JP2019150990A - Metal-thermoplastic fiber reinforced resin material composite member processing method, metal-thermoplastic fiber reinforced resin material composite member, and automotive parts - Google Patents

Abstract

To provide a method of processing a metal-thermoplastic fiber reinforced resin material composite in which a metal member and a fiber reinforced resin material are firmly bonded, allowing for integral processing at low cost.SOLUTION: The method of processing the metal-thermoplastic fiber reinforced resin material composite member comprises: an integrally processing step of heating a metal plate having, at least on one surface, a fiber reinforced resin material having a matrix resin containing a thermoplastic resin, and a reinforcing fiber material, to a predetermined temperature at which the shape of the fiber reinforced resin material cannot be maintained by itself, and then applying a predetermined pressure thereto through a die having a predetermined shape for integrally processing; and a releasing step of releasing the integrally processed metal plate and fiber reinforced resin material from the die at a predetermined temperature at which the shape of the fiber reinforced resin material is not yet settled.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a method for processing a metal-thermoplastic fiber reinforced resin material composite member, a metal-thermoplastic fiber reinforced resin material composite member, and an automotive part.

  Fiber reinforced plastics (FRP: Fiber Reinforced Plastics) in which reinforced fibers (for example, glass fibers, reinforced fibers, etc.) are mixed into a matrix resin are lightweight and excellent in tensile strength and workability. For this reason, it is widely used from the consumer field to industrial applications. Also in the automobile industry, in order to meet the needs for lighter vehicle bodies that lead to improved fuel economy and other performances, focusing on the light weight, tensile strength, workability, etc. of FRP, the application of FRP to automobile members is being studied. .

  When the FRP itself is used as an automobile member, for example, there are various problems as follows. First, since FRP has low compressive strength, it is difficult to use it as it is for automobile members that require high compressive strength. Secondly, since the matrix resin of FRP is generally brittle because it is a thermosetting resin such as an epoxy resin, there is a possibility of brittle fracture when it is deformed. Thirdly, FRP (particularly, reinforced fiber reinforced plastic (CFRP: Carbon Fiber Reinforced Plastics) using reinforced fiber as the reinforced fiber) is expensive and causes an increase in the cost of automobile components. Fourthly, as described above, since the thermosetting resin is used as the matrix resin, the curing time is long and the tact time is long. Therefore, it is not suitable for manufacturing an automobile member requiring a short tact time. Fifth, FRP using a thermosetting resin as a matrix resin does not undergo plastic deformation, and therefore cannot be bent once cured.

  In order to solve these problems, recently, a metal member-FRP composite material in which a metal member and FRP are laminated and integrated (composited) has been studied. About the said 1st problem, the compression strength of a composite material can also be raised by making a metal member and FRP with high compression strength compound. About the said 2nd problem, brittleness falls by compounding with metal members, such as a steel material which has ductility, and it becomes possible to deform | transform a composite material. About the said 3rd problem, since the usage-amount of FRP can be reduced by compounding a low-cost metal member and FRP, the cost of a motor vehicle member can be reduced.

  In order to combine the metal member and FRP, it is necessary to join or bond the metal member and FRP. As a joining method, a method of using an epoxy resin thermosetting adhesive is generally used. Are known.

  For example, in the following Patent Document 1, a structural material in which a light metal material and CFRP are bonded with an adhesive is proposed.

  Further, in the production of a metal member-FRP composite, development of a method that can be produced with low energy consumption and low cost is underway.

  Patent Document 2 below proposes a method of manufacturing a metal-CFRP composite structure by press-molding a CFRP prepreg made of a reinforcing fiber material and a thermosetting resin material on the surface of a hot-pressed metal material. ing.

International Publication No. 1999/10168 JP 2014-1000082 A

  Although the above-mentioned Patent Document 1 describes a metal-CFRP structure material in which CFRP is bonded to a metal material previously processed into a predetermined shape with an adhesive, a method for integrally processing the metal-CFRP structure material is described. Is not listed.

  Further, the technique disclosed in Patent Document 2 requires a bending process such as hot pressing of a metal material before joining the metal member and CFRP, and thus has a problem that the manufacturing cost is still high. Furthermore, a metal-CFRP composite structure using a thermosetting resin as a CFRP matrix resin has a problem that peeling is likely to occur at the bonding interface between the metal and CFRP.

  The present invention has been made in view of the above problems, and is a metal-thermoplastic fiber reinforced resin material composite in which a metal member and a fiber reinforced resin material are firmly bonded and can be integrally processed at a low cost. An object is to provide a processing method.

  In order to solve the above-described problems, according to an aspect of the present invention, a metal plate in which a matrix resin containing a thermoplastic resin and a fiber reinforced resin material having a reinforced fiber material are disposed on at least one surface, An integrated processing step of integrally processing by heating to a predetermined temperature that cannot be maintained by a fiber reinforced resin material alone, and then applying a predetermined pressure through a mold having a predetermined shape, and the integrally processed metal plate And a mold release step of releasing the fiber reinforced resin material from the mold at a predetermined temperature at which the shape of the fiber reinforced resin material is not fixed, and a metal-thermoplastic fiber reinforced resin material composite member. A processing method is provided.

The thermoplastic resin is a crystalline resin having a melting point T _m, the heating temperature in the integrated processing step is the temperature of _{(T m -20) ~ (T} m +10) ℃ temperature range, the release It is preferable that the mold release temperature in a process is a temperature of the temperature range of ( _Tm- 30)-( _Tm + 10) degreeC.

The thermoplastic resin is a noncrystalline resin having a glass transition temperature T _g, the heating temperature in the integrated processing step, and low temperature, than the decomposition temperature of the thermoplastic resin in the amorphous, (Tg + 50) ~ The temperature in the temperature range of (Tg + 200) ° C. The mold release temperature in the mold release step is lower than the decomposition temperature of the amorphous thermoplastic resin and is in the temperature range of (Tg + 20) to (Tg + 200) ° C. It is preferable that it is the temperature of.

  The thermoplastic resin is preferably included in an amount of 20 to 80% by volume with respect to the total volume of the fiber reinforced resin material, and the total of the reinforced fiber material and the matrix resin is preferably 100% by volume.

  The reinforcing fiber material may be contained in an amount of 20 to 70% by volume with respect to the total volume of the fiber reinforced resin material, and the total of the reinforcing fiber material and the matrix resin may be 100% by volume. preferable.

It is preferable that the thickness of the metal plate is 0.1 to 6.0 mm, and the ratio of the yield stress to the Young's modulus of the metal plate is 0.8 × 10 ⁻³ or more.

  The material of the metal plate is preferably a steel material.

  The reinforcing fiber material is preferably a carbon fiber material.

  It is preferable that a predetermined mold release treatment is performed on the surface of the mold.

  It is preferable that a phenoxy resin is contained as the amorphous thermoplastic resin.

In order to solve the above problems, according to another aspect of the present invention, a metal having a thickness of 0.1 to 6 mm and a yield stress to Young's modulus ratio of 0.8 × 10 ⁻³ or more. A fiber reinforced resin material having a plate and a matrix resin having a thickness of 2 to 12 mm and containing a thermoplastic resin and a reinforced fiber material, the fiber reinforced resin being disposed on at least one surface of the metal plate The material contains at least 20 to 80% by volume of the thermoplastic resin, and the metal-thermoplastic fiber reinforced resin material composite member in which the metal plate and the fiber reinforced resin material integrally form a predetermined shape. Provided.

  The metal-thermoplastic fiber reinforced resin material composite member according to the present invention is a test piece having a width of 15 mm, measured by a 90 ° peel adhesion strength test defined by a T-shaped peel test described in JIS K 6854-3. The peel strength is preferably 20N or more.

In order to solve the above problem, according to another aspect of the present invention, the thickness is 0.1 to 6.0 mm, and the ratio of yield stress to Young's modulus is 0.8 × 10 ⁻³ or more. And a fiber reinforced resin material that is disposed on at least one surface of the metal plate, has a thickness of 2 to 12 mm, and includes a matrix resin containing a thermoplastic resin and a reinforced fiber material. The reinforced resin material includes at least 20 to 80% by volume of the thermoplastic resin, and an automotive part is provided in which the metal plate and the fiber reinforced resin material have a predetermined shape.

  As described above, according to the present invention, the metal member and the fiber reinforced resin material have high adhesiveness, and the metal-thermoplastic fiber reinforced resin material composite member can be integrally processed.

It is a schematic diagram which shows the cross-section of the metal-FRP composite member which concerns on the 1st Embodiment of this invention. It is a schematic diagram which shows the cross-section of another aspect of the metal-FRP composite member which concerns on the same embodiment. It is explanatory drawing which shows an example of the processing method of the metal-FRP composite member which concerns on the same embodiment. It is a schematic diagram which shows the test piece used for the peeling strength test of the metal-FRP composite member which concerns on the same embodiment. It is explanatory drawing which shows an example of the processing method of another aspect of the metal-FRP composite member which concerns on the same embodiment. It is a schematic diagram which shows the cross-section of the metal-FRP composite member which concerns on the 2nd Embodiment of this invention. It is a schematic diagram which shows the cross-section of another aspect of the metal-FRP composite member which concerns on the same embodiment. It is explanatory drawing which shows an example of the processing method of the metal-FRP composite member which concerns on the same embodiment. It is explanatory drawing which shows an example of the processing method of another aspect of the metal-FRP composite member which concerns on the same embodiment.

  Exemplary embodiments of the present invention will be described below in detail with reference to the accompanying drawings. In addition, in this specification and drawing, about the component which has the substantially same function structure, duplication description is abbreviate | omitted by attaching | subjecting the same code | symbol.

