JP2017160572A - Base material for preform, fiber-reinforced resin preform, and fiber-reinforced resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a base material for preform, made of fiber-reinforced resin base material having no value for use in design application due to including fiber defects, allowing a molding with excellent designability to be produced.SOLUTION: A base material for preform includes reinforced fiber threads A orientated at least in one direction. At least one surface of the base material includes fiber defects along the orientation of the reinforced fiber threads A. Reinforced fiber threads B are embedded in the fiber defects.SELECTED DRAWING: Figure 1

Description

  The present invention is a preform substrate, a reinforced fiber preform, and a fiber reinforced resin molded body using the preform, and in particular, in order to improve the appearance quality and the raw material yield in the molded body, The present invention relates to a preform base material in which a fiber defect portion contained is filled with reinforcing fiber yarns.

  Fiber reinforced plastic (FRP) composed of reinforced fibers and matrix resin is widely used in various industrial applications because of its excellent light weight and mechanical properties. Among these, FRP using a reinforcing fiber base material such as a woven fabric or a knitted fabric has an increased utility value as a design member due to its design. In such a design member, in order to emphasize the design of the reinforcing fiber base material, there are many cases in which clear coating is adopted as the finish of the molded body, and the appearance quality is high even with respect to the reinforcing fiber base material used as a raw material. Required.

  In general, a reinforcing fiber base material is processed into a sheet by weaving and knitting a bundle of reinforcing fibers, but it is virtually impossible to eliminate the appearance defect in the manufacturing process. In particular, in automotive outer panel applications where there are many application examples for design purposes, a thin base material is preferably used, so that gaps are formed between parallel reinforcing fiber yarns due to poor placement of reinforcing fibers, poor opening, etc. It is known that the defect of the fiber defect portion is particularly likely to occur. When a substrate including the defect is applied in the vicinity of the surface of the molded body, surface irregularities, patterns, color unevenness, and the like are generated, and in particular, the appearance of the design member is often incompatible. Therefore, since the base material containing the defect has a low utility value in the CFRP for design and is often discarded, there is a problem in that the material yield is reduced and the product cost is thereby increased.

  As a reinforcing fiber base material used for such a design member, Patent Document 1 discloses a multiaxial stitch fabric using a low-melting-point polymer yarn as a stitch yarn. Patent Documents 2 and 3 disclose inventions related to laminates of reinforcing fiber base materials intended for design members. In the laminate, a method of applying a unidirectional base material or non-woven fabric in which carbon fibers are not organized in the outermost surface layer corresponding to the surface of the molded body is shown.

JP 2002-227066 A JP 2006-27091 A JP 2008-132705 A

  However, the invention described in Patent Document 1 has a problem that it is not an effective means for macroscopic defects such as fiber defects. Further, in the inventions described in Patent Documents 2 and 3, as in Patent Document 1, attention is not paid to macroscopic defects, and it is assumed that one layer is added to the outermost layer of the laminate. It cannot be applied to applications for surfaceizing the design of the substrate. Therefore, in the prior art as described above, although a technique for pursuing further surface quality in the molded body has been studied, a technique for improving a substrate containing macroscopic defects has not been studied. However, this is the case.

  Accordingly, the present invention provides a preform substrate that can be applied to design applications by embedding the defect portion in a carbon fiber substrate including a fiber defect portion that has no inherent utility value, in response to the technical problem described above. It is to provide.

  The present invention for solving the above-described problems is as follows.

  The reinforcing fiber yarn A is a base material oriented in at least one direction, including a fiber defect portion along the orientation of the reinforcing fiber yarn A on at least one surface of the base material, and the fiber defect portion is reinforced. A preform base material in which the fiber yarn B is embedded.

  According to the preform base material of the present invention, the dent in the fiber defect portion can be reduced by embedding the fiber defect portion included in the substrate with the reinforcing fiber yarn, and the preform substrate is applied. In a molded object, generation | occurrence | production of surface unevenness | corrugation, a stripe pattern, a color nonuniformity, etc. can be suppressed. Therefore, a base material that was not originally used for design purposes can be effectively used, and it can contribute to improvement of raw material yield and reduction of product cost associated therewith.

The schematic perspective view which shows one embodiment of the base material for preforms in this invention Schematic which shows an example of the generation | occurrence | production aspect of the fiber defect part in the base material for preforms of this invention Simplified diagram showing another mode of occurrence of a fiber defect in the preform substrate of the present invention The simplification figure which shows another one generation | occurrence | production aspect of the fiber defect part in the base material for preforms of this invention Schematic diagram and schematic cross-sectional view showing an example of an embedding aspect of the fiber defect portion in the preform substrate of the present invention Schematic diagram and schematic cross-sectional view showing another embedment mode of the fiber defect portion in the preform substrate of the present invention Schematic diagram and schematic cross-sectional view showing still another embedment mode of the fiber defect portion in the preform substrate of the present invention

  The preform base material of the present invention is a base material in which the reinforcing fiber yarn A is oriented in at least one direction, and the fiber defect portion along the orientation of the reinforcing fiber yarn A is provided on at least one surface of the base material. The reinforcing fiber yarn B is embedded in the fiber defect portion.

  Hereinafter, the structure of the preform substrate of the present invention will be described in detail.

  The preform base material of the present invention includes a base material in which the reinforcing fiber yarns A are oriented in at least one direction as a constituent element. Examples of the reinforcing fibers constituting the reinforcing fiber yarn A used for the base material include carbon fibers, glass fibers, and organic fibers such as aramid, paraphenylenebenzobisoxazole, polyvinyl alcohol, polyethylene, polyarylate, and polyimide. These can be used in combination of one or more of these.

  Among these, carbon fibers are particularly suitable as the reinforcing fibers constituting the reinforcing fiber yarn A because they are excellent in specific strength and specific elastic modulus and have an excellent sense of quality as a design material. As such carbon fibers, polyacrylonitrile (PAN) -based carbon fibers, pitch-based carbon fibers, cellulose-based carbon fibers, and reinforcing fiber yarns formed by blending a plurality of these can be used.

