knitting, weft knitting, or stitching. Of these, warp knitting is preferred from the viewpoint of production efficiency.

  Both the biaxial stitch base material and the multiaxial stitch base material described above can be applied to the present invention. Among these, the first layer in which the reinforcing fiber yarns are arranged in one direction and the first layer are orthogonal to each other. Two-layer laminated biaxial stitch base material (for example, “−45 ° / + 45 °”, “0 ° / 90 °”) in which a second layer in which reinforcing fiber yarns are arranged in one direction is cross-laminated. Is preferred. With such a configuration, since the fabric easily shears and deforms, for example, it has excellent followability to complex shapes and deep-drawn shapes (formability), and a reinforcing fiber base material is laminated and molded into a fiber reinforced resin. In this case, since the resin material is evenly arranged in the fiber reinforced resin, the above-described interlayer reinforcement of the resin material can be sufficiently exhibited. Furthermore, in the production of the reinforcing fiber base (fixing of the resin material), the same process as that of the woven fabric described above can be applied, and the versatility is excellent.

In the reinforcing fiber substrate of the present invention, the basis weight of the reinforcing fibers is in the range of 100 to 400 g / m ² (more preferably 130 to 290 g / m ² , and still more preferably 140 to 220 g / m ² ). preferable.

  The type of reinforcing fiber yarn used in the present invention is not particularly limited, and examples thereof include glass fiber, organic (aramid, PBO, PVA, PE, etc.) fiber, carbon fiber, and the like. Since carbon fiber is excellent in specific strength and specific elastic modulus and excellent in water absorption resistance, it is preferably used as a reinforcing fiber yarn for aircraft structural materials and automobiles. When carbon fiber is used as the reinforcing fiber yarn, the 6,000 to 70,000 filament and the fineness (Tc) are preferably in the range of 400 to 5000 tex. The 12,000 to 25,000 filament and the fineness are more preferably in the range of 800 to 1800 tex. Within such a range, there is an advantage that high-performance carbon fibers can be obtained relatively inexpensively. Moreover, it is preferable that the reinforcing fiber yarn of the present invention is substantially untwisted. Substantially no twist means that it is usually less than 1 turn / m. When it is substantially untwisted yarn, the thickness of the reinforcing fiber yarn can be reduced, and the straightness of the reinforcing fiber is excellent, so that a high reinforcing fiber content can be expressed in the molded fiber reinforced resin, and excellent mechanical properties can be obtained. Because it can be brought.

  In the present invention, when a unidirectional woven fabric, a biaxial stitch base material, or a multiaxial stitch base material is used as the fabric, the auxiliary fiber yarn used in the fabric has a fineness of 1 of the reinforcing fiber yarn. / 5 or less is preferable. The fineness (Ta) of the auxiliary fiber yarn group is preferably 1/5 or less of the fineness (Tc) of the reinforcing fiber yarn, that is, 20% or less. Specifically, (Ta × 100) / Tc2 ≦ 20. More preferably, it is 5% or less, More preferably, it is 3% or less. The lower limit of the ratio is not particularly limited, and the lower the better, the better, but it is generally 0.05% or more from the viewpoint of the form stability and production stability of the fabric.

  Since the auxiliary fiber yarn group penetrates in the thickness direction of the fabric and extends in the longitudinal direction of the fabric, the reinforcing fiber yarn group is bent (crimped) in the in-plane direction and the thickness direction of the fabric. . In other words, by making the auxiliary fiber yarn group as thin as possible, the formation of crimps can be suppressed to the minimum, and a fiber reinforced resin having excellent mechanical properties can be obtained. Such crimps are more pronounced as the reinforcing fiber volume content of the fiber reinforced resin is higher (excellent weight reduction effect), and the mechanical properties are likely to be lowered. That is, with the auxiliary fiber yarn group of the above-described aspect, it is possible to easily obtain a fiber reinforced resin that can be applied to an aircraft primary structural member or the like that requires an excellent lightening effect and extremely high mechanical properties. When Ta is within the above range, the reinforcing fiber yarns are slightly crimped, but hardly affect the straightness of the reinforcing fiber yarns, and the deterioration of the mechanical properties is substantially ignored. This makes it possible to obtain a fiber reinforced resin exhibiting extremely high mechanical properties while having a high reinforcing fiber volume content. The fineness of the auxiliary fiber yarn group is unlikely to be a suitable index alone, but assuming that the reinforcing fiber yarn is a carbon fiber yarn in the range of 800 to 1700 tex, from the viewpoint of reducing the influence of the above-mentioned crimp, the auxiliary fiber The fineness (Ta) is preferably 8 tex or less. More preferably, it is 5 tex or less, More preferably, it is 2 tex or less. However, even if it is too thin, thread breakage may be caused in the production process of the reinforcing fiber base, and as a result, the productivity may be lowered.

  From the viewpoint of suppressing crimping, the auxiliary fiber yarn is preferably a multifilament. Preferably it is more than 5 filaments. When it is a multifilament, the fineness (diameter) of the filament single yarn can be further reduced, and the crimp can be further reduced to increase the straightness of the reinforcing fiber yarn. Further, it is preferable because the auxiliary fiber yarns can be cut less and are excellent in terms of handleability and production stability of the reinforcing fiber substrate. In the case of a multifilament, it is preferable to use a substantially non-twisted fiber-reinforced resin in order to achieve high mechanical properties and a reinforced fiber volume content.

  In the present invention, when a unidirectional woven fabric and a stitch base material are used as the fabric, the auxiliary fiber yarn used in the fabric is not particularly limited in type, but polyester, polyamide, polyethylene, vinyl alcohol, It can be selected from polyphenylene sulfide, polyaramid, compositions thereof and the like. Of these, polyester and polyamide are preferred. From the viewpoint of the formability of the fabric, it is preferably a processed thread of spandex (polyurethane elastic fiber), polyamide or polyester.

  When the reinforcing fiber base material of the present invention is laminated, the resin material has a melting point or a glass transition temperature in the range of 50 to 150 ° C. from the viewpoint of workability, although the tackiness is expressed by heat treatment. Is preferred. More preferably, it has a melting point or glass transition temperature in the range of 70 to 140 ° C, more preferably 90 to 120 ° C.

  The component of the resin material is not particularly limited as long as it improves the handleability of the reinforcing fiber base and improves the mechanical properties of the fiber reinforced resin obtained by using it. As the resin material, various thermoplastic resins and / or thermosetting resins can be used, and any of them may be the main component. In the present invention, the main component usually means that it contains more than 50% by weight with respect to the resin material.

  When a thermoplastic resin is used as a main component for the resin material in the present invention, polyester, polyolefin, styrene resin, polyoxymethylene, polyamide, polyurethane, polyurea, polydicyclopentadiene, polycarbonate, polymethylene methacrylate, polyvinyl chloride, Polyphenylene sulfide, polyphenylene ether, polyetherimide, polysulfone, polyarylate, polyethersulfone, polyketone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyarylate, polyethernitrile, polyimide, polyamideimide, phenol, phenoxy , Fluorine-based resins such as polytetrafluoroethylene, and elastomers (preferably butadiene acrylonitrile, Modified rubonic acid or amine, fluoroelastomer, polysiloxane elastomer), rubber (butadiene, styrene / butadiene, styrene / butadiene / styrene, styrene / isoprene / styrene, natural rubber, etc.), RIM resin (eg polyamide 6, polyamide) 12, one containing a catalyst for forming polyurethane, polyurea, polydicyclopentadiene) and a cyclic oligomer (including a catalyst for forming polycarbonate resin, polybutylene terephthalate resin, etc.) Two or more types of copolymers, modified products, or a mixture of two or more types can be used. Among them, one, two or more selected from the group consisting of polyamide, polysulfone, polyether sulfone, polycarbonate, polyvinyl formal, polyether imide, polyphenylene ether, polyimide, polyamide imide, polyvinyl formal, phenoxy, and phenol It is preferable that it is a copolymer of these, a modified body, or a mixture of 2 or more types. The main component of the resin material used in the present invention is particularly preferably one or a mixture of two or more selected from the group consisting of polyether sulfone, polyamide, polyvinyl formal, phenoxy resin, and polycarbonate.