<1. Background>
As explained earlier, in order to meet the needs for weight reduction in the automobile industry, focusing on the light weight, tensile strength, workability, etc. of FRP, for example, automobile members including skeleton members such as side sills, pillars, and back doors. The application of FRP is being studied. For example, when an automobile receives an impact such as a collision, a method of applying FRP to a part of a portion subjected to compressive stress and absorbing the impact energy by preferentially destroying the FRP is studied. ing. In addition, when an automobile receives an impact, it has been studied to improve the strength of the member by using FRP having a high tensile strength in a portion that receives a tensile stress.

  As the FRP for the automobile member, CFRP formed of a thermosetting resin is generally used for carbon fiber and matrix resin having both strength and light weight. The present inventors have obtained knowledge that FRP breaks and peels from the metal member by applying a process such as bending to the member in which the metal member and the FRP using the thermosetting resin are integrated. In addition, when a metal member and a thermosetting CFRP are combined by hot pressing, when the composite returns to room temperature after processing, the CFRP has a difference due to the difference between the linear expansion coefficient of the metal member and the linear expansion coefficient of the CFRP. As a result of the occurrence of compressive stress, it has been found that the problem of peeling at the bonding surface between the metal member and CFRP occurs. CFRP fracture due to press load is caused by low bending strength due to CFRP's low compressive strength, and peeling at the adhesive surface is caused by cooling from hot press due to the difference between the linear expansion coefficient of the metal member and the linear expansion coefficient of CFRP. It is thought that the cause is that the resin at the interface between the FRP and the steel sheet sometimes does not follow the contraction of the steel sheet and peels from the metal member. Although it is possible to solve the above problems by individually shaping the metal member and CFRP and attaching CFRP to the metal member shaped using an adhesive, in such a method, the steps are In addition, the use of an adhesive increases the manufacturing cost.

  Further, high-strength steel is often used for the automobile members as described above for the purpose of reducing the weight of the vehicle body. When a composite of high-strength steel and FRP is pressed, the high-strength steel undergoes deformation (springback) to return to its pre-working shape after unloading. The present inventors have found that this spring back causes peeling at the interface between the high-strength steel and the FRP.

  Therefore, the present inventors changed the thermosetting resin such as an epoxy resin as the matrix resin of FRP in order to integrally process the metal member and FRP to obtain a metal-FRP composite member with high product stability. The idea was to use a thermoplastic FRP (Fiber Reinforced Thermo Plastics: FRTP) using a thermoplastic resin as a main component. The present inventors thought that since the thermoplastic resin is used as the main component of the matrix resin, the FRTP can be plastically deformed at a high temperature, so that the brittleness can be reduced and integrated processing is facilitated. As a result of conducting research based on this idea, the present inventors have laminated a metal member and FRTP, and by heating the laminate of the metal member and FRTP to a temperature at which the shape cannot be maintained by a single FRTP, We obtained the knowledge that integrated processing using a mold is possible. Furthermore, the present inventors release the composite material of the integrally processed metal member and FRTP from the mold at a temperature at which the matrix resin constituting the FRTP can be easily deformed even after the laminate is integrally processed. By doing so, it was discovered that interfacial peeling between the metal member and FRTP caused by springback can be suppressed.

  Then, the present inventors conducted extensive research and heated a metal plate on which at least one surface of a matrix resin containing a thermoplastic resin and a fiber reinforced resin material having a reinforced fiber material is disposed at a predetermined temperature. Thereafter, an integrated processing step of applying a predetermined pressure through a mold having a predetermined shape and integrally processing the integrated metal plate and the fiber reinforced resin material from the mold at a predetermined temperature. Invented a method for processing a metal-thermoplastic fiber reinforced resin material composite member including a mold release step for releasing. In the present invention, a metal member and FRTP are laminated, and after processing FRTP at a temperature at which the shape cannot be maintained by FRTP alone, the metal member and FRTP are integrated by releasing at a temperature at which the shape of FRTP is not fixed. The composite body in which the metal member and FRTP are firmly joined can be processed by processing and following the spring back of the metal member.

  In the present embodiment, the heating temperature and the release temperature during processing differ depending on whether the thermoplastic resin is a crystalline resin or an amorphous resin. Therefore, in the following, the embodiments will be described separately for the case where the thermoplastic resin according to the present embodiment is a crystalline resin and the case where it is an amorphous resin.

<2. First Embodiment>
<2.1. Structure of metal-fiber reinforced resin material composite>
First, the configuration of the metal-fiber reinforced resin material composite according to the first embodiment of the present invention will be described with reference to FIGS. 1 and 2 are schematic views showing a cross-sectional structure in the stacking direction of a metal-FRTP composite member 1 as a metal-fiber reinforced resin material composite according to the present embodiment.

  The metal-FRTP composite member 1 is composited with a matrix resin 101 containing a crystalline thermoplastic resin of FRTP12. As shown in FIG. 1, the metal-FRTP composite member 1 includes a metal member 11 and an FRTP 12. The metal member 11 and the FRTP 12 are combined with a matrix resin 101 included in the FRTP 12. Here, “composite” means that the metal member 11 and the FRTP 12 are joined and integrated. In addition, “integrated” means that the metal member 11 and the FRTP 12 move as a unit during processing and deformation.

  In the present embodiment, the FRTP 12 is provided so as to contact at least one surface of the metal member 11. However, the FRTP 12 may be provided not only on one side of the metal member 11 but also on both sides. Moreover, you may make it the structure where the laminated body containing FRTP12 is pinched | interposed between the two metal members 11. FIG.

  Hereinafter, each component of the metal-FRTP composite member 1 and other configurations will be described in detail.

<2.1.1. Metal member 11>
The material of the metal member 11 is not particularly limited, and examples thereof include iron, titanium, aluminum, magnesium, and alloys thereof. Here, examples of the alloy include iron-based alloys (including stainless steel), Ti-based alloys, Al-based alloys, Mg alloys, and the like. As the metal member according to the present embodiment, a metal material having a large springback amount such as high-tensile steel can be used, and when using the metal member 11 having such a large springback amount, the present invention is particularly effective. Exhibits excellent effects. Although the thickness of the metal member 11 will not be specifically limited if the shaping | molding process by a press etc. is possible, It is preferable in it being 0.1-6.0 mm. When the thickness of the metal member 11 is thinner than 0.1 mm, it is difficult to obtain a sufficient material strength when used for a skeleton member for an automobile. Further, when the thickness of the metal member 11 is thicker than 6.0 mm, the effect of reducing the weight of the vehicle body is reduced. The metal member 11 is preferably a thin plate.

In general, the higher the yield stress and the smaller the Young's modulus, the greater the springback amount. The processing method according to the present embodiment obtains a composite material that is integrally processed while maintaining high adhesion to the metal member 11 having a yield stress to Young's modulus ratio of 0.8 × 10 ⁻³ or more. be able to. As described above, when the metal member 11 having a large springback amount is used, the present invention exhibits a particularly excellent effect. Therefore, the ratio between the yield stress and the Young's modulus of the metal member 11 is more preferably 1.0. X10 ⁻³ or more, and even more preferably 2.0 × 10 ⁻³ or more.

  The steel material used as the material of the metal member 11 may be subjected to any surface treatment. Here, the surface treatment is, for example, various plating treatments such as zinc plating and aluminum plating, chemical treatment such as chromate treatment and non-chromate treatment, and chemical surface such as physical or chemical etching such as sandblasting. Although a roughening process is mentioned, it is not restricted to these. Moreover, multiple types of surface treatment may be performed. As the surface treatment, it is preferable that at least a treatment for the purpose of imparting rust prevention is performed.

  The surface of the metal member 11 may be treated with a primer in order to improve the adhesion with the FRTP 12. As a primer used in this treatment, for example, a silane coupling agent or a triazine thiol derivative is preferable. Examples of silane coupling agents include epoxy silane coupling agents, amino silane coupling agents, and imidazole silane compounds. Examples of triazine thiol derivatives include 6-diallylamino-2,4-dithiol-1,3,5-triazine, 6-methoxy-2,4-dithiol-1,3,5-triazine monosodium, and 6-propyl-2. , 4-dithiolamino-1,3,5-triazine monosodium, 2,4,6-trithiol-1,3,5-triazine and the like.

<2.1.2. FRTP12>
The FRTP 12 includes a matrix resin 101 containing a crystalline thermoplastic resin as a main component and reinforcing fibers 102 contained in the matrix resin 101 and combined. As FRTP12, for example, a composite formed by using a prepreg for FRP molding or a solidified matrix resin 101 containing reinforcing fibers 102 can be used. The FRTP 12 is not limited to one layer, and may be two or more layers, for example, as shown in FIG. What is necessary is just to set suitably the thickness n of FRTP12, and the number n of layers of FRTP12 in case FRTP12 is made into multiple layers according to a use purpose. When the FRTP 12 has a plurality of layers, each layer may have the same configuration or may be different. Further, the type and content ratio of the reinforcing fibers 102 constituting the FRTP 12 may be different for each layer.

(Matrix resin 101)
The metal member 11 and the FRTP 12 are firmly bonded to each other by the matrix resin 101 including the thermoplastic resin of the crystalline resin as a main component, and the processing method according to the present embodiment is performed, so that the strongly bonded state is obtained. The metal member 11 and the FRTP 12 can be integrally processed while being held.