  Further, the reinforcing fiber yarn A is preferably provided with a sizing agent from the viewpoints of handleability and higher workability. The adhesion amount of the sizing agent is preferably in the range of 0.2 to 2.5% by mass, more preferably 0.5 to 1.2% by mass with respect to 100% by mass of the reinforcing fiber yarn including the sizing agent. %. The composition of the sizing agent to be applied is not particularly limited. For example, a compound having a plurality of aliphatic type epoxy groups, an epoxy adduct of polyalkylene glycol, diglycidyl ether of bisphenol A, polyalkylene oxide addition of bisphenol A 1 type or multiple types, such as the thing which added the epoxy group to the product, the polyalkylene oxide addition product of bisphenol A, can be used together.

  The number of filaments of the reinforcing fiber yarn A is preferably 500 to 100,000, more preferably 3,000 to 50,000. The yarn fineness is preferably 33 to 8,000 tex, more preferably 198 to 4,000 tex. In particular, a yarn having a large number of filaments and a large fineness is preferable because it can be obtained at a relatively low cost and the substrate can be manufactured at a low cost. On the other hand, when the basis weight of the reinforcing fiber is low, the number of reinforced fiber yarns to be driven is reduced, so that a gap is easily formed between the yarns, and the frequency of occurrence of a fiber defect portion described later is common. Tend to be higher. Therefore, it can be said that it is a particularly significant aspect to apply the special effect of the present invention.

  In the preform base material of the present invention, the reinforcing fiber yarns A are oriented in at least one direction. If the reinforcing fiber yarn A is oriented in at least one direction, the orientation of the reinforcing fiber yarn A in the substrate is not particularly limited, but one or two directions are preferably used from the viewpoint of practicality, For example, one direction or combination of 0 °, 90 °, + 45 °, and −45 ° is a common configuration. Specific examples of the preform base material of the present invention in which the reinforcing fiber yarns A are oriented in at least one direction include woven fabrics, knitted fabrics, sheets, and the like, and can be appropriately selected according to the use and required performance. In particular, in Non Crimp Fabric (NCF) classified as a knitted fabric, a fiber defect portion along the orientation of the reinforcing fiber yarn is likely to occur on at least one surface of the base material, and thus the effect of the present invention is exhibited. Is a particularly preferred embodiment.

The basis weight of the reinforcing fibers of the preform substrate of the present invention, preferably from 100 to 1000 g / ^{m 2,} more preferably from 200 to 600 g / ^{m 2.} In particular, the range is preferred because there are many thin plate-like members for design purposes. Here, the basis weight of the reinforcing fiber refers to a numerical value measured according to the mass per unit area of JIS R7602 (1995).

  The preform substrate of the present invention includes a fiber defect portion along the orientation of the reinforcing fiber yarn A on at least one surface of the substrate, and the reinforcing fiber yarn B is embedded in the fiber defect portion. .

  A fiber defect | deletion part means the state in which the reinforcing fiber does not exist locally in the surface direction of a base material, and can confirm it as a dent on a base material. This fiber defect portion is a defect that occurs due to, for example, missing of the reinforcing fiber yarn A in the manufacturing process of the base material, fine yarn, twisting, spreading failure, or the like. More specifically, a fiber defect portion occurs due to an abnormal gap or the like that is unintentionally generated due to a production trouble between the yarns.

  Since the fiber defect portion is generated in the process of inserting the yarn in the production of the base material, the arrangement is inevitably generated along the orientation of the reinforcing fiber yarn A, but is not necessarily parallel to the orientation of the reinforcing fiber yarn A. You don't have to. It only needs to be adjacent to the reinforcing fiber yarn A, and includes a case where the shape changes or curves while the fiber defect portion extends.

  Since the reinforcing fiber is not substantially present in the fiber defect part, the thickness is reduced with respect to the surrounding healthy part of the base material, and a dent is formed on the base material. By disposing the dent on the outermost surface of the reinforcing fiber preform described later or in the vicinity thereof, appearance defects such as sink marks, streak patterns, and uneven color transfer on the surface occur when the molded body is formed. Sexuality is impaired. The appearance defect becomes obvious when the fiber defect portion is included on at least one surface of the base material, and is naturally the same even when it is included on both surfaces.

  That is, the base material including the fiber defect portion in the past is greatly restricted in use for a molded product for which the design is used, and in some cases is disposed of, so that the material yield is reduced and the cost of the product is increased. There was a fatal problem such as being connected.

  In order to solve this problem, the present invention provides a preform base material that can be used for design purposes by embedding reinforcing fiber yarns B in the fiber defect part even if the substrate includes the fiber defect part. . That is, by embedding the reinforcing fiber yarn B in the fiber defect portion in the preform base material, the difference in thickness with the peripheral portion can be reduced, and the occurrence and degree of appearance defects when formed into a molded body can be suppressed. Can do. Furthermore, the base material originally discarded can be used effectively, the material yield can be improved, and the cost of the product can be reduced.

  The reinforcing fiber yarn B embedded in the fiber defect portion is not particularly limited as long as it can be embedded in the fiber defect portion, but can be selected from the group of reinforcing fibers similar to the above-described reinforcing fiber yarn A. . Especially, it is preferable that it is the same material as the reinforced fiber yarn A, More preferably, it is the same kind as the reinforced fiber yarn A. By selecting a material closer to the reinforcing fiber yarn A as the reinforcing fiber yarn B, there is no need to consider the difference in performance from the reinforcing fiber yarn A and the compatibility with the matrix resin, and when it is a molded body Homogeneous performance can be expressed. The identity with the reinforcing fiber yarn A is related to the composition and mechanical properties of the reinforcing fiber yarn, the composition and the amount of the sizing agent, and the shape characteristics of the number of filaments and the fineness are the fiber defect portion. Depending on the size, it may be selected as appropriate.