  Moreover, when using a thermosetting resin as a main component, from epoxy, phenol, polybenzimidazole, benzoxazine, cyanate ester, unsaturated polyester, vinyl ester, urea, melamine, bismaleimide, polyimide, and polyamideimide 1 type, 2 or more types of mixtures selected from the group consisting of, or a modified product, or 1 type, 2 or more types of mixtures selected from the above group, or a modified product, an elastomer, a rubber component, and a cured product. A resin to which an agent, a curing accelerator, a catalyst and the like are added can be used. Among these, at least one kind or a mixture of two or more kinds selected from the group consisting of epoxy, phenol, vinyl acetate, unsaturated polyester, and vinyl ester is preferable. In particular, the use of epoxy is preferable because not only the handling property of the reinforcing fiber substrate is excellent because of high adhesiveness, but also high mechanical properties can be exhibited when an epoxy resin is used as a matrix resin described later. When using an epoxy, a curing agent, a curing catalyst, or the like may or may not be included, but the latter is preferable from the viewpoint of life. Even in the former case, if the curing agent or the curing catalyst has a high potential, it is not a big problem.

  When using the resin material which has a thermoplastic resin as a main component as a resin material used for the reinforced fiber base material of this invention, it is preferable that the mixture ratio of the thermoplastic resin in a resin material is 60 to 100 weight%. More preferably, it is 70-97 weight%, More preferably, it is 80-95 weight%. If the blending amount is less than 60% by weight, it may be difficult to obtain a fiber reinforced resin excellent in mechanical properties (particularly CAI). Moreover, when using the resin material which has a thermoplastic resin as a main component as a resin material used for the reinforced fiber base material of this invention, depending on the frame | skeleton and molecular weight of the thermoplastic resin to be used, melt viscosity or melting temperature (or glass transition temperature) Therefore, when adhering to a fabric by heating, it may be insufficiently fixed to the reinforcing fiber yarns, or high temperatures may be required when laminating the reinforcing fiber base material, resulting in poor workability. In such a case, it is also preferable to add a small amount of a tackifier, a plasticizer or the like as a subcomponent to the resin material. Such subcomponent is preferably at least one selected from the group consisting of epoxy, phenol, vinyl acetate, unsaturated polyester, and vinyl ester. In particular, application of what is used as a matrix resin when the fiber reinforced resin described later is applied has an advantage of excellent adhesion and compatibility between the matrix resin and the resin material.

  When a thermosetting resin is used as the main component of the resin material in the present invention, an epoxy resin is preferable. Examples of such an epoxy resin include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, 2,2 ′, 6,6′-tetramethyl-4,4. '-Biphenol diglycidyl ether, N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3- Methylphenol, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline, N, N, N ′, N′-tetraglycidyl-2,2′-diethyl-4,4′-methylenedianiline, , N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (diglycidylaminomethyl) cyclohexane, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, Neopentylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, vinylcyclohexene diepoxide, 3,4-epoxycyclohexanecarboxylic acid 3,4- Epoxycyclohexylmethyl, bis-3,4-epoxycyclohexylmethyl adipate, 1,6-dihydroxynaphthalene diglycidyl ether, , 9-bis (4-hydroxyphenyl) fluorene diglycidyl ether, tris (p-hydroxyphenyl) methane triglycidyl ether, tetrakis (p-hydroxyphenyl) ethane tetraglycidyl ether, phenol novolac glycidyl ether, cresol novolac glycidyl Ether, glycidyl ether of a condensation product of phenol and dicyclopentadiene, glycidyl ether of phenol aralkyl resin, or the like can be used.

  Thermosetting resins have lower melt viscosity and melting temperature (or glass transition temperature) than thermoplastic resins, so that the reinforcing fibers can be sufficiently wetted by hot melt, making it easy to handle reinforcing fiber substrates and preforms. It is suitable when considering tackiness and tackiness. As the effect, for example, the breakage of the reinforcing fibers at the reinforcing fiber base and the preform end is suppressed, and the end processing amount in the molded product is reduced, leading to cost reduction.

  When a resin material mainly composed of a thermosetting resin is used as the resin material used for the reinforcing fiber base of the present invention, the blending ratio of the thermosetting resin in the resin material is 51 to 100% by weight. More preferably, it is 53-80 weight%, More preferably, it is 55-70 weight%. When the blending ratio is less than 51%, the handleability and tackiness in the above-described reinforcing fiber base and preform may be impaired.

  As such a resin material, a component other than the thermosetting resin may be further contained, and for example, an antioxidant, insoluble organic particles, inorganic particles, and the like can be used. In particular, among the organic particles, crosslinked rubber particles and insoluble thermoplastic resin particles are effective in improving the toughening effect. In addition, a curing agent or a curing catalyst may be blended, but when there is self-curing property, the glass transition temperature of the resin material rises during storage, and the function as a binder is lost. It is better not to mix.

  Such a resin material preferably has a melt viscosity at a shear rate of 1000 / s at a melting point Tm + 50 ° C. within a range of 100 to 1000 Pa · s. More preferably, it is 200-800 Pa.s, More preferably, it is 250-600 Pa.s. If the melt viscosity is too small, when the resin material is heat-bonded to the reinforcing fiber yarn group, it diffuses or penetrates into the reinforcing fiber yarn surface on the surface of the reinforcing fiber yarn group, and the reinforcing fiber yarn group. In some cases, it is difficult to form an exposed portion (spacer) on the surface. On the other hand, if the melt viscosity is too large, the resin material does not easily penetrate into the reinforcing fiber yarn group, and the interface of the resin material cannot be formed in the reinforcing fiber yarn group, and the fiber reinforced resin is used as described above. In some cases, the interlayer strengthening effect cannot be fully exhibited. From this viewpoint, when the present invention is within the above range, the reinforcing fiber substrate of the present invention can be easily produced. Here, the said melt viscosity points out the value measured according to JISK7117-2 (1999) using the rotational viscometer. Moreover, melting | fusing point Tm points out the value measured at the temperature increase rate of 20 degrees C / min in the absolutely dry state according to JISK7121 (1987) using DSC (differential scanning calorimeter). In addition, about what does not show melting | fusing point (for example, amorphous polymer), glass transition temperature +100 degreeC obtained by measuring similarly shall be considered as melting | fusing point (Tm) for convenience.

  The laminate of the present invention is a laminate in which a plurality of fabrics composed of a group of reinforcing fiber yarns formed by arranging reinforcing fiber yarns in parallel are laminated, and a fabric that forms an interlayer in each laminated interlayer part The resin material is disposed in a form having a gap within the range of 2 to 40% by weight, and each of the resin materials is located between the layers and does not include the reinforcing fiber yarn, and both sides thereof Further, the reinforcing fiber base material is bonded to each other in a form in which a plurality of single yarns among the reinforcing fiber yarns of both fabrics forming the interlayer have an embedded portion penetrating the resin material. . The definitions of the fabric and the resin material here are the same as those of the reinforcing fiber substrate of the present invention described above.

  Here, it is necessary that the resin material is disposed in an interlayer portion of the laminate in a form having a gap. When the resin material is arranged in the interlayer part of the laminate in a form having a gap, the presence and absence of the resin material are mixed so that the projected area of the resin material occupying the interlayer part is 80% or less. In this manner, the resin material is arranged. Note that the projected area of the resin material in the laminate is different from that of the reinforcing fiber substrate and is estimated from the cross section. That is, it confirms from the cross section cut out in the direction orthogonal to the reinforcing fiber yarn which comprises a laminated body from the arbitrary at least 10 places of a laminated body. From each of the cross sections, for each layer of the fabric constituting the laminate, the position of the single yarn forming the outermost surface of the fabric among the plurality of single yarns constituting the reinforcing fiber yarn penetrating through the resin material described above, and Of the plurality of single yarns constituting the reinforcing fiber yarn penetrating through the other resin material facing the fabric thickness direction, the position of the single yarn forming the fabric surface, that is, the fabric surface of the fabric of each layer Determine the position. Draw a straight line at such a position, draw a straight line that bisects between the straight lines corresponding to the positions of both surfaces sandwiching the layers, a distance where the resin material does not exist on the straight line = a portion that is not covered by the resin material, The distance where the resin material exists = the length is measured assuming that the resin material is covered, and the ratio of each distance is used as a projected area for convenience. This is carried out for all the layers and all the cross sections, the average value of each result is calculated for each layer, and this value is defined as the projected area of the resin material in the laminated interlayer part of the laminate of the present invention. In the length measurement of the distance where the resin material exists and the distance where the resin material does not exist, when it is assumed that the length is measured from the left direction to the right direction, on the straight line located on the fabric surface of each fabric layer in the laminate, The distance from the left end of the arranged resin material to the left end of the resin material that passes through the inside of the resin material and passes through the right end portion to the right is 1 unit, and at least 10 units between each layer Measured points will be provided.