  The crystalline resin is a resin in which a melting point Tm is observed when a melting point measurement is performed using a differential scanning calorimetry (DSC) or a suggestive thermal analysis (Differential Thermal Analysis: DTA). Examples of the crystalline thermoplastic resin contained in the matrix resin 101 include polyethylene (PE), polypropylene (PP), polymethylpentene (PMP), polyester (PEs), nylons, and aromatic polyether ketone (PAEK). ), Polyphenylene sulfide (PPS), polyacetal (POM), modified polyimide, and the like. For example, polyethylene (PE) includes low density polyethylene (LDPE), high density polyethylene (HDPE), ultra high molecular weight polyethylene (UHPE), and the like (polyester) (polyethylene terephthalate (PET), Polybutylene terephthalate (PBT) and the like, and nylons include 6 nylon (PA6), 6,6-nylon (PA66), and aromatic polyether ketone (PAEK) includes polyether. Examples include ether ketone (PEEK), polyether ether ketone ketone (PEEKK), and polyether ketone (PEK). By containing a crystalline thermoplastic resin in the matrix resin 101, it becomes possible to eliminate the fact that FRP has brittleness and cannot be bent because it is used when a thermosetting resin is used.

  Further, in order to improve the adhesion between the metal member 11 and the FRTP 12, a crystalline thermoplastic resin having a modified skeleton or terminal group may be contained in the matrix resin 101. For modification of the crystalline thermoplastic resin, an acid such as maleic anhydride or carboxylic anhydride can be used.

  The matrix resin 101 has, for example, natural rubber, synthetic rubber, elastomer and the like, various inorganic fillers, solvents, pigments, colorants, antioxidants, ultraviolet light inhibitors, difficult to the extent that the adhesiveness and physical properties are not impaired. Other additives such as a flame retardant and a flame retardant aid may be blended. As the elastomer, for example, styrene elastomer, olefin elastomer, alkene elastomer, vinyl chloride elastomer, urethane elastomer, amide elastomer, and the like can be used. The additive content is preferably blended so that the total content of the thermoplastic resin, the reinforcing fiber 102 and the additive is 100% by volume.

  The content of the thermoplastic resin contained in the matrix resin 101 is preferably 20% by volume or more and 80% by volume or less with respect to the entire volume of FRTP12. When the content of the thermoplastic resin is less than 20% by volume, the thermocompression bonding between the metal member 11 and the FRTP 12 becomes insufficient, and there is a possibility of peeling at the crimping surface. On the other hand, if the content of the thermoplastic resin is more than 80% by volume, the resin softened and melted during the pressing process flows out to the mold and promotes the introduction of voids and defects in the thermoplastic carbon fiber reinforced plastic (CFRTP). There may be a problem that the strength of the composite material is reduced. More preferably, the content of the thermoplastic resin contained in the matrix resin 101 is not less than 35% by volume and not more than 75% by volume. The matrix resin 101 is preferably contained so that the total content of the matrix resin 101 and the reinforcing fibers 102 is 100% by volume.

(Reinforcing fiber 102)
Although there is no restriction | limiting in particular as the reinforced fiber 102, For example, a carbon fiber, a boron fiber, a silicon carbide fiber, glass fiber, an aramid fiber etc. are preferable, and a carbon fiber is more preferable from a viewpoint of weight reduction. For the type of carbon fiber, for example, either PAN-based or pitch-based can be used, and may be selected according to the purpose and application. Moreover, as the reinforcing fiber 102, the above-described fibers may be used alone or in combination of two or more.

  In the FRP used for the FRTP 12, as the reinforcing fiber base material used as the base material of the reinforcing fiber 102, for example, a nonwoven fabric base material using chopped fibers, a cloth material using continuous fibers, a unidirectional reinforcing fiber base material (UD material) ), A short fiber base material and the like can be used. From the viewpoint of the reinforcing effect, it is preferable to use a cloth material or a UD material as the reinforcing fiber base material.

(Fiber density)
The fiber density (VF) of FRTP12 is a factor that affects strength. Generally, the strength of FRTP12 increases as VF increases. In the present embodiment, the reinforcing fibers 102 are preferably included in an amount of 20 to 70% by volume with respect to the entire volume of the FRTP 12. When continuous fibers are used as the reinforcing fibers 102, the VF of the FRTP 12 is preferably 40% by volume or more and 70% by volume or less. When the VF of the reinforcing fiber 102 when continuous fibers are used exceeds 70% by volume, it becomes difficult to produce the FRTP 12 having high orientation. In addition, when the VF of the reinforcing fiber 102 when using continuous fibers is less than 40% by volume, the reinforcing fiber 102 is difficult to be oriented in the resin during the heat curing process, so that the strength specific to the continuous fibers cannot be obtained. There is. If the VF is too large, voids and defects are likely to occur in the FRTP 12 and it is difficult to obtain high strength. Therefore, the VF of the FRTP 12 when the continuous fiber is used as the reinforcing fiber 102 is 55% by volume or more and 65% by volume. The following is more preferable.

  Moreover, when the fiber used as the reinforced fiber 102 is a short fiber, it is preferable that it is 20 volume% or more and 50 volume% or less. When the VF of the reinforcing fiber 102 when short fibers are used exceeds 50% by volume, it becomes difficult to produce FRTP12 having high orientation. Further, if the VF of the reinforcing fiber 102 when using short fibers is less than 20% by volume, sufficient strength as a strength member may not be obtained. When short fibers are used as the reinforcing fibers 102, the VF of the FRTP 12 is more preferably 25% by volume or more and 45% by volume or less. The short fiber refers to a fiber having a length of 0.1 mm to 12 mm.

  In the metal-FRTP composite member 1 according to this embodiment, the FRTP 12 is formed using at least one CFRTP molding prepreg. The FRTP 12 is not limited to one layer, and may be two or more layers as shown in FIG. 3, for example. What is necessary is just to set suitably the thickness n of FRTP12, and the number n of layers of FRTP12 in case FRTP12 is made into multiple layers according to a use purpose. When the FRTP 12 has a plurality of layers, each layer may have the same configuration or may be different. Further, the type and content ratio of the reinforcing fibers 102 constituting the FRTP 12 may be different for each layer.

<2.2. Processing Method for Metal-FRTP Composite Member 1>
Heretofore, the configuration of the metal-FRTP composite member 1 as the metal-fiber reinforced resin material composite according to the present embodiment has been described in detail. Then, the processing method of the metal-FRTP composite member 1 which concerns on this embodiment is demonstrated, referring FIG. 3 and 4 are explanatory views showing examples of processing steps for the metal-FRTP composite member 1.

  The metal-FRTP composite member 1 is integrally processed by heating a FRTP 12 and a metal member 11 having a predetermined shape to a predetermined heating temperature and then applying a predetermined pressure via a mold having a predetermined shape. It is obtained by going through an integrated process step and a mold release step of releasing the integrally processed metal member 11 and FRTP 12 from the mold at a predetermined temperature. The integral processing in the present invention is to bond the FRTP 12 and the metal member 11 with the matrix resin 101 and process the metal member 11 and the FRTP 12 without peeling. Hereinafter, a method of combining (integrating) the metal member 11 and the FRTP 12 by thermocompression bonding will be described.

<2.2.1. Method 1>
First, as shown to Fig.3 (a), FRTP12 is arrange | positioned and laminated | stacked on the surface of at least one side of the metal member 11, and it is set as a laminated body. In FIG. 3, the mold having a convex shape is an upper mold m1, the mold having a concave shape is a lower mold m2, and the FRTP 12 is arranged on the upper side of the metal member 11, that is, on the upper mold m1 side. Show. At this time, it is preferable that the bonding surface of the FRTP 12 to be bonded to the metal member is activated by, for example, roughening by blasting or the like, plasma processing, corona treatment, or the like. Moreover, it is preferable to remove the deposits on the surface and degrease the metal member 11 in advance. Such removal of deposits and degreasing can be performed by a known technique.

  In FIG. 3 (a), instead of FRTP12, it is also possible to integrally process the laminated body in which the FRP molding prepreg is laminated while combining the FRP molding prepreg and the metal member 11 at the time of integral processing described later. is there. In addition, a composite of the metal member 11 and the FRTP 12 in advance can be integrally processed by a method described later. Further, the FRTP 12 is not limited to a single layer as shown in FIG.

Then, the metal member 11 and heating the laminate of FRTP12 to a predetermined heating temperature _{T 1} (Figure 2 (b)). Above, the heating temperatures T ₁ is, FRTP alone is long, for example, is held 1 hour or more to the temperature variations due to the weight of the FRTP occurs, that is, in itself is a temperature that can not retain its shape. Specifically, the heating temperature T ₁ is a temperature within the range of (Tm−20) ° C. or more and (Tm + 10) ° C. or less, where Tm is the melting point of the thermoplastic resin contained in the FRP matrix resin 101. It is preferable. When the heating temperature _{T 1} is less than (Tm-20) ℃, possibly interface at peeling occurs between the metal member 11 and FRTP12 increases. Further, if the heating temperature _{T 1} is less than (Tm-20) ℃, because the fluidity of the matrix resin 101 is low, shear when FRTP12 multiple layers are stacked, during bending between the layers of FRTP12 There is a high possibility of deviation. When the heating temperature _{T 1} is is (Tm + 10) ℃ greater than that flowability of the matrix resin 101 is too high, the matrix resin 101 flows out from the mold m, the content of the matrix resin 101 to the total volume of FRTP12 is It decreases and increases the possibility that the strength of the composite will decrease. By reducing the content of the matrix resin 101, voids are likely to be generated in the FRTP 12, and the strength of the FRTP 12 may be reduced. In addition, a decrease in the content of the thermoplastic resin contained in the matrix resin 101 with respect to the entire volume of the FRTP 12 reduces the adhesive strength between the metal member 11 and the FRTP 12 and promotes peeling, resulting in a decrease in strength. There is. The heating temperature T ₁ is more preferably (Tm−10) ° C. or higher and (Tm + 0) ° C. or lower.