  In order to show the effectiveness of the present invention, the width of the fiber defect portion may be 0.5 mm or more, but in the sense of making the present invention more effective, the width of the fiber defect portion is preferably 2 to 100 mm. The greater the width of the fiber defect portion, the greater the frequency and / or degree of appearance defects in the molded body. This is particularly significant when the width is 2 mm or more, and the effects of the present invention can be further exhibited. On the other hand, the upper limit of the width is not particularly limited, but if it is too large, the repair man-hour of the fiber defect portion is increased and, on the contrary, the cost is increased. In addition, the width | variety of a fiber defect part is the maximum width Wmax in the direction where a fiber defect part extends, and means the length in the direction orthogonal to the orientation direction of the reinforced fiber yarn A. FIG. On the other hand, the length direction LD of the fiber defect portion described later refers to the orientation direction of the reinforcing fiber yarn A.

  As a method of embedding the reinforcing fiber yarn B, there is no particular limitation as long as the reinforcing fiber yarn B is arranged on the fiber defect portion in order to express the effect of the present invention, but the handling property in the subsequent process is improved. From the viewpoint of suppressing misalignment at the time of molding, it is preferable that the reinforcing fiber yarn B is bonded and integrated with the fiber defect portion by the engaging material.

Examples of the form of the engagement material include a porous film, a short fiber nonwoven fabric, a cut fiber, or a powder, and among these, a powder is preferable. By taking this form, the engagement material can be uniformly applied to the fiber defect portion, and the application amount and the application range can be freely adjusted. The adhesion amount of the engaging material applied to the fiber defect portion is not particularly limited, but is preferably in the range of 1 to 20 g / m ² from the viewpoint of achieving both the adhesive strength to the base material and the matrix resin impregnation property.

  Further, the preform base material of the present invention preferably has an engaging material disposed on at least one surface. In this embodiment, the engaging material is adhered to the base material by heat treatment, so that workability is improved. In consideration, the engagement material preferably has a melting point or glass transition temperature in the range of 50-150 ° C.

  As a component of the engaging material, various thermoplastic resins and / or thermosetting resins can be used, and any of them may be a main component. Here, the main component refers to a component contained in excess of 50% by mass in 100 mass of the engaging material.

  For example, when a thermoplastic resin is used as the main component of the engagement material, polyamide, polysulfone, polyether sulfone, polycarbonate, polyvinyl formal, polyether imide, polyphenylene ether, polyimide, polyamide imide, polyvinyl formal, phenoxy One type, two or more types of copolymers selected from the group consisting of phenol, etc., a modified product, or a mixture of two or more types can be used. Among them, the main component of the engaging material is preferably one or a mixture of two or more selected from the group consisting of polyethersulfone, polyamide, polyvinyl formal, phenoxy resin, and polycarbonate.

  Also, when using a thermosetting resin as the main component of the engagement material, epoxy, phenol, polybenzimidazole, benzoxazine, cyanate ester, unsaturated polyester, vinyl ester, urea, melamine, bismaleimide, polyimide, and 1 type, a mixture of 2 or more types selected from the group consisting of polyamideimide, etc., or a modified body, and further a resin added with an elastomer, a rubber component, a curing agent, a curing accelerator, a catalyst, etc. Can do. Among them, the main component of the engagement material is preferably 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. In particular, when epoxy is used as the engagement material, not only is the handleability of the reinforcing fiber base excellent because of its high adhesiveness, but also high mechanical properties can be exhibited when an epoxy resin is used as the matrix resin described later. preferable.

  In the preform base material of the present invention, the engaging material may be disposed on at least one surface of the base material separately from the above viewpoint. With such an embodiment, when the reinforcing fiber preform of the present invention described later is formed, the layers of the laminated reinforcing fiber substrate and the preform substrate of the present invention can be bonded and integrated with each other in a subsequent step. As a result, the shape can be maintained after shape shaping. Here, as long as the engaging material is disposed on at least one surface of the preform base material of the present invention, it may be uniformly dispersed over the entire surface of the base material, or locally on the surface of the base material. It may be scattered, may be patterned on the surface of the substrate, and the mode is not limited as long as adhesion between layers can be ensured at the time of forming a preform described later.

  Here, the preform substrate of the present invention will be described in more detail with reference to the drawings. FIG. 1 is a schematic perspective view showing an embodiment of a preform substrate in the present invention.

  The preform substrate 1 in FIG. 1 includes a first sheet of reinforcing fiber yarns A2 oriented in the + 45 ° direction and a second sheet of reinforcing fiber yarns A2 oriented in the −45 ° direction. The preform substrate 1 of the present invention, which is laminated so as to be orthogonal and integrated by stitch yarns 3, includes a fiber defect portion in the first sheet in which the reinforcing fiber yarns A2 are oriented in the + 45 ° direction. The reinforcing fiber yarn B (not shown) is disposed immediately above the fiber defect portion, and the reinforcing fiber yarn B is bonded and integrated to the fiber defect portion by the engaging material (not shown) of the granular material. Has been.

  The preform base material of the present invention shown in FIG. 1 is generally called a non-crimp fabric (NCF), and is classified into a knitted fabric because stitch yarns form a warp knitting structure. In such an NCF, since a plurality of sheets in which reinforcing fiber yarns are aligned can be formed in an arbitrary direction, for example, “−45 ° / 0 ° / + 45 ° / 90” is provided so as to be pseudo-isotropic. It is also possible to configure as “° ...”. Although the warp knitting structure forms a chain knitting in the drawing, for example, a 1/1 tricot knitting or a composite structure with a chain knitting can be appropriately selected. The stitch yarn to be organized is not particularly limited, and can be selected from monofilament yarns such as polyester, polyamide, polyethylene, polylactic acid, aramid fiber, cotton yarn, silk yarn, and multifilament yarn.

  Furthermore, the embedding method by the fiber defect | deletion part and reinforced fiber yarn B of this invention is demonstrated in more detail using FIGS. 2-7 is the schematic and sectional drawing which showed the one generation | occurrence | production aspect or one embedding aspect of the fiber defect part in the base material for preforms of this invention.