  The ratio of the area of the existing portion where the resin material is arranged in such a form is preferably within a range of 5 to 50%, and the gap (non-existing portion) is preferably in a more uniformly dispersed state. Examples of the resin material include a porous film, a short fiber nonwoven fabric, a cut fiber, and a granular material. Among these, a granular material is preferable.

  In addition, in the laminate of the present invention, the resin material is fixed in a manner in which each of the resin materials includes a buried portion where a plurality of single yarns of the reinforcing fiber yarns penetrate at least the resin material, and an interlayer. It is necessary to be fixed in an embodiment having an interlayer arrangement portion that is positioned and does not include a reinforcing fiber yarn. The form of the buried part and the interlayer arrangement part will be described later, but by fixing in this manner, the interlayer strengthening effect of the resin material is manifested with extremely high efficiency when the matrix resin is injected into the fiber reinforced resin. It can be made. On the other hand, outside this mode (when there is an embedded part only on one fabric side or when there is no embedded part on either fabric side), the resin material cannot function effectively in the fiber reinforced resin, and the fiber reinforced In resin, the function as a crack stopper cannot be expressed to the maximum.

  In addition, the thickness of the embedded portion of the resin material in the laminate of the present invention needs to be thinner than the thickness of the fabric. By having such a thickness of the embedded portion, the excellent handling property and the resin impregnation property of the reinforcing fiber base material are compatible without impairing the interlayer reinforcing effect of the resin material. On the other hand, outside of this mode, the embedded portion is arranged through the reinforcing fiber yarns in the thickness direction, so that when the fiber reinforced resin is molded, impregnation of the matrix resin is inhibited and the resin impregnation property of the laminate is reduced. I will let you.

  In the laminate of the present invention, it is necessary that 50 to 100% of the total projected area of the resin material is fixed in the above manner between the respective layers. By being fixed in this manner, the effect (particularly the interlayer strengthening effect) of the resin material can be more reliably and widely applied over the entire surface of the laminate. On the other hand, outside of this mode, the effect of the resin material (particularly the interlayer reinforcement effect) is not only localized, but also the variation becomes large, and the above effect is not brought about in the laminate and the fiber reinforced resin.

  FIG. 6 is a cross-sectional view schematically showing the laminate of the present invention. 36 and 37 are fabrics, 38 is a resin material, and a plurality of fabrics form a laminate 40 in which resin materials are arranged in an interlayer portion. The laminated body having such a configuration can be obtained by laminating the reinforcing fiber base of the present invention and heating and pressing under predetermined conditions described later.

FIG. 7 is an enlarged cross-sectional view schematically showing an interlayer portion of the laminate of the present invention. This figure is an enlarged view of an interlayer portion formed by the cloth 36 and the cloth 37 sandwiching the resin material 38 of FIG.
In FIG. 7, the resin material 38 is an embedded portion (a region indicated by reference numerals 42 and 44 in the resin material 38) in which a plurality of single yarns 41 and 43 constituting the fabric 36 and the fabric 37 penetrate the resin material 38. ), And an interlayer arrangement portion (a region between broken lines 42a and 44a in the resin material 38) that is located between the layers and does not include the reinforcing fiber yarns. Here, the position (boundary of each region) indicated by each broken line will be described in detail. The broken lines 42a and 44a shown in FIG. 7 indicate the positions of the single yarns positioned on the interlayer side between the layers among the plurality of single yarns 41 and 43 constituting the fabric 36 and the fabric 37 penetrating the resin material 38. The broken lines 42b and 44b indicate the positions where the resin material penetrates most into the fabric in the direction substantially perpendicular to the surface of the fabric of the resin material 38.

  The positions of the broken lines 42a and 44a correspond to the position of the broken line 13 in FIG. 2 described above, and in each layer among the plurality of single yarns 41 and 43 constituting the cloth 36 and the cloth 37 penetrating through the resin material 38. The position of the single yarn located on the interlayer side corresponds to the position of the single yarn 9 forming the fabric surface among the plurality of single yarns constituting the reinforcing fiber yarn penetrating through the resin material, and among the resin material 38 The position where the resin material most penetrates into the cloth in the direction substantially perpendicular to the surface of the cloth corresponds to the position 14 where the resin material penetrates most into the cloth. Follow.

  The resin material in such a laminate plays a role as an engaging material that joins adjacent fabrics and integrates them. When the resin material works as an engaging material, excellent handling properties and form stability as a laminated body can be imparted in work processes such as processing and transportation of the laminated body. For example, in a laminate laminated in a predetermined orientation, the orientation angle can be prevented from being disturbed. As a result, the manufacturing cost is reduced and the product quality is stabilized.

  As another role of the resin material, the resin material disposed between the laminate layers serves as a spacer to form a space between the layers of the fabric adjacent in the thickness direction. This space serves as a flow path for the matrix resin when the fiber reinforced resin is formed by injection molding described later (interlayer flow path forming effect). This not only facilitates the impregnation of the matrix resin, but also increases the impregnation speed, resulting in excellent productivity of the fiber reinforced resin.

  The laminated body having such a structure is formed by laminating a resin material disposed between interlayers of the respective fabrics when laminating fabrics composed of reinforcing fiber yarn groups formed by arranging reinforcing fiber yarns in parallel. Alternatively, it can be obtained by laminating the reinforcing fiber base material of the present invention in which a resin material is arranged on the surface of a fabric composed of reinforcing fiber yarn groups formed by arranging reinforcing fiber yarns in parallel. However, the latter is preferred.

  In the latter case, the exposed portion of the resin material of the reinforcing fiber base forms the other embedded portion in the reinforcing fiber yarn of the other reinforcing fiber base forming the interlayer. Such an aspect is obtained by applying a pressure to the temporary laminated body in which the reinforcing fiber base is simply laminated in the thickness direction so that the exposed portion of the resin material of the reinforcing fiber base forms an interlayer. Forming a state of being physically embedded in the reinforcing fiber yarn of the material, heating the temporary laminate in this state, softening or melting the resin material, reinforcing fiber of the other reinforcing fiber base An embedded portion can be formed in the yarn. When the resin material is arranged on one surface of the reinforcing fiber base, if the thickness of the exposed portion of the resin material is larger than the thickness of the buried portion, the interlayer arrangement portion and the buried portion of the resin material when the laminate is formed The resin material is preferably arranged in a well-balanced manner, and when the resin material is arranged on both surfaces of the reinforcing fiber base, it is also preferable that the thickness of the exposed portion of the resin material is smaller than the thickness of the embedded portion.

  Moreover, the latter brings about the outstanding productivity of a laminated body by using the reinforced fiber base material by which the resin material is arrange | positioned previously. In the former, a resin material must be arranged and laminated for each piece of fabric cut out in an arbitrary area, whereas in the latter, the reinforcing fiber substrate obtained continuously is cut and laminated. Therefore, labor saving is possible in the lamination process.

  By laminating the reinforcing fiber base material of the present invention to obtain the laminated body of the above aspect, the above-described interlayer reinforcing effect can be exhibited to the maximum.

  As described above, in the laminate of the present invention, the resin material 38 has an embedded portion in each reinforcing fiber yarn of the reinforcing fiber substrate adjacent to the resin material 38. The embedded portion has the same function as that of the above-described reinforcing fiber base, but a lump of resin material is fixed to each of the adjacent layers via such embedded portions, so that the fiber reinforced resin The aforementioned anchor effect is brought about in each of the adjacent layers. That is, when the laminated body in which these effects are combined is made into a fiber reinforced resin, adjacent layers are connected to each other with a strong adhesion through the resin material. Thereby, the delamination strength in the fiber reinforced resin can be improved.

  In the present invention, it is preferable that each of the resin materials existing between the layers in the laminate has a substantially equal weight per unit area. In such an embodiment, when the laminate is made of a fiber reinforced resin, unevenness of the reinforcing fiber volume content (Vf) described later can be eliminated in the fiber reinforced resin. Furthermore, a uniform interlayer is formed, resulting in excellent mechanical properties. In addition, the resin material here includes both the exposed portion and the embedded portion, and the substantially same amount indicates that it is within a range of ± 5% or less.