  In order to improve the mold releasability of the metal-FRTP composite member 1, it is preferable that the surface of the mold m is subjected to a mold release treatment. The release treatment method is not particularly limited, and examples thereof include application of a release agent, surface modification of the mold m, and film formation. As the mold release agent, those mainly composed of silicone, mineral water, ester, etc. can be used as appropriate, and oil type, solution type, emulsion type, oil compound type, and baking type mold release agents are appropriately selected. Can be used.

  The mold m is preferably preheated. The preheating of the mold m is not particularly limited, and can be performed by, for example, combustion heating with a gas burner, infrared heating, high frequency dielectric heating, or the like. By preheating the mold m, it is possible to shorten the time until the laminated body of the metal member 11 and the FRTP 12 reaches a predetermined temperature, and to improve the production efficiency.

Then, as shown in FIG. 3 (c), by using a mold m, integral machining by applying a predetermined pressure to the metal member 11 and FRTP12, processed into a predetermined shape by integrating the above heating temperature T ₁ of I do.

  The press load during processing is preferably 0.1 kN or more and 100 kN or less. If it is less than 0.1 kN, the FRTP 12 having a thickness of less than 12 mm and a steel plate composite having a thickness of 0.1 mm or more may not be processed into a predetermined shape. On the other hand, if the press load is 100 kN, there is a possibility that the fiber breaks, which is not preferable.

The processing speed of the laminated body of the metal member 11 and FRP is defined by the strain rate of the material, and the range is preferably 0.05 to 10 s ⁻¹ . The strain rate of the material is a value obtained by dividing the speed of the mold m by the thickness of the material. When this strain rate is less than 0.05 s ⁻¹ , integral molding is possible, but productivity is significantly reduced. If it exceeds 10 s ⁻¹ , the resin in the FRTP 12 cannot follow the processing of the steel sheet, and there is a possibility that deviation occurs between the layers of the FRTP 12. More preferably, the processing speed is the processing speed in the range of strain rate of the laminate of the metal member 11 and the FRP is 0.5 s ^-1 or more ^{5s -1} or less.

  If the pressing time is at least 1 minute or more, the resin in FRTP moves to the steel plate and adhesion is ensured, so that the integrated metal-FRTP composite member 1 can be processed, and it is 5 minutes or more. And preferred. Although there is no particular upper limit, it is preferably 10 minutes or less from the viewpoint of productivity.

Thereafter, as shown in FIG. 3 (d), to remove the pressure with a die m with a mold release temperature T _2, to obtain a metal -FRTP composite member 1 is removed from the mold m.

Releasing temperature T ₂ at this time, when the FRTP alone is held at the above temperature, small forces, such as cracks in the carbon fiber or the resin in the FRTP when a force more than 1N is applied is not enter It is a temperature at which deformation easily occurs, that is, a temperature at which the shape is not completely determined. Specifically, the heating temperature _{T 2} is preferably a temperature within the range of (Tm-30) ℃ least (Tm + 10) ℃ or less. When releasing temperature _{T 2} is less than (Tm-30) ℃, can not follow FRTP12 springback of the metal member 11, there is a case where peeling at the interface between the metal member 11 and FRTP12 occurs. Further, when the release temperature T ₂ is at (Tm + 10) ℃ greater than that flowability of the matrix resin 101 becomes too high, sometimes the matrix resin 101 flows out from the mold m. As a result, there is a possibility that the matrix resin in FRTP12 is reduced and the strength of the composite is lowered. Releasing temperature _{T 2} is more preferably, (Tm-20) ℃ least (Tm + 0) ℃ or less.

If the releasing temperature T ₂ is in the above temperature range, the resin in FRTP12 has a fluidity that allows follow the springback of the metal member 11, the pressure removal rate of metal -FRTP composite member 1 There are no particular restrictions.

  The peel strength between the metal member 11 and the FRTP 12 can be measured by a method defined in “JIS K 6854-3 Adhesive—Peel Adhesive Strength Test Method—Part 3: T-Peeling”. FIG. 4 is a diagram showing a test piece 2 used for a peel strength test. Specifically, a test piece having a width of 15 mm and a length of 90 mm in which the metal member 11 is bonded to both surfaces of the FRTP 12 is cut out from the processed metal-FRTP composite member 1. The metal member 11 of the cut test piece is peeled off from the FRTP 12 by 30 mm, and only the metal part is bent at 90 degrees. The metal part bent at 90 degrees is held by a chuck and set in a peel tester, a peel strength test is performed with the crosshead speed of the peel tester set to 300 mm / min, and the maximum load obtained is defined as the peel strength. Moreover, about the metal-FRTP composite member which joined the metal member 11 only to one side of FRTP12, and processed integrally, a test piece can be produced with the following method and a peeling strength test can be performed. A composite member having a width of 15 mm and a length of 90 mm is cut out from the metal-FRTP composite member, the metal member 11 of the cut out composite member is peeled off from the FRTP 12 by 30 mm, and the peeled metal portion is bent at 90 degrees. A metal member bent at 90 degrees using a room temperature curable adhesive is bonded to the surface of the FRTP 12 opposite to the surface to which the metal member 11 is bonded. The test piece produced as described above can be set in a peel tester in the same manner as described above and used for a peel strength test. In addition, when the adhesive strength between the room temperature curable adhesive to be used and FRTP12 was separately examined, it was 200 N or more, and thus the peel strength test result reflected the peel strength between the metal member 11 and FRTP12. It becomes.

  In the above description, the case where the FRTP 12 is laminated on the upper part of the metal member 11 has been described. However, as shown in FIG. 5, the metal member 11 can be laminated and processed on the upper part of the FRTP 12. Below, the method of laminating | stacking the metal member 11 on the upper part of FRTP12 and integrally processing is demonstrated, referring FIG.

<2.2.2. Method 2>
When the metal member 11 is laminated on the upper part of the FRTP 12 and integrally processed, as shown in FIG. 5A, a laminate in which the metal member 11 is laminated on the upper part of the FRTP 12, as shown in FIG. It mounts on the support plate b, and heat-pressure-bonds by applying a pressure through the metal mold m.

As in the method 1, the bonding surface of the FRTP 12 bonded to the metal member 11 is preferably activated by, for example, roughening by blasting or the like, plasma processing, corona treatment, or the like. In FIG. 5A, a prepreg for FRP molding can be laminated instead of FRTP12. Further, the FRTP 12 is not limited to a single layer as shown in FIG.

Next, as shown in FIG. 5 (b), placing the stack of FRTP12 and the metal member 11 to the support plate b, and heated to a predetermined heating temperature _{T 1.} Heating temperatures T ₁ at this time is the same as the heating temperature T ₁ of the method 1.

  In order to improve the releasability of the metal-FRTP composite member 1, it is preferable that the surface of the mold m is subjected to a release treatment similar to the method 1. Further, it is preferable that the surface of the support plate b is subjected to the same release treatment as in the method 1. Further, it is preferable that the mold m is preheated by the same method as the method 1 when the laminate is heated.

Then, as shown in FIG. 5 (c), using a die m, applying pressure to the molded body and the support plate b of the metal member 11 and FRTP12, the above heating temperature T _1, processed into a predetermined shape To do. At this time, it is preferable that the shape of the mold m considers the thickness of the support plate b so that the laminated body of the metal member 11 and the FRTP 12 becomes the metal-FRTP composite member 1 having a desired shape.

  The press load, processing speed, pressure application time, and the like can be set to the same conditions as in Method 1.

Thereafter, as shown in FIG. 5 (d), to remove the pressure with a die m with a mold release temperature T _2, to obtain a metal -FRTP composite member 1 is removed from the mold m. In this case, the releasing temperature T ₂ is similar to the release temperature T ₂ of Method 1.

  In the present embodiment, the case where the FRTP 12 is provided so as to be in contact with at least one surface of the metal member 11 has been described, but the FRTP 12 is not only provided on only one surface of the metal member 11 but also both surfaces. May be provided respectively. When the FRTP 12 is provided on both surfaces of the metal member 11, the method 2 can be applied for processing. Moreover, you may make it the structure where the laminated body containing FRTP12 is pinched | interposed between the two metal members 11. FIG.

  According to the present embodiment described above, the metal-FRTP composite member 1 in which the metal member 11 and the FRTP 12 are firmly joined without requiring a step of pasting the metal member 11 and the FRTP 12 or a step of shaping the metal member 11 in advance. Integrated processing is possible. In this method, the metal member 11 and the FRTP 12 may be integrally processed in the next step using a material that is bonded in advance.

<3. Second Embodiment>
<3.1. Structure of metal-fiber reinforced resin material composite>
The metal-fiber reinforced resin material composite according to the second embodiment of the present invention is a composite containing an amorphous thermoplastic resin as the matrix resin 101A. The configuration of the metal-fiber reinforced resin material composite according to the second embodiment of the present invention will be described with reference to FIGS.

  The metal-FRTP composite member 1A is composited with a matrix resin 101A containing an amorphous thermoplastic resin of FRTP12A. As shown in FIG. 6, the metal-FRTP composite member 1A includes a metal member 11 and an FRTP 12A. The metal member 11 and the FRTP 12A are combined with a matrix resin 101A included in the FRTP 12A.

  In the present embodiment, the FRTP 12A is provided so as to be in contact with at least one surface of the metal member 11. However, the FRTP 12A may be provided not only on one side of the metal member 11 but also on both sides. Moreover, you may make it the structure where the laminated body containing FRTP12A is pinched | interposed between the two metal members 11. FIG.