  FIG. 2 shows one form of occurrence of a fiber defect portion in the preform substrate of the present invention. 2 has a length L and a maximum width Wmax along the orientation of the reinforcing fiber yarn A on the base material 6 in which the reinforcing fiber yarn A (not shown) is oriented in the + 45 ° direction. And it extends with a substantially constant width. Here, as the length L, the maximum width in the orientation direction of the reinforcing fiber yarn A is adopted. Further, as the average width Wave of the fiber defect portion, the average value of the maximum width Wmax of the fiber defect portion and the two widths WS and WE at both ends, and the widths W1 to Wn every 200 mm in the length direction of the fiber defect portion. Calculated. When the length L of the fiber defect portion is less than 400 mm, the widths W1 to W3 are measured at three points equally divided in the length direction LD, and the average value of Wmax, WS, and WE is determined as the average width of the fiber defect portion. Let it be Wave. Further, the area S of the fiber defect portion is obtained by the product of the length L and the average width Wave.

  FIG. 3 shows another form of occurrence of the fiber defect in the preform substrate of the present invention. 3 has a length L and a maximum width Wmax along the orientation of the reinforcing fiber yarn A on the base material 8 in which the reinforcing fiber yarn A (not shown) is oriented in the + 45 ° direction. And it is a tapered shape (triangle) and extends with a variation in width. Here, the average width Wave and the area S of the fiber defect portion 7 can be calculated in the same manner as in FIG.

  FIG. 4 shows still another generation mode of the fiber defect portion in the preform substrate of the present invention. 4 has a length L and a maximum width Wmax along the orientation of the reinforcing fiber yarn A on the base material 10 in which the reinforcing fiber yarn A (not shown) is oriented in the + 45 ° direction. Thus, it extends in a circular arc shape (crescent shape) with a width variation. Here, the average width Wave and the area S of the fiber defect portion can be calculated in the same manner as in FIG.

  FIG. 5 shows an embodiment of embedding the fiber defect in the preform substrate of the present invention. In FIG. 5, one of the reinforcing fiber yarns B12 is disposed immediately above the fiber defect portion 11 of FIG. 2, and the reinforcing fiber yarn B12 is formed of the fiber defect portion in the engaging material 13 taking the form of a granular material. 11 is bonded and integrated. Here, the reinforcing fiber yarns B are arranged to such an extent that the fiber defect portion is almost buried. By setting it as this aspect, the effect of this invention is fully expressed, However, From a viewpoint of managing the amount of embedding of the reinforcing fiber yarn B more appropriately, the charge rate R can be used as an index.

The above charge rate R, the volume V ₁ of the fiber defect, represented a ratio between the volume V ₂ of the reinforcing fiber yarns B in equation (1).

The volume V ₁ of the fiber defect portion is a product of the area S of the fiber defect portion and the theoretical thickness T. And the theoretical thickness T (mm) is the basis weight FAW (g / m ² ) of the base material where the fiber defect portion exists and the specific gravity ρ _A (g / cm ³ ) of the reinforcing fiber yarn A constituting the base material. It is a quotient and is calculated by the equation (2).

Further, the volume V ₂ of the reinforcing fiber yarn B is calculated from the length L _B , the fineness Y _B (tex) and the specific gravity ρ _B (g / cm ³ ) of the reinforcing fiber yarn B to be used in the formula (3). Calculated. Here, in the volume V ₂ of the reinforcing fiber yarns B and the volume V ₁ of the fiber defect, since it contains a void portion, it is necessary to consider the fiber volume fraction in the preform step described below, the same pressure Since it is accompanied by a load, it is assumed that the fiber volume content is substantially the same, so it can be ignored in this formula.

  In the present invention, the charge rate of the reinforcing fiber yarn B in the fiber defect portion is preferably 80 to 120%, more preferably 90 to 110%. By setting it as such a range, the effect of this invention can be made more reliable and the molded object excellent in surface quality can be obtained.

  FIG. 6 shows another embedment mode of the fiber defect portion in the preform base material of the present invention. In FIG. 6, two reinforcing fiber yarns B15 having the same fineness are arranged immediately above the fiber defect portion 14 of FIG. 3, and the reinforcing fiber yarns B15 are formed by the engaging material 16 that takes the form of powder particles. Bonded and integrated with the fiber defect.

  FIG. 7 shows still another embedding mode of the fiber defect portion in the preform substrate of the present invention. In FIG. 7, two reinforcing fiber yarns B18 having different fineness are arranged immediately above the fiber defect portion 17 of FIG. 4, and the reinforcing fiber yarn is formed by the engaging material 19 in the form of a granular material from above. The strip B18 is bonded and integrated with the fiber defect portion.

  As shown in FIGS. 6 and 7, in embedding the reinforcing fiber yarn B in the fiber defect portion, the reinforcing fiber yarn B to be embedded does not necessarily need to be one, and the number to be used depends on the shape of the fiber defect portion. It is preferable to appropriately adjust the layout and end shape.

  The preform substrate of the present invention can be laminated with another reinforcing fiber substrate to form a reinforcing fiber preform. In the reinforcing fiber preform, when the outermost layer is the first layer and the layer adjacent to the first layer is the second layer, at least one of the first layer and the second layer is used for the preform of the present invention. Arrange the substrate.

  The reinforcing fiber preform is an intermediate for producing a molded body, and a molded body is obtained by injecting a matrix resin into the preform. Therefore, the laminated structure in the preform is directly reflected in the final product. However, in the case of a base material including a conventional fiber defect portion, this base material is used as the first layer or the second layer of the reinforcing fiber preform. When arranged, since the appearance of poor transfer due to the depression of the fiber defect portion and the transfer of the pattern and the color unevenness occurs in the formed body when the molded body is formed, the base material including the fiber defect portion is further provided in the third and subsequent layers. They could only be used for the inner layer or discarded.