  The fiber reinforced resin of the present invention uses the reinforced fiber substrate or the laminate as a reinforced fiber. Such a fiber reinforced resin is produced by impregnating the reinforcing fiber substrate or the laminate with a matrix resin and solidifying (curing or polymerizing) after the impregnation.

  The matrix resin used for obtaining the fiber reinforced resin of the present invention is not particularly limited, but is preferably a thermosetting resin. As the thermosetting resin, for example, at least one or a mixture of two or more selected from the group consisting of epoxy, phenol, vinyl ester, unsaturated polyester, cyanate ester, bismaleimide benzoxazine, and acrylic, Since both the moldability and the mechanical properties of the resin are well balanced, it is preferable because the problem of the present invention can be easily solved. Among them, for example, epoxy or bismaleimide is preferable, and epoxy is particularly preferable in order to achieve very high mechanical properties (particularly, compressive strength after impact application) required for the primary structural member of an aircraft. Further, those added with an elastomer, rubber, a curing agent, a curing accelerator, a catalyst or the like can also be used.

  When the matrix fiber is impregnated into the reinforcing fiber base by injection molding described later, if the viscosity of the matrix resin is low, the impregnation time can be shortened, and a very thick laminated reinforcing fiber base can be impregnated. The viscosity is preferably 400 mPa · s or less, more preferably 200 mPa · s or less, at the injection temperature. Furthermore, in order to make the impregnation time as long as possible, the viscosity after 1 hour at the injection temperature is preferably 600 mPa · s or less, and more preferably 400 mPa · s or less. The injection temperature is preferably 100 ° C. or lower because the equipment can be simplified.

  The fiber reinforced resin of the present invention includes various molding methods such as injection molding (RTM (Resin Transfer Molding), RFI (Resin Film Infusion), RIM (Resin Injection Molding), vacuum assist RTM, etc.), press molding, and the like. It can be molded by a combined molding method.

  A more preferable method for molding a fiber reinforced resin includes an injection molding method with high productivity. As such an injection molding method, RTM is preferable. For example, RTM includes a molding method in which a matrix resin is pressurized and injected into a cavity formed by a male mold and a female mold. A more preferred molding method is vacuum assist RTM. The vacuum assist RTM is as described above. For example, either a male type or a female type (for example, metal, FRP or the like, preferably a high-rigidity material that is difficult to deform) and a bag material such as a film (for example, The cavity formed by nylon film, silicon rubber or the like that can be reused is decompressed, and the matrix resin is injected at a pressure difference from atmospheric pressure. In this case, a resin diffusion medium (media) is disposed on the reinforcing fiber base in the cavity, and diffusion and impregnation of the matrix resin is promoted by such media. After molding, it is preferable to separate the media from the fiber reinforced resin. These injection molding methods are preferably applied in terms of molding cost.

The above-mentioned fiber reinforced resin has a reinforced fiber volume content (Vf) in the range of 53 to 65%, and the normal temperature compressive strength after impact application described in SACMA-SRM-2R-94 is 240 MPa or more. Good. In addition, Vf (a unit is vol%) refers to the volume ratio which a reinforced fiber occupies in a fiber reinforced resin, and is specifically defined by following Formula, The symbol used here is as showing below.

Vf = (W × 100) / (ρ × T)
W: Weight of reinforcing fiber per 1 cm ² of fabric in reinforcing fiber substrate or laminate (g / cm ² )
ρ: Density of reinforcing fiber (g / cm ³ )
T: thickness of fiber reinforced resin (cm)

When the Vf of the fiber reinforced resin is in the range of 53 to 65%, the excellent mechanical properties of the fiber reinforced resin can be expressed to the maximum. If Vf is less than 53%, the weight reduction effect is inferior. If it exceeds 65%, molding by the above-described injection molding becomes difficult, and mechanical properties (particularly impact resistance) may be lowered. That is, in such a Vf range, when the normal temperature compressive strength after impact application described in SACMA-SRM-2R-94 of the fiber reinforced resin is 240 MPa or more, a material satisfying both the lightening effect and the mechanical properties, can do. The fiber reinforced resin satisfying such requirements is used for various applications because of its excellent mechanical properties and light weight effect. Although it is not particularly limited, it is used for primary structural members, secondary structural members, exterior members, interior members, or parts thereof in transportation equipment such as aircraft, automobiles, and ships, and the effects are maximized.

  SACMA is an abbreviation for Suppliers of Advanced Composite Materials Association, and SACMA-SRM-2R-94 is a test method standard defined here. The room temperature compressive strength after impact is measured under Dry conditions according to SACMA-SRM-2R-94.

The present invention will be further described below using examples. The raw materials and molding methods used in the examples and comparative examples are as follows.
<Reinforcing fiber yarn>
Carbon fiber yarn: PAN-based carbon fiber, 24,000 filament, fineness: 1,033 tex, tensile strength: 6.0 GPa, tensile elastic modulus: 294 GPa, elongation at break: 2.0%.
<Auxiliary fiber yarn 1>
Polyamide fiber yarn: polyamide 66, 7 filament, fineness: 1.7 tex, melting point: 255 ° C., oil content: 0.6%.

Low melting point polyamide fiber yarn: copolymer polyamide, 10 filament, fineness: 5.5 tex, melting point: 115 ° C.
<Auxiliary fiber yarn 2>
Polyester fiber yarn: polyethylene terephthalate, 24 filaments, fineness: 54 tex, melting point: 260 ° C
<Resin material>
Resin material A: Non-woven fabric of polyamide 12 (manufactured by Japan Vilene Co., Ltd.), basis weight: 10 g / m ² , melting point: 175 ° C., glass transition point: 50 ° C.

  Resin material B: polyamide 12 particles.

Resin material C: Non-woven fabric of resin composition 1, basis weight: 18 g / m ² , glass transition point: 85 ° C.

  Resin composition 1: 60% by weight (main component) of a polyethersulfone resin (Sumitomo Chemical Co., Ltd. Sumika Excel (registered trademark) “5003P”) and a liquid bisphenol F epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd.) Epicoat (registered trademark) “806” 21 parts by weight, biphenyl aralkyl type epoxy resin (NC-3000 manufactured by Nippon Kayaku Co., Ltd.) 12.5 parts by weight, and trivalent epoxy resin having a triazine nucleus as a skeleton (Nissan) 4 parts by weight of TEPIC-P manufactured by Chemical Industry Co., Ltd., each of which was measured and melted and kneaded with a 40 wt% (subcomponent) epoxy resin composition stirred at 100 ° C. until uniform. What was made compatible.

Resin material D: particles of resin composition 2, glass transition point: 71 ° C.
Resin composition 2: Polyvinyl formal ("Vinylec (registered trademark)" K type, manufactured by Nitrogen Corporation) 60 parts by weight, liquid bisphenol A type epoxy resin ("Epicoat (registered trademark)" 828, Japan Epoxy Resin Co., Ltd. 10 parts by weight and 30 parts by weight of solid bisphenol A type epoxy resin ("Epicoat (registered trademark)" 1001, manufactured by Japan Epoxy Resin Co., Ltd.) melted and kneaded with a twin screw extruder to be compatible .

Resin material E: Non-woven fabric of resin composition similar to resin material C, basis weight: 50 g / m ² , glass transition point: 85 ° C.
<Matrix resin>
An epoxy resin composition obtained by adding 39 parts by weight of the next curing liquid to 100 parts by weight of the next main liquid and stirring uniformly at 80 ° C. Viscosity by E-type viscometer at 80 ° C .: 55 mPa · s, viscosity after 1 hour: 180 mPa · s, glass transition point after curing at 180 ° C. for 2 hours: 197 ° C., flexural modulus: 3.3 GPa.

  As the main liquid-epoxy, tetraglycidyldiaminodiphenylmethane type epoxy (“Araldite (registered trademark)” MY-721, manufactured by Vantico Co., Ltd.) 40 parts by weight, liquid bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd. (Registered trademark) "825" 35 parts by weight, diglycidylaniline (GAN, Nippon Kayaku Co., Ltd.) 15 parts by weight, and triglycidylaminophenol type epoxy resin ("Epicoat (registered trademark)" 630, Japan Epoxy 10 parts by weight of Resin Co., Ltd. were weighed and stirred at 70 ° C. for 1 hour for uniform dissolution.