  Hereinafter, each component of the metal-FRTP composite member 1A and other configurations will be described in detail. Since the metal member 11 according to this embodiment is the same as that of the first embodiment, detailed description thereof is omitted here.

<3.1.1. FRTP12A>
The FRTP 12A includes a matrix resin 101A containing an amorphous thermoplastic resin, and a composite reinforcing fiber 102 contained in the matrix resin 101A. As the FRTP 12A, as in the method 1, for example, a composite formed by using a prepreg for FRP molding or a solidified matrix resin 101A containing the reinforcing fiber 102 can be used. For example, as shown in FIG.

(Matrix resin 101A)
The metal member 11 and the FRTP 12A are firmly bonded to each other by the matrix resin 101A including the thermoplastic resin of the crystalline resin as a main component, and the processing method according to the present embodiment is performed, so that the strongly bonded state is obtained. The metal member 11 and the FRTP 12A can be integrally processed while being held.

  An amorphous resin is a resin in which no exothermic peak accompanying crystallization is observed and only the glass transition point Tg is observed when the melting point is measured using a differential scanning calorimeter or suggested thermal analysis. is there. Examples of the amorphous resin contained in the matrix resin 101A include phenoxy resin, polymethyl methacrylate (PMMA), polystyrene (PS), polycarbonate (PC), amorphous polyarylate (PAR), and polysulfone (PSU). Can be mentioned. By containing a crystalline thermoplastic resin in the matrix resin 101, it becomes possible to eliminate the fact that FRP has brittleness and cannot be bent because it is used when a thermosetting resin is used.

  In addition, when carbon fiber is used as the reinforcing fiber 102A, the matrix resin 101A preferably contains a phenoxy resin from the viewpoint of adhesion to the metal member 11 and affinity with the carbon fiber surface. Preference is given to using phenoxy resins. “Phenoxy resin” is a linear polymer obtained from a condensation reaction of a dihydric phenol compound and an epihalohydrin or a polyaddition reaction of a dihydric phenol compound and a bifunctional epoxy resin, and is an amorphous thermoplastic resin. It is. The phenoxy resin can be obtained by a conventionally known method in a solution or in the absence of a solvent, and can be used in any form of powder, varnish and film.

  Since the molecular structure of the phenoxy resin is very similar to that of the epoxy resin, the phenoxy resin has the same heat resistance as that of the epoxy resin, and the adhesiveness with the metal member 11 is good. Furthermore, by adding a curable component such as an epoxy resin to phenoxy resin and copolymerizing it, a so-called partially curable resin can be obtained. By using such a partially curable resin as the matrix resin 101A, a matrix resin excellent in the impregnation property to the reinforcing fibers 102 can be obtained. Furthermore, by thermally curing the curing component in the partially curable resin, it is possible to suppress melting or softening of the matrix resin 101A in the FRTP 12A when it is exposed to a high temperature like a normal thermoplastic resin. The amount of the curable component added to the phenoxy resin may be appropriately determined in consideration of the impregnation property of the reinforcing fiber 102 and the brittleness, tact time, and workability of the FRTP 12A. As described above, by using the phenoxy resin as the matrix resin 101A, it is possible to add and control the curing component with a high degree of freedom.

  For example, the surface of the reinforcing fiber 102 is often provided with a sizing agent that is familiar with the epoxy resin. Since the phenoxy resin is very similar to the structure of the epoxy resin, the sizing agent for the epoxy resin can be used as it is by using the phenoxy resin as the matrix resin 101A. Therefore, cost competitiveness can be improved.

  Among the thermoplastic resins, the phenoxy resin has good moldability and is excellent in adhesion to the reinforcing fiber 102. In addition, by using an acid anhydride, an isocyanate compound, caprolactam or the like as a crosslinking agent, it has high heat resistance after molding. It is also possible to have the same properties as the thermosetting resin. Therefore, in this embodiment, it is preferable to use a solidified product or a cured product of a resin composition containing 50 parts by mass or more of phenoxy resin with respect to 100 parts by mass of the resin component as the resin component of the matrix resin 101A. By using such a resin composition, the metal member 11 and the FRTP 12A can be firmly bonded. More preferably, the resin composition contains 55 parts by mass or more of phenoxy resin out of 100 parts by mass of the resin component. The form of the adhesive resin composition may be, for example, a liquid such as powder or varnish, or a solid such as a film. The term “solidified product” simply means that the resin component itself is solidified, and the term “cured product” means that the resin component is cured by containing various curing agents. . The curing agent that can be contained in the cured product includes a crosslinking agent as described later, and the above-mentioned “cured product” includes a crosslinked cured product.

  The content of the phenoxy resin can be measured using infrared spectroscopy (IR) as follows, and the content of the phenoxy resin is determined from the resin composition targeted by infrared spectroscopy. In the case of analysis, it can be measured by using a general method of infrared spectroscopic analysis such as transmission method or ATR reflection method.

  The FRTP 12A is cut out with a sharp blade or the like, the fibers are removed with tweezers as much as possible, and the resin composition to be analyzed is sampled from the FRTP 12A. In the case of the permeation method, the KBr powder and the resin composition powder to be analyzed are crushed while uniformly mixed in a mortar or the like to prepare a thin film as a sample. In the case of the ATR reflection method, as in the transmission method, a tablet may be prepared by crushing the powder with uniform mixing in a mortar to prepare a sample, or a single crystal KBr tablet (for example, a diameter of 2 mm × thickness of 1. 8 mm) may be scratched with a file or the like, and a resin composition powder to be analyzed may be applied and adhered to form a sample. In any method, it is important to measure the background of KBr alone before mixing with the resin to be analyzed. As the IR measuring apparatus, a commercially available general apparatus can be used, but the accuracy is such that the absorption (Absorbance) can be distinguished in units of 1% and the wave number (Wavenumber) can be distinguished in units of 1 cm-1. An apparatus is preferable, and examples thereof include FT / IR-6300 manufactured by JASCO Corporation.

  When investigating the content of the phenoxy resin, the absorption peak of the phenoxy resin exists, for example, in the vicinity of 1450 to 1480 cm −1, 1500 cm −1, 1600 cm −1 or the like. Therefore, the content of the phenoxy resin is calculated based on a calibration curve prepared in advance and showing the relationship between the intensity of the absorption peak and the content of the phenoxy resin and the intensity of the measured absorption peak. Is possible.

  The average molecular weight of the phenoxy resin is, for example, in the range of 10,000 to 200,000 as the mass average molecular weight (Mw), preferably in the range of 20,000 to 100,000, more preferably Is in the range of 30,000 to 80,000. By setting the Mw of the phenoxy resin within the range of 10,000 or more, the strength of the molded body can be increased, and this effect is further achieved by setting the Mw to 20,000 or more, and further to 30,000 or more. Rise. On the other hand, when the Mw of the phenoxy resin is 200,000 or less, the workability and workability can be improved, and this effect is achieved by setting the Mw to 100,000 or less, and further 80,000 or less. And further increase.

  The hydroxyl equivalent (g / eq) of the phenoxy resin used in the present embodiment is, for example, in the range of 50 to 1000, preferably in the range of 50 to 750, more preferably 50 to 500. Within range. By setting the hydroxyl group equivalent of the phenoxy resin to 50 or more, the water absorption decreases as the number of hydroxyl groups decreases, so that the mechanical properties of the cured product can be improved. On the other hand, since the hydroxyl group equivalent of the phenoxy resin is set to 1000 or less, it is possible to suppress the reduction of hydroxyl groups, and therefore the mechanical properties of the metal-FRTP composite member 1A can be improved. This effect is further enhanced by setting the hydroxyl equivalent to 750 or less, more preferably 500 or less.

  The phenoxy resin is not particularly limited as long as it satisfies the above physical properties. Preferred examples include bisphenol A type phenoxy resins (for example, phenototo YP-50, phenototo YP-50S manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Phenototo YP-55U), bisphenol F-type phenoxy resin (for example, available as phenototox FX-316 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), copolymerized phenoxy resin of bisphenol A and bisphenol F (for example, Nippon Steel & Sumikin) YP-70 manufactured by Chemical Co., Ltd.), special phenoxy resins such as brominated phenoxy resins other than those listed above, phosphorus-containing phenoxy resins, and sulfone group-containing phenoxy resins (for example, Nippon Steel & Sumikin Chemical Co., Ltd. Tote YPB- 3C, available as fenofibrate tote FX293, YPS-007, etc.) and the like. These resin can be used individually by 1 type or in mixture of 2 or more types.

◇ Crosslinkable resin composition A resin composition containing a phenoxy resin (hereinafter also referred to as "phenoxy resin (A)") is crosslinked by, for example, blending an acid anhydride, isocyanate, caprolactam, or the like as a crosslinking agent. Resin composition (that is, a cured product of the resin composition). Since the heat resistance of the resin composition is improved by performing a crosslinking reaction using the secondary hydroxyl group contained in the phenoxy resin (A), the crosslinkable resin composition can be applied to a member used in a higher temperature environment. It is advantageous for application. For the cross-linking formation utilizing the secondary hydroxyl group of the phenoxy resin (A), it is preferable to use a cross-linking resin composition in which the cross-linking curable resin (B) and the cross-linking agent (C) are blended. As the cross-linking curable resin (B), for example, an epoxy resin can be used, but it is not particularly limited. By using such a crosslinkable resin composition, a cured product (crosslinked cured product) in the second cured state in which the glass transition point Tg of the resin composition is greatly improved as compared with the case of the phenoxy resin (A) alone is obtained. It is done. The glass transition point Tg of the cross-linked cured product of the cross-linkable resin composition is, for example, 160 ° C. or higher and preferably in the range of 170 ° C. or higher and 220 ° C. or lower.