  On the other hand, the preform substrate according to the present invention is applied to the first layer or the second layer of the preform because the reinforced fiber yarn B is embedded in the fiber defect portion and the dent is reduced. However, the occurrence of the appearance defect described above is reduced or eliminated, and the degree of freedom of lamination is greatly expanded. In particular, in a member intended for design, the shape of a thin wall and a large area is the mainstream, and it is often the case that a laminated structure of 5 layers or less is obtained, so that the effect of the present invention is further exhibited.

  In the present invention, the outermost surface layer, which is the first layer of the reinforcing fiber preform, refers to the layers disposed on the lowermost surface and the uppermost surface in the laminated structure. And the layer adjacent to the first layer, which is the second layer of the reinforcing fiber preform, refers to the first layer immediately above and the layer immediately below. Then, the preform substrate of the present invention may be appropriately selected according to the handling in the final molded body, for example, when only the lowermost one surface is a design surface in the molded body, When at least the preform substrate of the present invention is arranged in the first and second layers on the lowermost surface and both surfaces of the molded body are designed surfaces, the first and second layers on the lowermost surface and the uppermost surface respectively. Just place it in your eyes.

  Further, as another viewpoint, it may be properly used depending on the coating method of the molded body. When the molded body is colored, the preform base material of the present invention is disposed in the first layer and the second layer of the preform. In the case of clear coating, since the embedded trace of the fiber defect portion becomes surface and impairs the appearance, the preform substrate of the present invention may be disposed from the second layer of the preform.

In the reinforcing fiber preform of the present invention, the reinforcing fiber base material is disposed in at least one first layer, the preform base material is disposed in at least one second layer, and the first layer is disposed in the first layer. As another reinforcing fiber base, it is preferable to use a bidirectional fabric. More specifically, when the design of the reinforcing fiber base is put on the surface by clear coating, it is preferable to use a bidirectional fabric having a beautiful design by the woven pattern. As the bidirectional fabric to be used, various structures such as a plain structure, a twill structure, and a satin structure can be appropriately selected. For even fineness of reinforcing fiber yarns to be used for bi-directional woven fabric, in view of design property, preferably thin line of the 50～400Tex, preferably 100~350g / ^{m 2} as with reinforcing fibers th substrate.

  The laminated base material for preform of the present invention constituting the reinforcing fiber preform of the present invention and the reinforcing fiber base material are joined and integrated with each other from the viewpoint of handling in the subsequent process and form stability. It is preferable to do. As a means for joining and integrating the preform base material of the present invention and the reinforcing fiber base material constituting the reinforcing fiber preform of the present invention, various engagement materials, stitches, needling, tufting, spray-up methods can be used. , Etc., can be appropriately selected from means for effecting bonding in the thickness direction of the reinforcing fiber preform. Among them, the method of adhering the layers with the above-described engaging material is preferable, and the reinforcing fiber base material is not damaged and the appearance is not surfaced as compared with mechanical means such as stitches and needle punches.

  Further, among the engaging materials, powder is preferable. By adopting such a form, the applied amount can be freely adjusted for each solid, and it is possible to uniformly disperse in the in-plane direction. In addition, a space is formed between the layers of adjacent reinforcing fiber substrates, and the resin is injected. In forming a molded body, it can serve as a matrix resin flow path.

  As a method for integrating the reinforcing fiber preform with the engaging material, whether to apply the engaging material to the preform base material and the reinforcing fiber base in advance or to apply each time the base material is laminated. In any case, the former is preferable from the viewpoint of productivity. Next, the laminated body stacked in an arbitrary configuration is bonded and integrated by applying a predetermined temperature and pressure by a hot press apparatus or a debulk apparatus.

  In the present invention, the preform substrate or the reinforced fiber preform described above is impregnated with a resin to form a fiber reinforced resin molded body. That is, the fiber-reinforced resin molded product of the present invention is obtained by impregnating the reinforcing fiber preform of the present invention with a resin.

  As a molding method of the fiber reinforced resin molding of the present invention, RTM (Resin Transfer Molding) molding, RFI (Resin Film Infusion) molding, RIM (Resin Injection Molding) molding, vacuum assist RTM, press molding, hand layup molding, A molding method such as can be applied. Among them, RTM molding is suitable for industrial applications with many design members since a molded product with high productivity and excellent surface quality can be obtained.

  In RTM molding, a reinforcing fiber preform shaped into a reinforcing fiber base or molded body is placed inside a mold consisting of an upper mold and a lower mold, and after the mold is clamped, the resin is decompressed from the resin injection hole. The fiber-reinforced resin molded article is obtained by injecting into the preform and impregnating the preform. After heat curing, the mold is opened and removed.

  As the resin used in the RTM molding, a thermosetting resin having a low viscosity and easily impregnating reinforcing fibers, or a monomer for RIM (Resin Injection Molding) that forms a thermoplastic resin is preferable. Examples of thermosetting resins include epoxy resins, unsaturated polyester resins, polyvinyl ester resins, phenol resins, guanamine resins, polyimide resins such as bismaleide and triazine resins, furan resins, polyurethane resins, polydiallyl phthalate resins, A melanin resin, a urea resin, an amino resin, etc. are mentioned.

  Further, polyamides such as nylon 6, nylon 66 and nylon 11, or copolymerized polyamides of these polyamides, polyesters such as polyethylene terephthalate and polybutylene terephthalate, or copolymerized polyesters of these polyesters, polycarbonate, polyamideimide, Examples thereof include polyphenylene sulfide, polyphenylene oxide, polysulfone, polyether sulfone, polyether ether ketone, polyether imide, and polyolefin, and thermoplastic elastomers represented by polyester elastomer and polyamide elastomer.

  Also, a resin obtained by blending a plurality selected from the above-mentioned thermosetting resins, thermoplastic resins, and rubbers can be used. Among them, an epoxy resin is preferable as a preferable resin from the viewpoint of suppressing thermal shrinkage at the time of molding which affects the design property.