As a curing solution, 70 parts by weight of modified aromatic polyamine (“Epicure (registered trademark)” W, manufactured by Japan Epoxy Resin Co., Ltd.), 20 parts by weight of 3,3′-diaminodiphenylsulfone (manufactured by Mitsui Chemicals Fine Co., Ltd.) And 10 parts by weight of 4,4′-diaminodiphenylsulfone (“SumiCure (registered trademark)” S, manufactured by Sumitomo Chemical Co., Ltd.), respectively, weighed and stirred at 100 ° C. for 1 hour to make uniform. The temperature was lowered to 0 ° C., and 2 parts by weight of t-butylcatechol (manufactured by Ube Industries) was measured as a curing accelerator, and further stirred at 70 ° C. for 30 minutes to be uniformly dissolved.
<Ratio of the projected area of the resin material to the surface of the reinforcing fiber base: Area ratio A>
About the reinforcing fiber base before making it into a laminated body, a size of 30 cm × 30 cm was cut out from three locations in the width direction, and the cut sample was measured by a CCD camera from a direction substantially perpendicular to the surface of the reinforcing fiber base. Images were taken with an accuracy of 10 mm / pixel. The obtained image is subjected to image processing using an image processing apparatus (manufactured by KEYENCE: CV-3000) (a material having a diameter of 0.5 mm or more is determined as a resin material), and a pixel of the resin material in the visual field range and the visual field. From the number, the ratio of the projected area of the resin material on the reinforcing fiber substrate was calculated and displayed as a percentage. This was carried out for each of the three samples, and the average value of each value was determined for this example and the comparative example.
<Proportion of the projected area of the resin material in the layers of the laminate: area ratio B>
(1) A sample is cut out in a direction perpendicular to the reinforcing fiber yarn so that the cross-sectional length is 2 cm from any 10 positions of the laminate obtained by laminating the reinforcing fiber base material, and the cut sample is cut out. Was placed in an embedding mold so as to be an observation surface, and embedding resin (manufactured by BUEHLER: EPO KWICK) was poured into the mold. After the embedding resin was cured, the observation surface was polished to prepare an embedding sample. The obtained embedded sample was observed by a digital microscope (“VHX-500” manufactured by KEYENCE Corporation) at a magnification of 500 times according to the following procedure.
(2) For each layer of the reinforcing fiber base constituting the laminate, among the plurality of single yarns constituting the reinforcing fiber yarns penetrating through the resin material, the position of the single yarn forming the outermost surface of the fabric, and The position of the single yarn forming the outermost surface of the fabric is determined from among the plurality of single yarns constituting the reinforcing fiber yarns penetrating through the other resin material facing the fabric thickness direction, and an intermediate between them is determined. A straight line serving as a reference was provided on the image. A reference line was provided for each observation field.
(3) On the reference line, the distance where the resin material does not exist and the distance where the resin material exist are measured. The distance of the resin material present and the distance not present is measured from the left to the right toward the screen, and the left end of the resin material arranged as an independent lump on the reference line of each layer in the laminate The distance from the left end of the resin material arranged right next to the left end of the resin material disposed through the right end through the inside of the resin material was 10 units, and 10 units were measured between each layer. The distance is measured as the distance where the resin material is not present and the distance where the resin material is present when the distance is 10 mm or more, and the distance below this is ignored (10 mm in the region where the resin material exists) Even if there is a region where there is less resin material, there should be resin material, and vice versa.
(4) The above measurement is performed on each cross section, the average value of values obtained from 10 units × number of layers × 10 locations is calculated, and the distance where the resin material exists is the distance where the resin material exists and the resin material exists The value divided by the sum of the distances that were not calculated was calculated and displayed as a percentage.
<Proportion of embedded portion in projected area of resin material on surface of reinforcing fiber base: Ratio C of embedded portion>
(1) A sample is cut out from a reinforcing fiber substrate in a direction perpendicular to the reinforcing fiber yarn so that the cross-sectional length is 2 cm at any 10 locations, and the cut sample is wrapped so that the cut surface becomes an observation surface. It arrange | positioned in an embedding mold and embedding resin (the product made from BUEHLER: EPO KWICK) was poured into the mold. After the embedding resin was cured, the observation surface was polished to prepare an embedding sample. The obtained embedded sample was observed by a digital microscope (“VHX-500” manufactured by KEYENCE Corporation) at a magnification of 500 times according to the following procedure.
(2) With respect to the reinforcing fiber base material, the position of the single yarn forming the outermost surface of the fabric among the plurality of single yarns constituting the reinforcing fiber yarn penetrating through the resin material is determined, and the position becomes a reference A straight line was provided on the image. A reference line was provided for each observation field.
(3) Next, on the reference line, the distance at which the resin material is present is measured on the same basis as in the measurement of the area ratio B, the distance of the embedded portion is measured, and the exposed portion connected to the corresponding embedded portion is described above. The distance at which the resin material is present in the measurement of the area ratio B is determined at the position of 1/2 of the thickness of the exposed portion from the reference line, based on the same reference as when measuring the area ratio B. Using the value obtained in this way, the value obtained by dividing the distance of the buried portion by the distance where the resin material exists was displayed as a percentage.
<Proportion of embedded portion in projected area of resin material between layers of laminate: Ratio D of embedded portion>
(1) From a laminate obtained by laminating reinforcing fiber base materials, a sample is cut out in a direction perpendicular to the reinforcing fiber yarns so that the cross-sectional length is 2 cm at any 10 locations, and the cut out sample is cut out. It arrange | positioned in an embedding mold so that a surface may become an observation surface, and embedding resin (the product made from BUEHLER: EPO KWICK) was poured in into the type | mold. After the embedding resin was cured, the observation surface was polished to prepare an embedding sample. The obtained embedded sample was observed by a digital microscope (“VHX-500” manufactured by KEYENCE Corporation) at a magnification of 500 times according to the following procedure.
(2) For each layer of the reinforcing fiber base constituting the laminate, among the plurality of single yarns constituting the reinforcing fiber yarns penetrating through the resin material, the position of the single yarn forming the outermost surface of the fabric, and The position of the single yarn forming the outermost surface of the fabric among the plurality of single yarns constituting the reinforcing fiber yarn penetrating through the other resin material facing the fabric thickness direction is determined, and A reference straight line (reference line 1) was provided on the image. Further, a straight line (reference line 2) serving as a reference for the interlayer portion is provided on the image at an intermediate position of the reference line 1. These reference lines were provided for each observation field.
(3) Next, on the reference line 1, the distance where the resin material is present is measured with the same standard as in the measurement of the area ratio B, and the distance of the buried portion is measured. The distance at which the resin material exists is determined for the interlayer arrangement portion connected to the buried portion. Using the value obtained in this way, the value obtained by dividing the distance of the buried portion by the distance where the resin material exists in the interlayer arrangement portion was displayed as a percentage.
<Molding method of fiber reinforced resin>
An example of the molding method of the present invention will be described with reference to the drawings.

  FIG. 8 is a cross-sectional view of one embodiment of an apparatus used for carrying out a method for molding a fiber reinforced resin.

As shown in FIG. 8, the reinforcing fiber base 46 was laminated on the surface of the aluminum mold 45 at a predetermined number and angle. A polyester fiber release fabric is disposed as the peel ply 47 on the outermost surface of the laminated reinforcing fiber base, a polypropylene mesh sheet as a resin diffusion medium 48 is disposed thereon, and further, An aluminum cowl plate 49 serving as a pressing plate was disposed. A plurality of non-woven fabrics of polyester fibers were laminated as the edge breather 50 around the periphery of the laminated reinforcing fiber base in contact with the mold. A resin diffusion medium smaller than the maximum outer shape of the reinforcing fiber base material by about 10 to 50 mm was arranged so that the distance from the vacuum suction port 51 or the edge breather to the nearest resin diffusion medium was 10 mm or more (not shown). The whole was covered with a nylon film as the bag material 52, and the bag material and the periphery of the mold were sealed with a seal material 53. The resin injection port 54 was attached so as to be in contact with the resin diffusion medium and sealed with a sealing material. The vacuum suction port was mounted on an edge breather far from the resin injection port and sealed in the same manner. Suction was performed from a vacuum suction port, and vacuum suction was performed so that the inside of the bag material had a pressure of 0.08 to 0.1 MPa. At this time, it was confirmed whether air was leaking, and if it was leaked, it was sealed again so as not to leak. The entire apparatus was heated to the matrix resin injection temperature (80 ° C.) at a rate of 3 ° C./min. While the vacuum suction was continued, the reinforcing fiber substrate was held for 1 hour after reaching the injection temperature. Then, the valve | bulb of the resin injection port was open | released and the required quantity of matrix resin was inject | poured from the resin diffusion medium. When the impregnation was completed, the resin injection valve was closed and the injection of the matrix resin was stopped. Vacuum suction was continued until the matrix resin gelled (1.5 hours from the start of injection). The entire apparatus was heated up to the curing temperature of the matrix resin at a rate of 1.5 ° C./min. Curing temperature: When the temperature reached 130 ° C., suction was stopped by sealing the vacuum suction port. At this time, the bag material was sealed so as to maintain a vacuum state. The matrix resin was sufficiently cured by holding for 2 hours after reaching the curing temperature. Thereafter, the temperature was lowered to room temperature at a rate of 3 ° C./min. The bag material, peel ply and resin impregnated medium were removed to obtain a fiber reinforced resin.
<Method for measuring the thickness of the buried portion, the thickness of the exposed portion, and the thickness of the interlayer arrangement portion>
The notation measuring method in the reinforcing fiber bases and laminates obtained in Examples 1 to 9 and Comparative Examples 1 to 4 described later will be described below.