  In the crosslinkable resin composition, the crosslinkable curable resin (B) to be blended with the phenoxy resin (A) is preferably a bifunctional or higher functional epoxy resin. Examples of the bifunctional or higher functional epoxy resin include bisphenol A type epoxy resins (for example, available as Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YD-011, Epototo YD-7011, Epototo YD-900), bisphenol F type epoxy resins (for example, , Available from Nippon Steel & Sumikin Chemical Co., Ltd. as Epototo YDF-2001), diphenyl ether type epoxy resin (for example, available from Nippon Steel & Sumikin Chemical Co., Ltd. as YSLV-80DE), tetramethylbisphenol F type epoxy resin (for example, Nippon Steel & Sumikin Chemical) Available as YSLV-80XY manufactured by Co., Ltd.), bisphenol sulfide type epoxy resin (for example, available as YSLV-120TE manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), hydroquinone type epoxy Shi resin (for example, available as Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDC-1312), phenol novolac type epoxy resin (for example, available as Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YDPN-638), orthocresol novolak type epoxy resin (For example, available as NS -355), triphenylmethane type epoxy resin (for example, available as EPPN-502H manufactured by Nippon Kayaku Co., Ltd.) and the like, but are limited thereto. Not to. Moreover, these epoxy resins may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  Further, the cross-linking curable resin (B) is not particularly limited, but is preferably a crystalline epoxy resin, having a melting point of 70 ° C. or higher and 145 ° C. or lower and a melt viscosity at 150 ° C. of 2.0 Pa · A crystalline epoxy resin that is s or less is more preferred. By using a crystalline epoxy resin exhibiting such melting characteristics, the melt viscosity of the crosslinkable resin composition as the resin composition can be reduced, and the adhesiveness of FRTP12A can be improved. If the melt viscosity exceeds 2.0 Pa · s, the moldability of the crosslinkable resin composition may decrease, and the homogeneity of the metal-FRTP composite member 1A may decrease.

  Examples of the crystalline epoxy resin suitable as the cross-linking curable resin (B) include, for example, Nippon Steel & Sumikin Chemical Co., Ltd. Epototo YSLV-80XY, YSLV-70XY, YSLV-120TE, YDC-1312, Mitsubishi Chemical Corporation YX-4000. , YX-4000H, YX-8800, YL-6121H, YL-6640, etc., DIC Corporation HP-4032, HP-4032D, HP-4700, etc., Nippon Kayaku Co., Ltd. NC-3000, etc. are mentioned.

  The crosslinking agent (C) crosslinks the phenoxy resin (A) three-dimensionally by forming an ester bond with the secondary hydroxyl group of the phenoxy resin (A). Therefore, unlike the strong cross-linking such as curing of the thermosetting resin, the cross-linking can be released by a hydrolysis reaction, so that the metal member 11 and the FRTP 12A can be easily peeled off.

  As the crosslinking agent (C), an acid anhydride is preferable. The acid anhydride is not particularly limited as long as it is solid at room temperature and does not have much sublimation property, but from the viewpoint of imparting heat resistance to the metal-FRTP composite member 1A and reactivity, phenoxy resin ( Aromatic acid anhydrides having two or more acid anhydrides that react with the hydroxyl group of A) are preferred. In particular, aromatic compounds having two acid anhydride groups, such as pyromellitic acid anhydride, are suitable because they have higher crosslink density and improved heat resistance than the combination of trimellitic acid anhydride and hydroxyl group. Is done. Examples of aromatic dianhydrides include phenoxy resins such as 4,4′-oxydiphthalic acid, ethylene glycol bisanhydro trimellitate, 4,4 ′-(4,4′-isopropylidenediphenoxy) diphthalic anhydride. An aromatic acid dianhydride having compatibility with the epoxy resin is more preferable because it has a large effect of improving the glass transition point Tg. In particular, an aromatic acid dianhydride having two acid anhydride groups, such as pyromellitic acid anhydride, has an improved crosslinking density compared to, for example, phthalic anhydride having only one acid anhydride group, Since heat resistance improves, it is used suitably. That is, the aromatic dianhydride has two acid anhydride groups and thus has good reactivity, and a crosslinked cured product having sufficient strength for demolding can be obtained in a short molding time, and the phenoxy resin (A) Since four carboxyl groups are generated by the esterification reaction with the secondary hydroxyl group therein, the final crosslink density can be increased.

  The reaction of the phenoxy resin (A), the epoxy resin as the cross-linking curable resin (B), and the cross-linking agent (C) is obtained by reacting the secondary hydroxyl group in the phenoxy resin (A) with the acid anhydride group of the cross-linking agent (C). Cross-linking and curing are carried out by the esterification reaction of the resin, and further by the reaction of the carboxyl group produced by the esterification reaction and the epoxy group of the epoxy resin. Although a crosslinked phenoxy resin can be obtained by the reaction of the phenoxy resin (A) and the crosslinking agent (C), the melt viscosity of the resin composition can be lowered by the coexistence of the epoxy resin. It exhibits excellent properties such as improved impregnation, acceleration of crosslinking reaction, improved crosslinking density, and improved mechanical strength.

  In the crosslinkable resin composition, the epoxy resin as the crosslinkable curable resin (B) coexists, but the phenoxy resin (A) which is a thermoplastic resin is a main component, and its secondary hydroxyl group and It is considered that the esterification reaction with the acid anhydride group of the crosslinking agent (C) has priority. That is, since the reaction between the acid anhydride used as the cross-linking agent (C) and the epoxy resin used as the cross-linking curable resin (B) takes time (slow reaction rate), the cross-linking agent (C) and The reaction with the secondary hydroxyl group of the phenoxy resin (A) occurs first, and then the cross-linking agent (C) remaining in the previous reaction or the residual carboxyl group derived from the cross-linking agent (C) reacts with the epoxy resin. This further increases the crosslink density. Therefore, unlike a resin composition mainly composed of an epoxy resin, which is a thermosetting resin, a crosslinked cured product obtained from the crosslinkable resin composition is a thermoplastic resin and has excellent storage stability.

  In the crosslinkable resin composition utilizing the crosslinking of the phenoxy resin (A), the crosslinkable curable resin (B) is in the range of 5 parts by mass or more and 85 parts by mass or less with respect to 100 parts by mass of the phenoxy resin (A). It is preferable to be contained. The content of the cross-linking curable resin (B) with respect to 100 parts by mass of the phenoxy resin (A) is more preferably in the range of 9 parts by mass to 83 parts by mass, and still more preferably 10 parts by mass to 80 parts by mass. Within range. By setting the content of the crosslinkable curable resin (B) to 85 parts by mass or less, the curing time of the crosslinkable curable resin (B) can be shortened, so that the strength necessary for demolding can be easily obtained in a short time. The recyclability of FRTP12A is improved. This effect is further enhanced by setting the content of the cross-linking curable resin (B) to 83 parts by mass or less, and further to 80 parts by mass or less. On the other hand, when the content of the cross-linkable curable resin (B) is 5 parts by mass or more, it becomes easy to obtain an effect of improving the cross-link density by adding the cross-linkable curable resin (B), and the crosslinkable resin composition is cured by cross-linking. The product easily develops a glass transition point Tg of 160 ° C. or higher, and fluidity is improved. Here, the crosslinkable resin composition includes 20 to 80% by volume of the phenoxy resin (A) with respect to the total volume of FRTP12A, and 20 to 70% by volume of the reinforcing fibers 102 with respect to the total volume of FRTP12A. In a range, it is preferable to contain so that the ratio of a phenoxy resin (A) and a crosslinkable resin composition described above may be satisfy | filled. The content of the cross-linking curable resin (B) is determined by measuring the peak derived from the epoxy resin in the same manner by the method using the infrared spectroscopy as described above. The amount can be measured.

  The compounding amount of the crosslinking agent (C) is usually an amount within the range of 0.6 mol or more and 1.3 mol or less of acid anhydride group with respect to 1 mol of the secondary hydroxyl group of the phenoxy resin (A), preferably The amount is in the range of 0.7 to 1.3 mol, more preferably in the range of 1.1 to 1.3 mol. When the amount of the acid anhydride group is 0.6 mol or more, the crosslink density is increased, so that mechanical properties and heat resistance are excellent. This effect is further enhanced by setting the amount of the acid anhydride group to 0.7 mol or more, further 1.1 mol or more. When the amount of the acid anhydride group is 1.3 mol or less, it is possible to suppress the unreacted acid anhydride or carboxyl group from adversely affecting the curing characteristics and the crosslinking density. For this reason, it is preferable to adjust the compounding quantity of a crosslinking curable resin (B) according to the compounding quantity of a crosslinking agent (C). Specifically, for example, an epoxy resin used as the cross-linking curable resin (B) reacts a carboxyl group generated by a reaction between the secondary hydroxyl group of the phenoxy resin (A) and the acid anhydride group of the cross-linking agent (C). For this purpose, the amount of the epoxy resin blended with the cross-linking agent (C) is preferably in the range of 0.5 mol or more and 1.2 mol or less. Preferably, the equivalent ratio of the crosslinking agent (C) and the epoxy resin is in the range of 0.7 to 1.0 mol.