  The above-obtained fiber reinforced resin molded product can be suitably used mainly in the field of production of design outer plate members including automobile panel members. Here, the design outer plate member is a so-called panel member such as a door panel or hood, roof, trunk lid, fender, spoiler, side skirt, front skirt, mud guard, door inner panel or the like in an automobile or truck, and other related panels. Examples of members include panels such as doors, side panels, interior panels, and cranes in railway vehicles. In addition to the construction machinery covers, building dividers, partyers, door panels, shielding plates, sports surfboards, skateboards, bicycle parts, and other parts that require design. It can also be applied to.

Hereinafter, the present invention will be described in more detail with reference to examples.
(1) Reinforcing fiber yarn <Carbon fiber 1>
“Torayca (registered trademark)” manufactured by Toray Industries, Inc., tensile strength 4,900 MPa, tensile elastic modulus 230 GPa, fineness 800 tex, specific gravity 1.80.

<Carbon fiber 2>
“Torayca (registered trademark)” manufactured by Toray Industries, Inc., tensile strength 4,900 MPa, tensile elastic modulus 230 GPa, fineness 1650 tex, specific gravity 1.80.

<Carbon fiber 3>
“Torayca (registered trademark)” manufactured by Toray Industries, Inc., tensile strength 4,900 MPa, tensile elastic modulus 230 GPa, fineness 200 tex, specific gravity 1.80.

<Carbon fiber 4>
“Torayca (registered trademark)” manufactured by Toray Industries, Inc., tensile strength 4,900 MPa, tensile elastic modulus 230 GPa, fineness 800 tex, specific gravity 1.80.

<Carbon fiber 5>
“Torayca (registered trademark)” manufactured by Toray Industries, Inc., tensile strength 3530 MPa, tensile elastic modulus 230 GPa, fineness 66 tex, specific gravity 1.76.

<Carbon fiber 6>
“Torayca (registered trademark)” manufactured by Toray Industries, Inc., tensile strength 3530 MPa, tensile elastic modulus 230 GPa, fineness 198 tex, specific gravity 1.76.

<Carbon fiber 7>
“Torayca (registered trademark)” manufactured by Toray Industries, Inc., tensile strength 3530 MPa, tensile modulus 230 GPa, fineness 396 tex, specific gravity 1.76.

<Carbon fiber 8>
Carbon fiber (product number: Panex35) manufactured by Zoltek, tensile strength 4137 MPa, tensile elastic modulus 242 GPa, fineness 3704 tex, specific gravity 1.81.

<Glass fiber 1>
Glass roving (product number: RS 110 QL-520) manufactured by Nittobo Co., Ltd., fineness 1150 tex, specific gravity 2.50 g / m ³ .

(2) Stitch yarn "Tetron (registered trademark)" manufactured by Toray Industries, Inc., 24 filaments, fineness 33 dtex, Woolley processed yarn (3) Engagement material polyvinyl formal ("Vinylec" K type manufactured by Nitrogen Corporation) 60 parts by mass 10 parts by mass of liquid bisphenol A type epoxy resin (“Epicoat” 828 made by Japan Epoxy Resin Co., Ltd.), 30 parts by mass of solid bisphenol A type epoxy resin (“Epicoat” 1001 made by Japan Epoxy Resin Co., Ltd.) Master batch pellets were obtained by kneading at 180 ° C. using an extruder. The master batch was freeze pulverized with liquid nitrogen using a hammer mill (“PULVERIZER” manufactured by Hosokawa Micron Corporation) to obtain a powder-like engagement material. The obtained engagement material had an average particle diameter of about 120 μm and a glass transition temperature of 71 ° C.

(4) Production of reinforcing fiber base material <Base material 1>
A first sheet in which a plurality of carbon fibers 1 are aligned in parallel in the + 45 ° direction so that the basis weight of the reinforcing fiber is 150 g / m ^2, and a plurality of carbon fibers 1 are similarly 150 g / m in the reinforcing fiber basis weight. ^2nd sheets aligned in parallel in the -45 ° direction so as to be 2 are stacked on each other, and then stitched with a stitch of 5.0 gauge / inch gauge and 9.0 chain / inch chain stitch The suture was integrated with the tissue to obtain an NCF substrate 1. The width of the obtained base material 1 was 1500 mm.

<Substrate 2>
An NCF base material 2 was obtained in the same manner as the base material 1 except that the orientation of the reinforcing fiber yarns in the first sheet was set to 0 ° and the orientation of the reinforcing fiber yarns in the second sheet was set to 90 °. .

<Substrate 3>
The NCF base material 3 was obtained in the same manner as the base material 1 except that the carbon fiber 8 was used as the reinforcing fiber yarn of each sheet and the basis weight of the reinforcing fiber was 200 g / m ² .

<Substrate 4>
A plain weave structure is formed with a rapier loom so that the carbon fiber 6 is a warp and a weft and the warp density is 12.5 / 25 mm and the weft density is 12.5 / 25 mm. 4 was obtained. The obtained base material 4 had a reinforcing fiber basis weight of 198 g / m ² , a width of 1500 mm, and an adhesion amount of engaging material of 6 g / m ² .

<Substrate 5>
NCF was obtained in the same manner as in the base material 1 except that the orientation of the reinforcing fiber yarns in the first sheet was changed to the −45 ° direction and the orientation of the reinforcing fiber yarns in the second sheet was changed to + 45 °. The obtained NCF is passed through a processing facility composed of a powder spraying device, a non-contact heating device (far infrared heater: substrate surface temperature 130 to 150 ° C.), and a conveying device, and the substrate one side (first sheet) ) Was applied evenly over the entire surface to obtain a substrate 5. Here, the adhesion amount of the engaging material was 6 g / m ² .

<Substrate 6>
A bi-directional woven fabric was obtained in the same manner as the base material 4 except that the carbon fiber 1 was a warp and a weft, and the warp density was 4.94 / 25 mm and the weft density was 4.94 / 25 mm. An engaging material was applied to the bidirectional fabric in the same manner as the base material 5 to obtain a base material 6. The obtained base material 6 had a reinforcing fiber basis weight of 300 g / m ² , a width of 1500 mm, and an adhesion amount of the engaging material of 6 g / m ² .