  First, three reinforcing fiber substrates or laminates were cut out in a size of 2 cm × 2 cm. In the case of a reinforced fiber base material, the cut-out angle is a direction orthogonal to the arrangement direction of the reinforcing fiber yarns. In the case of a laminate, the cut-out angle is reinforced for at least one of the predetermined number of reinforced fiber base materials to be laminated. It cut out in the direction orthogonal to the arrangement direction of fiber yarns. The cut sample was placed in an embedding mold so that the cut surface was on the observation surface side, and an embedding resin (manufactured by BUEHLER: EPO KWICK) was poured into the embedding mold. After the embedding resin was cured, the observation surface was polished to prepare an embedding sample.

The obtained embedded sample was observed at 500 times using a digital microscope (“VHX-500” manufactured by KEYENCE Co., Ltd.). In the observation, each sample shown in FIG. 2 or FIG. 7 for each sample was measured for 10 points, and an average value was calculated for each of the 10 points.
<Normal temperature compressive strength after impact application (hereinafter sometimes referred to as CAI)>
A fiber reinforced resin was molded into a test piece size defined in SACMA-SRM-2R-94, and the normal temperature compressive strength after application of impact was evaluated under the Dry condition by the method defined in SACMA-SRM-2R-94.
Example 1
The carbon fiber yarns were aligned in parallel and arranged in one direction at a density of 1.8 yarns / cm to form a sheet-like carbon fiber yarn group. Auxiliary fiber yarns (polyamide fiber yarns) are arranged at a density of 3 / cm in a direction perpendicular to the carbon fiber yarn group, the carbon fiber yarns and the polyamide fiber yarns are crossed, and the loom is A plain weave fabric was formed (unidirectional fabric).

  The resin material A is pulled so as to overlap the front surface of the unidirectional woven fabric, and the unidirectional woven fabric and the resin material A are combined and sandwiched between release papers, 180 ° C., linear pressure 3 kN / m, 0 The resin material was bonded to the entire surface of the fabric by passing it through a hot press roll at a condition of 0.5 m / min. The resin material A was adhered only to the front surface and not adhered to the back surface.

The obtained reinforcing fiber base was excellent in shape stability because the polyamide fiber yarns crossed firmly to fix the fabric in addition to the resin material A. Further, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 5.3% by weight, the area ratio A is 73%, the thickness of the fabric is 213 μm, the thickness of the embedded portion of the resin material is 67 μm, and the resin material The thickness of the exposed portion was 56 μm, and the ratio C of the buried portion was 87%.
(Example 2)
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

The resin material B was spontaneously dropped while being measured with an embossing roll and a doctor blade, and 11.4 g / m ² (3.0 wt%) was dispersed on the surface while being uniformly dispersed through a vibration net. Thereafter, a far-infrared heater was passed under conditions of 200 ° C. and 0.3 m / min, and the resin material was temporarily bonded to the entire surface of the fabric. The resin material B was adhered only to the front surface and not adhered to the back surface.

  A unidirectional woven fabric, which is a fabric to which resin material B is temporarily bonded, is passed through a press roll under conditions of a linear pressure of 6 kN / m and 0.3 m / min, and the resin material B is reinforced fiber yarn over the entire surface of the fabric. Pressure was applied toward the inside of the strip to form an embedded part. Furthermore, the far-infrared heater was passed again continuously at 180 ° C. and 0.3 m / min.

The obtained reinforcing fiber base was excellent in form stability because the polyamide fiber yarns crossed firmly to fix the fabric in addition to the resin material B. In addition, the amount of the resin material attached to the carbon fiber basis weight (380 g / m ² ) is 3.0% by weight, the area ratio A is 60%, the thickness of the fabric is 393 μm, the thickness of the embedded portion of the resin material is 72 μm, and the resin material The thickness of the exposed portion was 63 μm, and the ratio C of the buried portion was 89%.
(Example 3)
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

The resin material B was naturally dropped while being measured with an embossing roll and a doctor blade, and 15.4 g / m ² (19.2% by weight) was dispersed on the surface while being uniformly dispersed through a vibration net. Thereafter, a far-infrared heater was passed under conditions of 200 ° C. and 0.3 m / min, and the resin material was temporarily bonded to the entire surface of the fabric. The resin material B was sprayed only on the front surface and not on the back surface.

  The unidirectional woven fabric, which is a fabric to which the resin material B is temporarily bonded, is passed through a press roll under the conditions of linear pressure of 4 kN / m and 0.3 m / min, and the resin material B is reinforced fiber yarn over the entire surface of the fabric. Pressure was applied toward the inside of the strip to form an embedded part. Furthermore, the far-infrared heater was passed again continuously at 180 ° C. and 0.3 m / min.

The obtained reinforcing fiber base was excellent in form stability because the polyamide fiber yarns crossed firmly to fix the fabric in addition to the resin material B. In addition, the amount of the resin material attached to the carbon fiber basis weight (80 g / m ² ) is 19.2% by weight, the area ratio A is 67%, the thickness of the fabric is 92 μm, the thickness of the embedded portion of the resin material is 36 μm, and the resin material The thickness of the exposed portion was 107 μm, and the ratio C of the buried portion was 92%.
Example 4
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

  The resin material A is pulled so as to overlap the front surface of the unidirectional fabric that is the fabric, and the unidirectional fabric and the resin material A are combined and sandwiched between release papers, 180 ° C., linear pressure 6 kN / m, 0 The resin material was bonded to the entire surface of the fabric by passing it through a hot press roll at a condition of 0.5 m / min. The resin material A was bonded only to one side.

The obtained reinforcing fiber base was excellent in shape stability because the polyamide fiber yarns crossed firmly to fix the fabric in addition to the resin material A. In addition, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 5.3% by weight, the area ratio A is 74%, the fabric thickness is 206 μm, the thickness of the embedded portion of the resin material is 94 μm, and the resin material The exposed portion had a thickness of 31 μm, and the buried portion ratio C was 96%.
(Example 5)
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

  The resin material C is pulled so as to overlap the front surface of the unidirectional woven fabric that is the fabric, and the unidirectional woven fabric and the resin material C are put together with release paper, 180 ° C., linear pressure 6 kN / m, 0 The resin material was bonded to the entire surface of the fabric by passing it through a hot press roll at a condition of 0.5 m / min. The resin material A was bonded only to one side.

The obtained reinforcing fiber base was excellent in form stability because the polyamide fiber yarns crossed firmly to fix the fabric in addition to the resin material C. Further, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 9.5% by weight, the area ratio A is 78%, the thickness of the fabric is 198 μm, the thickness of the embedded portion of the resin material is 97 μm, and the resin material The thickness of the bonded portion was 83 μm, and the ratio C of the buried portion was 98%.
(Example 6)
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

The resin material B was naturally dropped while being measured with an embossing roll and a doctor blade, and was dispersed on the surface by 15 g / m ² (7.9 wt%) while being uniformly dispersed through a vibration net. Thereafter, a far-infrared heater was passed under conditions of 200 ° C. and 0.3 m / min, and the resin material was temporarily bonded to the entire surface of the fabric. The resin material B was adhered only to the front surface and not adhered to the back surface.