  If the cross-linking agent (C) is blended with the phenoxy resin (A) and the cross-linking curable resin (B), a cross-linking resin composition can be obtained, but an accelerator as a catalyst to ensure the cross-linking reaction. (D) may be further contained. The accelerator (D) is not particularly limited as long as it is solid at room temperature and has no sublimation property. For example, a tertiary amine such as triethylenediamine, 2-methylimidazole, 2-phenylimidazole, Examples thereof include imidazoles such as 2-phenyl-4-methylimidazole, organic phosphines such as triphenylphosphine, and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate. These accelerators (D) may be used alone or in combination of two or more. In the case where the matrix resin 101A is formed by making the crosslinkable resin composition into a fine powder and adhering it to the reinforcing fiber substrate using a powder coating method using an electrostatic field, the catalyst activation temperature is as the accelerator (D). It is preferable to use an imidazole-based latent catalyst that is solid at room temperature of 130 ° C. or higher. When using an accelerator (D), the compounding quantity of an accelerator (D) is 0 with respect to 100 mass parts of total amounts of a phenoxy resin (A), a crosslinking curable resin (B), and a crosslinking agent (C). It is preferable to be within the range of 1 part by weight to 5 parts by weight.

  The crosslinkable resin composition is solid at room temperature, and its melt viscosity is such that the minimum melt viscosity, which is the lower limit of the melt viscosity in the temperature range of 160 to 250 ° C., is 3,000 Pa · s or less. Preferably, it is 2,900 Pa · s or less, more preferably 2,800 Pa · s or less. By setting the minimum melt viscosity in the temperature range within the range of 160 to 250 ° C. to 3,000 Pa · s or less, the adherend can be sufficiently impregnated with the crosslinkable resin composition at the time of thermocompression bonding by hot press or the like. Since it can suppress that defects, such as a void, arise in FRTP12A, the mechanical physical property of 1 A of metal-FRTP composite members improves. This effect is further enhanced by setting the minimum melt viscosity in the temperature range of 160 to 250 ° C. to 2,900 Pa · s or less, and further to 2,800 Pa · s or less.

  The matrix resin 101 has, for example, natural rubber, synthetic rubber, elastomer and the like, various inorganic fillers, solvents, pigments, colorants, antioxidants, ultraviolet light inhibitors, difficult to the extent that the adhesiveness and physical properties are not impaired. Other additives such as a flame retardant and a flame retardant aid may be blended. As the elastomer, for example, styrene elastomer, olefin elastomer, alkene elastomer, vinyl chloride elastomer, urethane elastomer, amide elastomer, and the like can be used. The additive is preferably blended so that the total including the thermoplastic resin and the reinforcing fibers 102 is 100% by volume.

  The content of the thermoplastic resin contained in the matrix resin 101A is preferably 20% by volume or more and 80% by volume or less with respect to the entire volume of FRTP12. When the content of the thermoplastic resin is less than 20% by volume, the thermocompression bonding between the metal member 11 and the FRTP 12 becomes insufficient, and there is a possibility of peeling at the crimping surface. On the other hand, if the content of the thermoplastic resin is more than 80% by volume, the resin softened and melted during the pressing process will flow out into the mold, prompting voids and defects in the CFRTP, and reducing the strength of the composite material. Problems can occur. More preferably, the content of the thermoplastic resin contained in the matrix resin 101 is not less than 35% by volume and not more than 75% by volume. The matrix resin 101A is preferably contained so that the total content of the matrix resin 101A and the reinforcing fibers 102 is 100% by volume.

(Reinforcing fiber 102)
The material of the reinforcing fiber 102 and the reinforcing fiber base used in the present embodiment are preferably the same as the reinforcing fiber 102 used in the first embodiment.

(Fiber density)
As for the fiber density (VF: Volume Fraction) of FRTP12A, it is preferable that 20-70 volume% of the reinforced fiber 102 is contained with respect to the whole volume of FRTP12 similarly to 1st Embodiment. When a continuous fiber is used as the reinforcing fiber 102, the VF of the FRTP 12 is preferably 40% by volume or more and 70% by volume or less, and more preferably 55% by volume or more and 65% by volume or less. When short fibers are used as the reinforcing fibers 102, the VF of the FRTP 12 is preferably 20% by volume or more and 50% by volume or less, and more preferably 25% by volume or more and 45% by volume or less.

  In the metal-FRTP composite member 1A according to this embodiment, the FRTP 12A is formed using at least one CFRTP molding prepreg. The FRTP 12A is not limited to one layer, and may be two or more layers as shown in FIG. 7, for example. The thickness of the FRTP 12A and the number n of FRTP 12A layers when the FRTP 12A includes a plurality of layers may be appropriately set according to the purpose of use. When the FRTP 12A has a plurality of layers, each layer may have the same configuration or may be different. In addition, the type and content ratio of the reinforcing fibers 102 constituting the FRTP 12A may be different for each layer.

<3.2. Processing Method for Metal-FRTP Composite Member 1A>
As described above, the configuration of the metal-FRTP composite member 1A as the metal-fiber reinforced resin material composite according to the present embodiment has been described in detail. Subsequently, the metal according to the present embodiment will be described with reference to FIGS. -The processing method of FRTP composite member 1A is demonstrated. 8 and 9 are explanatory views showing examples of processing steps for the metal-FRTP composite member 1A.

  In the metal-FRTP composite member 1A, the FRTP 12A processed into a desired shape and the metal member 11 are heated to a predetermined heating temperature, and then a predetermined pressure is applied via a mold having a predetermined shape. The integrated machining process is performed, and the integrally processed metal member 11 and FRTP 12A are integrally processed through a mold releasing process for releasing the mold from the mold at a predetermined temperature. The integrated processing in the present invention means that the FRTP 12A and the metal member 11 are bonded by the matrix resin 101A, and the metal member 11 and the FRTP 12A are processed without being peeled off. Hereinafter, a method of combining (integrating) the metal member 11 and the FRTP 12A by thermocompression bonding will be described.

<3.2.1. Method 1>
First, as shown to Fig.8 (a), FRTP12A is arrange | positioned and laminated | stacked on the surface of at least one side of the metal member 11, and it is set as a laminated body. In FIG. 8, similarly to the first embodiment, the mold having a convex shape is an upper mold m1, the mold having a concave shape is a lower mold m2, and the upper part of the metal member 11, that is, the upper mold m1. The case where FRTP12 is arrange | positioned at the side is shown. The case where FRTP12A is arrange | positioned at the upper part of the metal member 11 is shown. At this time, it is preferable that the bonding surface of FRTP12A bonded to the metal member is activated by the same method as in the first embodiment. Moreover, it is preferable to remove the surface deposits and degrease the metal member 11 in advance by the same method as in the first embodiment. In FIG. 8A, a prepreg for FRP molding can be laminated instead of FRTP 12A.

  In FIG. 8A, instead of FRTP 12A, a laminated body in which FRP molding prepregs are laminated can be integrally processed while combining the FRP molding prepreg and the metal member 11A at the time of integral processing described later. is there. In addition, a composite of the metal member 11A and the FRTP 12A can be integrally processed by a method described later. Further, the FRTP 12A is not limited to a single layer as shown in FIG.

Next, as shown in FIG. 8 (b), heating the laminate of the metal member 11 and FRTP12A to a predetermined heating temperature _{T 1.} The heating temperatures T ₁ is, FRTP alone for a long time, for example 1 hour or more thereof as the temperature is held in the deformation due to the weight of the FRTP occurs temperature, that is, in itself is a temperature that can not retain its shape. Specifically, the heating temperature T ₁ is lower than the decomposition temperature of the thermoplastic resin and is equal to or higher than (Tg + 50) ° C., where Tg is the glass transition point of the thermoplastic resin contained in the FRP matrix resin 101A. The temperature is preferably within the range of (Tg + 200) ° C. or lower. When the heating temperature T ₁ is located above the decomposition temperature of the thermoplastic resin, heat thermoplastic resin is decomposed to decrease the adhesion between the metal member 11, as a result, possibility that the strength of the metal -FRTP composite member 1A is reduced There is. The decomposition temperature in the present embodiment refers to a temperature at which the weight loss is 1% when the thermogravimetric measurement of the resin contained in the FRTP 12 is performed in an air atmosphere. When the heating temperature _{T 1} is less than (Tg + 50) ℃, there is a case where peeling occurs at the interface between the metal member 11 and FRTP12A. Further, if the heating temperature _{T 1} is less than (Tg + 50) ℃, because the fluidity of the matrix resin 101A is low, when the FRTP12A multiple layers are laminated, the shear displacement between the bending during FRTP12A layer May occur. When the heating temperature _{T 1} is is (Tg + 200) ℃ greater than that flowability of the matrix resin 101A is too high, sometimes the matrix resin 101A flows out from the mold m. As a result, the matrix resin in FRTP12A may decrease, and the strength of the composite may decrease. The heating temperature T ₁ is more preferably (Tg + 90) ° C. or higher and (Tg + 150) ° C. or lower.

  In order to improve the releasability of the metal-FRTP composite member 1A, the surface of the mold m may be subjected to mold release treatment and preheating of the mold m in the same manner as in the first embodiment. preferable.

Then, as shown in FIG. 8 (c), using a die m, by applying a pressure to the metal member 11 and FRTP12A, the above heating temperature _{T 1,} it is processed into a predetermined shape.

  The press load during processing is preferably 0.1 kN or more and 100 kN or less. If it is less than 0.1 kN, the FRTP 12 having a thickness of less than 12 mm and the steel plate composite having a thickness of 0.1 mm or more may not be processed into a predetermined shape. On the other hand, if the press load is 100 kN, there is a possibility that the fiber breaks, which is not preferable.