(5) Production of Reinforcing Fiber Preform The reinforcing fiber base was cut into a 1000 mm × 1000 m square, and any four layers were stacked to form a laminate. In addition, in the said process, when a reinforced fiber base material has a fiber defect | deletion part, a base material is cut | disconnected so that a fiber defect | deletion part may be arrange | positioned in the center of a base material (For example, a reinforced fiber yarn is +45 degrees). In the case of orientation, the fiber defect portion is positioned on the diagonal line in the base material after cutting). Next, the laminate is placed in a 1000 mm × 1000 mm flat plate cavity installed in a press molding machine, pressed at a mold temperature of 100 ° C. and a pressure of 0.06 MPa for 3 minutes, and the mold temperature is kept at 50 while maintaining the pressure. After cooling to ° C., the mold was opened and the laminate was taken out to obtain a reinforcing fiber preform.

(6) Production of Fiber Reinforced Resin Molded Body The reinforcing fiber preform is placed between an upper mold and a lower mold of a mold having a 1000 mm × 1000 mm flat plate cavity installed in a press molding machine. Next, the mold was clamped, and the mold was heated to 120 ° C. by flowing heat medium oil. Subsequently, the mold is kept in a vacuum state with the temperature of the mold kept at 120 ° C. In this state, a resin discharge hole installed in the upper mold is opened, and the resin is injected into the mold using a resin injecting machine. A low viscosity epoxy resin for RTM was injected. The resin was cured while maintaining this state, and then removed from the mold to obtain a fiber-reinforced resin molded body.

(7) Evaluation of surface quality Surface quality evaluation was performed on the fiber reinforced resin molded product obtained in (6) using a molded product that had been subjected to clear coating or colored coating. The evaluation items were two items of surface irregularities and streak patterns, and each was visually evaluated according to the following criteria.
◎: Not visible at all ○: Not visible without position information △: Faintly visible ×: Visible clearly (8) In the manufacturing process of workability preform base material (hereinafter referred to as PF base material) The time required for the work to embed the reinforcing fiber yarns B1 and B2 and optionally bond and integrate them with the engaging material was evaluated according to the following criteria.
○: Within 15 minutes Δ: Over 15 minutes within 45 minutes ×: Over 45 minutes (Example 1)
In the 1st sheet | seat of the base material 1, the insertion pitch of the reinforced fiber yarn A was intentionally operated, and the fiber defect part was formed. The fiber defect portion had a maximum width Wmax 1.5 mm, an average width Wave 1.4 mm, and a length L2121 mm. A carbon fiber 6 having a length of 2121 mm was embedded as a reinforcing fiber yarn B1 in the fiber defect portion to obtain a preform substrate (PF substrate).

  Next, the PF base material is [base material 4 / PF base material / base material 5 / base material 6] (where the orientation of the reinforcing fiber yarn is [(0/90) / (+ 45 / −45) / (− 45 / + 45) / (0/90)], and a reinforced fiber preform was obtained by the procedure (5).

  The reinforced fiber preform was made into a fiber reinforced resin molded article by the procedure (6), and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 2)
In the substrate 1, a fiber defect portion having a maximum width Wmax of 3.0 mm, an average width Wave of 2.8 mm, and a length of L2121 mm was formed. Engagement material was applied evenly in the base material surface direction using a sieve to the fiber defect portion, and carbon fibers 7 were arranged thereon as reinforcing fiber yarns B1. Here, the engagement material was applied in a masked state leaving the fiber defect portion, and the adhesion amount was about 2 g / m ² from the application area and the amount of the engagement material used. In this state, the surface temperature of the base material was heated at 130 to 150 ° C. using a far infrared heater, and the carbon fiber 7 was melt bonded to the fiber defect portion to obtain a PF base material.

  A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 3)
In the base material 1, a fiber defect portion having a maximum width Wmax of 7.0 mm, an average width Wave of 6.8 mm, and a length of L2121 mm was formed. Next, the base material was passed through a processing facility including a powder spraying device, a non-contact heating device (far-infrared heater), and a conveying device, and the engaging material was uniformly applied to the entire surface of the base material. The adhesion amount of the engaging material on the obtained base material was about 6 g / m ² . Then, the glass fiber 1 was arrange | positioned just above the said fiber defect | deletion part, and it carried out similarly to Example 2 in this state, and melt-bonded the glass fiber 1 to the base material with the engagement material, and obtained the PF base material.

  A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

Example 4
A PF base material was obtained in the same manner as in Example 3 except that three carbon fibers 6 were used as the reinforcing fiber yarns B1 and one carbon fiber 5 was used as the reinforcing fiber yarns B2 in the embedding of the fiber defect portion. It was. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 5)
A PF base material was obtained in the same manner as in Example 3 except that one carbon fiber 1 was used as the reinforcing fiber yarn B1 and three carbon fibers 6 were used as the reinforcing fiber yarn B2 in embedding the fiber defect portion. It was. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 6)
A PF base material was obtained in the same manner as in Example 3 except that one carbon fiber 1 was used as the reinforcing fiber yarn B1 and one carbon fiber 3 was used as the reinforcing fiber yarn B2 in the embedding of the fiber defect portion. It was. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 7)
A PF base material was obtained in the same manner as in Example 3 except that one carbon fiber 1 was used as the reinforcing fiber yarn B1 and one carbon fiber 5 was used as the reinforcing fiber yarn B2 in the embedding of the fiber defect portion. It was. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 8)
A PF base was obtained in the same manner as in Example 3 except that the base material of the PF base was used as the base 2. The obtained PF base material is referred to as [PF base material / base material 1 / base material 5 / base material 6] (where the orientation of the reinforcing fiber yarn is [(0/90) / (+ 45 / −45) / (-45 / + 45) / (0/90)]), and a reinforcing fiber preform was obtained by the procedure of (5). The reinforced fiber preform was made into a fiber reinforced resin molded article by the procedure (6), and the surface quality and workability were evaluated according to (7) and (8). The molded body was colored. The evaluation results are shown in Table 1.