  The unidirectional woven fabric, which is a fabric to which the resin material B is temporarily bonded, is passed through a press roll under the conditions of linear pressure of 4 kN / m and 0.3 m / min, and the resin material B is reinforced fiber yarn over the entire surface of the fabric. Embedded in the article. Further continuously, a far-infrared heater was passed again under the conditions of 180 ° C. and 0.3 m / min, and the resin material was adhered to the entire surface of the fabric.

The obtained reinforcing fiber base material was excellent in form stability because the polyamide fiber yarns crossed firmly to fix the fabric in addition to the resin material B. In addition, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 7.9% by weight, the area ratio A is 65%, the thickness of the fabric is 201 μm, the thickness of the resin material embedded portion is 34 μm, The thickness of the exposed part was 125 μm, and the ratio C of the buried part was 93%.
(Example 7)
A laminate obtained by alternately laminating a predetermined number of the same fabric and resin material A as in Example 1 was placed on the surface of an aluminum mold. A release film is disposed on the surface of the laminate, and an aluminum cowl plate serving as a pressing plate is disposed thereon. A plurality of non-woven fabrics of polyester fibers, which are edge breathers, were laminated around the periphery of the laminated reinforcing fiber substrate in contact with the mold. The edge breather was provided with a vacuum suction port connected to a vacuum pump, the whole was covered with a nylon film as a bag material, and the bag material and the mold were sealed with a sealing material. After carrying these into the autoclave, they were sucked from the vacuum suction port and vacuum sucked so that the pressure inside the bag material was 0.08 to 0.1 MPa. In this state, the inside of the autoclave was pressurized to 0.6 MPa and heated to 180 ° C. at a rate of 1.5 ° C./min. After maintaining for 15 minutes, the temperature was returned to normal temperature and normal pressure at a rate of 2.5 ° C./min. The backing material and the release film were removed to obtain a laminate.

The obtained laminate exhibited tackiness due to the resin material, and was excellent in handleability and form stability as a laminate. Further, the amount of the resin material attached to the carbon fiber basis weight per layer (190 g / m ² ) is 5.3% by weight, the area ratio B is 74%, the thickness of the fabric is 205 μm, and the thickness of the embedded portion of the resin material is 79 μm. The thickness of the interlayer arrangement part of the resin material was 45 μm, and the ratio D of the buried part was 97%.
(Example 8)
The carbon fiber yarns were aligned in parallel and arranged in one direction at a density of 0.9 / cm to form a sheet-like carbon fiber yarn group. Carbon fiber yarns were arranged at a density of 0.9 yarns / cm in a direction perpendicular to the carbon fiber yarn group, and the carbon fiber yarns were interlaced to form a plain weave fabric using a loom. (Bidirectional fabric). Resin material B was bonded in the same manner as in Example 4.

The obtained reinforcing fiber base was excellent in shape stability because the resin material B fixed the fabric in addition to the crossing of the carbon fibers. Further, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 7.9% by weight, the area ratio A is 62%, the thickness of the fabric is 226 μm, the thickness of the embedded portion of the resin material is 148 μm, the resin material The thickness of the exposed portion was 27 μm, and the ratio C of the buried portion was 89%.
Example 9
The carbon fiber yarns were aligned in parallel and arranged in one direction at a density of 0.9 / cm to form a sheet-like carbon fiber yarn group. Similarly, carbon fiber yarns are arranged in one direction at a density of 0.9 yarns / cm to form a sheet-like carbon fiber yarn group, and cross-laminated in a direction perpendicular to the previous carbon fiber yarn group. Then, they were integrated by stitching with a warp knitting machine to form a fabric (biaxial stitch base material). Resin material D was temporarily bonded and bonded in the same manner as in Example 4.

The obtained reinforcing fiber base was excellent in form stability because the reinforcing fiber yarn groups were constrained by warp knitting and the resin material D fixed the fabric. Further, the adhesion amount of the resin material to the carbon fiber basis weight (225 g / m ² ) is 11.3 wt%, the area ratio A is 69%, the thickness of the fabric is 210 μm, the thickness of the embedded portion of the resin material is 97 μm, and the resin material The exposed portion had a thickness of 138 μm, and the ratio C of the buried portion was 91%.
(Comparative Example 1)
The fabric used for the reinforcing fiber base of Example 1 was used as the reinforcing fiber base as it was without adhering the resin material.

Such a reinforcing fiber base material could be handled as a fabric because the bundled yarn A and the polyamide fiber yarn were interlaced and organized. However, since the resin material is not bonded, the reinforcing fiber yarn, the bundled yarn A, and the polyamide fiber yarn are bent. In addition, the thickness of the obtained reinforcing fiber base material was 206 μm.
(Comparative Example 2)
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

  Resin material E is sandwiched between the above fabrics, and the unidirectional woven fabric and resin material E are combined and sandwiched between release papers, and hot pressed under conditions of 180 ° C., linear pressure of 3 kN / m, and 0.5 m / min. The roll was passed and the resin material was adhered to the surface. The resin material E was adhered only to the front surface and not adhered to the back surface.

In addition to the resin material, the obtained reinforcing fiber base material was excellent in form stability because the bundled yarn A and the polyamide fiber yarn were firmly crossed to fix the fabric. In addition, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 26.3% by weight, the area ratio A is 100%, the thickness of the fabric is 207 μm, the thickness of the embedded portion of the resin material is 125 μm, and the resin material The thickness of the exposed portion was 239 μm, and the ratio C of the buried portion was 100%.
(Comparative Example 3)
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

The resin material B was naturally dropped while being measured with an embossing roll and a doctor blade, and was dispersed on the surface by 15 g / m ² (7.9 wt%) while being uniformly dispersed through a vibration net. Thereafter, a far-infrared heater was passed under conditions of 200 ° C. and 0.3 m / min, and the resin material was temporarily bonded to the entire surface of the fabric. The resin material B was adhered only to the front surface and not adhered to the back surface.

  A temporary reinforcing fiber base material, which is a fabric to which the resin material B is temporarily bonded, was cut into a predetermined size and placed on the surface of a mold. A release film was disposed on the surface of the temporary reinforcing fiber base, and a crimping jig was further disposed thereon. The crimping jig is provided with a plurality of indenters at regular intervals in the background, and the total tip area of these indenters is designed to cover 30% of the total projected area of the temporary reinforcing fiber substrate. ing. All of these were installed in a press machine and subjected to hot pressing so that the pressure of each indenter was 0.1 MPa and 90 ° C. to obtain a reinforced fiber base material.

The obtained reinforcing fiber base was inferior in handleability and form stability because the resin material was only partially pressed. Further, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 7.9% by weight, the area ratio A is 64%, the thickness of the fabric is 221 μm, and the thickness of the embedded portion of the resin material in the crimped portion is 79 μm. The thickness of the exposed portion was 45 μm, and in the non-thermocompression bonding portion, the thickness of the embedded portion was 7 μm, and the thickness of the exposed portion was 131 μm. In the embedded portion of the non-crimped portion, the embedded portion in which the resin material included a plurality of single yarns of the reinforcing fiber yarns was not formed, and the ratio C of the embedded portion remained at 27%. .
(Comparative Example 4)
The same fabric as in Example 1 was used as the fabric used for the reinforcing fiber substrate.

  The resin material A is pulled so as to overlap the front surface of the fabric, and the unidirectional fabric and the resin material A are combined and sandwiched between release papers, 150 ° C., linear pressure 3 kN / m, 0.5 m / min. A hot press roll was passed under conditions, and the resin material was adhered to the surface. The resin material A was adhered only to the front surface and not adhered to the back surface.

In addition to the resin material, the obtained reinforcing fiber base was excellent in form stability because the bundled yarn A and the polyamide fiber yarn were firmly crossed to fix the fabric. Further, the amount of the resin material attached to the carbon fiber basis weight (190 g / m ² ) is 5.3% by weight, the area ratio A is 76%, the thickness of the fabric is 223 μm, the thickness of the embedded portion of the resin material is 14 μm, and the resin material The thickness of the exposed portion was 123 μm, and the ratio C of the buried portion was 42%.

  Regarding the mechanical properties (CAI) of the fiber reinforced resin, Examples 1 to 9 showed very high values. Among them, Examples 4, 5, 7 and 9 were particularly excellent. As a result of observing the cross section of the fiber reinforced resin, in Example 7, the resin material adhered to each of the layers facing each other with the interlayer interposed between the fiber reinforced resin layers to form an embedded portion. In other examples, the resin material adhered to only one of the layers to form an embedded portion, and among those in Examples 4, 5 and 9, the embedded portion was formed deeper in the layer. That is, it is estimated that Examples 4, 5 and 9 exhibited an extremely high CAI due to the effect of the interlayer reinforcement effect of the embedded portion in the fiber reinforced resin acting more efficiently.