Example 9
Example 3 except that the raw material of the PF base material is the base material 3, the fiber defect part is the maximum width Wmax 18.5 mm, the average width Wave 18.2 mm, the length L 2121 mm, and the reinforcing fiber yarn B 1 is carbon fiber 8. Similarly, a PF base material was obtained. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 10)
A PF base material was obtained in the same manner as in Example 9, except that the fiber defect portion had a maximum width Wmax of 117 mm, an average width of Wave 111 mm, and a length L2121 mm, and seven reinforced fiber yarns B1 had seven carbon fibers 8. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 11)
A PF base material was obtained in the same manner as in Example 3 except that one of the carbon fibers 7 was used as the reinforcing fiber yarn B1 in embedding the fiber defect portion. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Example 12)
A PF base material was obtained in the same manner as in Example 3 except that one of the carbon fibers 2 was used as the reinforcing fiber yarn B1 in embedding the fiber defect portion. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Comparative Example 1)
A PF substrate was obtained in the same manner as in Example 3 except that the fiber defect portion had a maximum width Wmax of 0.20 mm, an average width Wave of 0.17 mm, and a length L2121 mm, and the fiber defect portion was not embedded. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

(Comparative Example 2)
A PF substrate was obtained in the same manner as in Example 3 except that the fiber defect portion was not embedded. A fiber reinforced resin molded article was prepared in the same manner as in Example 1 except that the PF substrate was used, and the surface quality and workability were evaluated according to (7) and (8). The molded body was a clear paint. The evaluation results are shown in Table 1.

  In Examples 1 to 3, the surface quality and workability of the molded body are good. In Example 2, the engagement material is applied to the entire surface of the base material in Example 3 in the fiber defect portion, so that the subsequent steps of PF base material and / or reinforcing fiber preform are applied to Example 1 respectively. Excellent handleability.

  In Examples 3-8, 11, 12, and Comparative Examples 2-4, a difference was recognized in the surface quality depending on the degree of the charge rate. Examples 4, 5, 11, and 12 are results that are slightly inferior to the surface quality, but are practically usable depending on the application. On the other hand, Comparative Example 2 in which the reinforcing fiber yarn is not embedded in the fiber defect portion has particularly high visibility of the appearance defect among all the Examples and Comparative Examples, and a clear superior difference is recognized in the quality. On the other hand, since Examples 3, 6, 7, and 8 had a relatively high charge rate, the surface quality was good. Among them, in Example 8, the PF base material was applied to the outermost layer. However, since the surface unevenness was excellent, the colored coating was applied so that the charge rate was inferior to those in Examples 1 and 2 having the same level. There was no finish. Moreover, in Example 3 using glass fiber as the reinforcing fiber yarn B1, the improvement effect of the same surface quality was confirmed as compared with that using carbon fiber.

  Further, in Examples 9 and 10, since the carbon fiber yarn having a finer fineness is used as the reinforcing fiber yarn A, the width of the fiber defect portion is larger than the above, but the charge rate is appropriate. Therefore, the surface quality was particularly good even when compared with other examples. In Comparative Example 1, since the width of the fiber defect portion was small, practical surface quality was ensured without embedding with the reinforcing fiber yarn B.

  On the other hand, from the viewpoint of workability, superiority or inferiority is indicated by the number of reinforcing fiber yarns B used for embedding the fiber defect portion, and it is preferable to minimize the number of fibers used. Therefore, Examples 1, 2, and 9 are the best among the examples.

  Among these examples, Example 9 was most excellent from the comprehensive viewpoints of handleability, surface quality, and workability.

  According to the preform substrate of the present invention, it is suitably used as a molding material for a design member. Further, the fiber reinforced resin molded body obtained in this way is preferably used mainly in the field of production of design outer plate members such as automotive panel members, and covers for automobiles and construction machinery, partition plates for construction, It is on the outside of sports panels, such as surfboards, skateboards, and bicycle parts, such as door panels and shielding plates.

1: Base material for preform 2: Reinforcing fiber yarn A
3: Stitch yarns 4, 5, 7, 9, 11, 14, 17: Fiber defect portions 6, 8, 10: Base materials 12, 15, 18: Reinforced fiber yarn B
13, 16, 19: engagement material

Claims (9)

  The reinforcing fiber yarn A is a base material oriented in at least one direction, including a fiber defect portion along the orientation of the reinforcing fiber yarn A on at least one surface of the base material, and the fiber defect portion is reinforced. A preform base material in which the fiber yarn B is embedded.   The preform substrate according to claim 1, wherein an engagement material is disposed on at least one surface.   The preform substrate according to claim 1 or 2, wherein the reinforcing fiber yarn B is bonded and integrated with the fiber defect portion by an engaging material.   The preform substrate according to any one of claims 1 to 3, wherein a width of the fiber defect portion is 2 to 100 mm.   The preform substrate according to any one of claims 1 to 4, wherein a charge rate of the reinforcing fiber yarn B in the fiber defect portion is 80 to 120%. The preform substrate according to any one of claims 1 to 5 and the reinforcing fiber substrate are laminated reinforcing fiber preforms,
When the outermost layer of the reinforcing fiber preform is the first layer and the layer adjacent to the first layer is the second layer, the preform substrate is disposed on at least one of the first layer and the second layer. Reinforced fiber preform. A reinforcing fiber base material is arranged in at least one first layer, a preform base material is arranged in at least one second layer,
The reinforcing fiber preform according to claim 6, wherein the reinforcing fiber base disposed in the first layer is a bidirectional fabric.   A fiber-reinforced resin molded article obtained by impregnating the reinforcing fiber preform according to claim 6 or 7 with a resin.   The fiber-reinforced resin molded body according to claim 8, wherein the molded body is used for a design outer plate member.

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