  On the other hand, since the thing of the comparative example 1 did not use the resin material, an interlayer was not formed in fiber reinforced resin and CAI was remarkably inferior. Further, in Comparative Example 2, the resin material was excessively bonded, and most of the resin material flowed into the reinforcing fiber yarn, thereby inhibiting the impregnation of the matrix resin and not impregnating the fiber reinforced resin. Since the portion was formed, sufficient mechanical properties were not developed. Further, as a result of observing the cross section of the fiber reinforced resin, Comparative Example 4 shows that the resin material was reinforced fiber yarn because a sufficient amount of heat was not supplied to melt and soften the resin material in the step of producing the reinforced fiber substrate. It was in a state where it was adhered only to the surface. Moreover, about the comparative example 3, although the resin material formed the burying part in the crimping | compression-bonding part, it was not formed in the non-crimping part. Due to these reasons, it is considered that the resin material cannot exhibit the interlayer strengthening effect satisfactorily and the CAI is inferior.

  About the handleability of a reinforced fiber base material, the thing of a present Example showed the outstanding handleability. Among them, the sample of Example 8 was more excellent because the shape stabilization effect by the crossing of the carbon fibers was given in addition to the tack by the resin material.

  On the other hand, in the comparative examples, except for the comparative example 1 in which no resin material is used and the comparative example 3 in which the crimping area is small, tackiness due to the resin material appears and the handling property is excellent.

  With regard to the impregnation property of the matrix resin, the present example showed excellent impregnation properties, and a good fiber reinforced resin having no unimpregnated portion could be obtained. Among them, Examples 1, 2, 6, 7, 8, and 9 were able to impregnate the resin in a short time.

On the other hand, in the comparative example, an unimpregnated portion was confirmed except for Comparative Examples 3 and 4. Since Comparative Example 1 did not use a resin material, the effect of forming an interlayer flow path was not exhibited, and Comparative Example 2 was caused by the excessive adhesion amount of the resin material. It is thought that impregnation was hindered.

  The fiber reinforced resin thus obtained is suitable for a wide range of fields including structural members, inner layer members or outer layer members in transportation equipment such as aircraft, automobiles and ships, but is particularly suitable for aircraft structural members. It is.

It is a perspective view which shows typically one embodiment of the reinforced fiber base material of this invention. It is a cross-sectional schematic diagram which shows the aspect of fixation to the fabric of the resin material in the reinforced fiber base material of this invention. It is a perspective view which shows the one aspect | mode of the fabric (unidirectional fabric) used for the reinforced fiber base material of this invention. It is a perspective view which shows one aspect | mode of the fabric (bidirectional fabric) used for the reinforced fiber base material of this invention. It is a perspective view which shows the one aspect | mode of the fabric (stitch base material) used for the reinforced fiber base material of this invention. It is sectional drawing which shows the laminated body of this invention typically. It is an expanded sectional view showing an interlayer part of a layered product of the present invention typically. It is sectional drawing of the one aspect | mode of the apparatus used for implementation of the shaping | molding method of fiber reinforced resin. It is a cross-sectional schematic diagram which shows the aspect of fixation to the cloth of the resin material in the reinforced fiber base material outside the scope of the present invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Reinforcing fiber base material 2 Cloth 3 Resin material 4 Reinforcing fiber yarn 5 Auxiliary fiber yarn 6 Reinforcing fiber base material 7 Reinforcing fiber yarn 8 Resin material 9 Single yarn 10 constituting reinforcing fiber yarn 10 Embedding part 11 of resin material The exposed portion 12 of the resin material The position 13 where the resin material protrudes most from the fabric 13 The position 14 of the single yarn forming the fabric surface 15 The position where the resin material most penetrates into the fabric 15 The thickness 16 of the exposed portion of the resin material 16 The embedded portion of the resin material Thickness 17 Resin material 18 Reinforcing fiber yarn 19 Single yarn 21 constituting reinforcing fiber yarn Position 22 where resin material protrudes most from fabric 22 Position of single yarn forming fabric surface 23 Resin material most penetrated into fabric Position 24 Thickness of exposed portion of resin material 25 Thickness of resin material infiltrated into fabric 26 Fabric 27 Reinforced fiber yarn 28 Auxiliary fiber yarn 29 Fabric 30 Reinforced fiber yarn 31 Reinforced fiber yarn 32 Fabric 33 Strong First layer 34 in which fiber yarn groups are arranged in one direction Second layer 35 in which reinforcing fiber yarn groups are arranged in one direction Auxiliary fiber yarns 36 Fabric 37 Fabric 38 Resin material 39 Resin material layer forming portion Thickness 40 Laminated body 41 Single yarn 42 constituting reinforcing fiber yarn Resin material embedded portion 43 Single yarn constituting reinforcing fiber yarn 44 Resin material embedded portion 45 Aluminum mold 46 Reinforcing fiber base material 46 Laminated body 47 Peel ply 48 Resin diffusion medium 49 Aluminum cowl plate 50 Edge breather 51 Vacuum suction port 52 Bag material 53 Sealing material 54 Resin injection port

Claims (12)

A fabric composed of a group of reinforcing fiber yarns formed by arranging reinforcing fiber yarns in parallel, and at least one surface of the fabric is arranged in a form having a gap within a range of 2 to 20% by weight of the fabric. Each of the resin materials includes a buried portion having a thickness of 15 μm or more and 97 μm or less, wherein a plurality of single yarns of the reinforcing fiber yarns penetrate the resin material, and a fabric The thickness of the embedded portion of the resin material is smaller than the thickness of the fabric constituting the reinforcing fiber base, and is fixed in a form having an exposed portion with an average thickness of 10 to 250 μm, which is present on the surface of And 50-100% of the total projected area of a resin material is being fixed to the surface of the fabric in the said form, The reinforced fiber base material characterized by the above-mentioned. The reinforcing fiber according to claim 1, wherein the thickness of the fabric is 70 to 400 μm, and the thickness of the embedded portion of the resin material is within a range of 50% or less of the thickness of the fabric constituting the reinforcing fiber base. Base material. The resin material is scattered on the surface of the fabric, and the average diameter of the resin material as seen from the surface of the fabric is Ru der less 1 mm, the reinforcing fiber substrate according to claim 1 or 2. The resin material is disposed on both surfaces of the fabric, the reinforcing fiber substrate according to any one of claims 1 to 3. The main component of the resin material is any one or a mixture of two or more thermoplastic resins selected from the group consisting of polyether sulfone, polyamide, polyvinyl formal, phenoxy resin, and polycarbonate. A reinforcing fiber substrate according to any one of the above. The reinforcing fiber according to any one of claims 1 to 4, wherein a main component of the resin material is one or a mixture of two or more thermosetting resins selected from epoxy, unsaturated polyester, vinyl ester, and phenol. Base material. The reinforcing fiber substrate according to any one of claims 1 to 6, wherein a melt viscosity at a shear rate of 1000 / s of the resin material is in a range of 100 to 1000 Pa · s. The fabric extends in a direction intersecting the reinforcing fiber yarns, and the fineness of the reinforcing fiber yarns is 1/5 of the fineness of the reinforcing fiber yarns. The reinforcing fiber substrate according to any one of claims 1 to 7, which is a unidirectional woven fabric composed of the following auxiliary fiber yarn groups. The fabric according to claim 1, wherein the fabric is a bi-directional woven fabric composed of the reinforcing fiber yarn groups arranged in one direction and the reinforcing fiber yarn groups arranged in one direction in different directions. The reinforced fiber base material in any one. In the fabric, at least two layers of the reinforcing fiber yarns arranged in one direction and the reinforcing fiber yarn groups arranged in one direction in different directions are cross-laminated, and the fineness is 1 of the reinforcing fiber yarns. The reinforcing fiber base material according to any one of claims 1 to 7, which is a stitch base material stitched and integrated by an auxiliary fiber yarn group of / 5 or less. The fiber reinforced resin containing the reinforced fiber base material in any one of Claims 1-10 as a reinforced fiber. The fiber-reinforced resin according to claim 11, wherein the reinforcing fiber volume content is in the range of 53 to 65%, and the normal temperature compressive strength after impact application described in SACMA-SRM-2R-94 is 240 MPa or more.