The processing speed of the laminated body of the metal member 11 and FRP is defined by the strain rate of the material, and the range is preferably 0.05 to 10 s ⁻¹ . The strain rate of the material is a value obtained by dividing the speed of the mold m by the thickness of the material. When this strain rate is less than 0.05 s ⁻¹ , integral molding is possible, but productivity is significantly reduced. If it exceeds 10 s ⁻¹ , the resin in the FRTP 12 cannot follow the processing of the steel sheet, and there is a possibility that deviation occurs between the layers of the FRTP 12. More preferably, the processing speed is the processing speed in the range of strain rate of the laminate of the metal member 11 and the FRP is 0.5 s ^-1 or more ^{5s -1} or less.

  If the pressing time is at least 1 minute or more, the resin in FRTP moves to the steel plate and adhesion is ensured, so that the integrated metal-FRTP composite member 1 can be processed, and it is 5 minutes or more. And preferred. Although there is no particular upper limit, it is preferably 10 minutes or less from the viewpoint of productivity.

Thereafter, as shown in FIG. 8 (d), to remove the pressure with a die m with a mold release temperature _{T 2,} to obtain a metal -FRTP composite member 1A is removed from the mold m.

Releasing temperature T ₂ at this time, when the FRTP alone is held at the above temperature, small forces, such as cracks in the carbon fiber or the resin in the FRTP when a force more than 1N is applied is not enter It is a temperature that easily deforms, that is, a predetermined temperature whose shape is not completely determined. Specifically, the heating temperature _{T 2} is preferably a temperature within the (Tg + 20) ℃ least (Tg + 200) ℃ the following ranges. When releasing temperature _{T 2} is less than (Tg + 20) ℃, can not follow FRTP12A springback of the metal member 11, there is a case where peeling at the interface between the metal member 11 and FRTP12A occurs. Further, when the release temperature _{T 2} is at (Tg + 200) ℃ greater than that flowability of the matrix resin 101A is too high, sometimes the matrix resin 101A is flowing out of the mold m. As a result, the matrix resin in FRTP12A may decrease, and the strength of the composite may decrease. Releasing temperature _{T 2} is more preferably not more than ℃ (Tg + 50) ℃ or more (Tg + 150).

If the releasing temperature T ₂ is in the above temperature range, the resin in FRTP12A has a fluidity that allows follow the springback of the metal member 11, the pressure removal rate of metal -FRTP composite member 1A is There are no particular restrictions.

  The peel strength between the metal member 11 and the FRTP 12 is defined in “JIS K 6854-3 Adhesive—Peel Adhesive Strength Test Method—Part 3: T-Peeling” as in the first embodiment. It can be measured by the method.

  In the above description, the case where the FRTP 12A is laminated on the upper part of the metal member 11 has been described. However, as shown in FIG. 9, the metal member 11 can be laminated and processed on the upper part of the FRTP 12A. Hereinafter, a method of laminating the metal member 11 on the FRTP 12A and integrally processing the FRTP 12A will be described with reference to FIG.

<3.2.2. Method 2>
When the metal member 11 is laminated on the upper part of the FRTP 12A and integrally processed, as shown in FIG. 9A, the laminate in which the metal member 11 is laminated on the upper part of the FRTP 12A, as shown in FIG. It mounts on the support plate b, and heat-pressure-bonds by applying a pressure through the metal mold m.

As in the first embodiment, the bonding surface of the FRTP 12A bonded to the metal member 11 is preferably activated by, for example, roughening by blasting or the like, plasma processing, corona treatment, or the like. In FIG. 9A, a prepreg for FRP molding can be laminated instead of the FRTP 12A. Further, the FRTP 12A is not limited to a single layer as shown in FIG.

Next, as shown in FIG. 9 (b), placing the stack of FRTP12A and the metal member 11 to the support plate b, and heated to a predetermined heating temperature _{T 1.} Heating temperatures T ₁ at this time is the same as the heating temperature T ₁ of the method 1.

  In order to improve the mold releasability of the metal-FRTP composite member 1A, it is preferable that the surface of the mold m is subjected to a mold release process similar to the method 1. Further, it is preferable that the surface of the support plate b is subjected to the same release treatment as in the method 1. Further, it is preferable that the mold m is preheated by the same method as the method 1 when the laminate is heated.

Then, as shown in FIG. 9 (c), using a die m, by applying a molding pressure in the molded body and the support plate b of the metal member 11 and FRTP12A, the above heating temperature T _1, in a predetermined shape Process. At this time, it is preferable that the shape of the mold m is such that the thickness of the support plate b is taken into consideration so that the laminate of the metal member 11 and the FRTP 12A becomes the metal-FRTP composite member 1 having a desired shape. The press load, processing speed, pressure application time, and the like can be set to the same conditions as in Method 1.

Thereafter, as shown in FIG. 9 (d), to remove the pressure with a die m with a mold release temperature _{T 2,} to obtain a metal -FRTP composite member 1A is removed from the mold m. In this case, the releasing temperature T ₂ is similar to the release temperature T ₂ of Method 1.

  According to the present embodiment described above, the metal-FRTP composite member 1A in which the metal member 11 and the FRTP 12A are firmly joined without requiring a step of pasting the metal member 11 and the FRTP 12A or a step of shaping the metal member 11 in advance. Integrated processing is possible. In this method, the metal member 11 and the FRTP 12A may be preliminarily bonded and may be integrally processed in the next step.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples. In addition, the various physical property tests and measurement methods in this example are as follows.

<4. First Example>
A crystalline resin was used as the thermoplastic resin contained in the matrix resin 101 of FRTP12, and the metal member 11 and FRTP12 were integrally processed by the method 1 described above to produce a specimen. Table 1-1 and Table 1-2 show the manufacturing conditions of each specimen.

As the metal member 11, a steel plate and an aluminum alloy plate (A5052) were used. The ratio of the yield stress to the Young's modulus of the steel sheet used was 5.5 × 10 ⁻³ , and the thickness of the steel sheet was 1.5 mm. The ratio of yield stress to Young's modulus of the used aluminum alloy was 3.56 × 10 ⁻³ , and the thickness of the aluminum alloy was 0.6 mm. Carbon fiber cloth (PAN-based carbon fiber STS60 manufactured by Toho Tenax Co., Ltd.) and unidirectional glass fiber were used as the reinforcing fibers 102 contained in FRTP12. Polypropylene and nylon were used as the crystalline thermoplastic resin contained in the matrix resin 101. Further, as an additive in the matrix resin 101, an olefin elastomer (manufactured by Sumitomo Chemical Co., Ltd., Espolex TPE series) was used. As FRTP12 containing a unidirectional glass fiber, a glass fiber prepreg: CETEX TC960 manufactured by TENCAT Corporation using nylon as the matrix resin 101 was used. The laminate in which FRTP 12 is laminated on the upper part of the metal member 11 is heated at the heating temperature T ₁ described in Table 1-1 and Table 1-2, the strain rate is 1 s ⁻¹ , the press load is set to 50 kN, The laminate was processed for a press time of 5 minutes. Thereafter, it was released from the mold m with a mold release temperature T ₂ shown in Table 1-1 and Table 1-2, to obtain a complex. At this time, Daikin Industries, Ltd. die-free was spray-coated on the mold as a release agent.

  About the sample obtained by the said method, the presence or absence of the interface peeling of the metal member 11 and FRTP12 and the shear shift | offset | difference of FRTP12 were confirmed. Regarding interface peeling between metal member 11 and FRTP 12, the interface between metal member 11 and FRTP 12 was observed using an optical microscope (manufactured by Keyence Corporation, VH-5500), and no interface peeling of 50 μm or more was observed. Was extremely good (◎), a case where peeling of 100 μm or more was not confirmed was judged as good (◯), and a case where peeling of 100 μm or more was confirmed was judged as rejected (×).

  Regarding the shear deviation of FRTP12, the surface of FRTP12 of the sample obtained by processing was observed, and the case where protrusions of 100 μm or more were not observed was extremely good (A), and the case where protrusions of 500 μm or more were not confirmed was good ( (Circle)) and the thing by which the protrusion of 500 micrometers or more was confirmed was made disqualified (x).

  Moreover, the peeling strength test was done with the following method. A test piece having a width of 15 mm and a length of 90 mm is cut out from the prepared sample, the metal member 11 of the test piece is peeled off from the FRTP 12 by 30 mm, and only the metal part is bent at 90 degrees. A metal member bent at 90 degrees using a room temperature curable adhesive is bonded to the surface of the FRTP 12 opposite to the surface to which the metal member 11 is bonded. The test piece produced as described above can be used for the peel strength test. In addition, when the adhesive strength between the room temperature curable adhesive used and FRTP12 was separately examined, it was 200 N or more, and thus the peel strength test result reflects the peel strength between the metal member 11 and FRTP12. It becomes.

Table 1-1 and as shown in Table 1-2, the heating temperature _{T 1} (Tm-20) ℃ least (Tm + 10) ℃ set within a temperature range of, integrally forming a metal member 11 and FRTP12 after the release temperature _{T 2} (Tm-30) ℃ least (Tm + 10) ℃ metal -FRTP composite member 1 is set within a temperature range of below by releasing from the mold, the moldability and processability It turned out that the outstanding metal-FRTP composite member 1 is obtained. Moreover, it turned out that the metal-FRTP composite member 1 obtained by the processing method which concerns on this embodiment shows peeling strength 20N or more.

<5. Second Embodiment>

  Using an amorphous resin as the thermoplastic resin contained in the matrix resin 101A of FRTP12A, the method 1 of the second embodiment described above is applied, and the metal member 11 and FRTP12A are integrally processed to produce a specimen. did. Tables 2-1 to 2-3 show the manufacturing conditions of each specimen.

As the metal member 11, a steel plate, an aluminum plate, and an aluminum alloy plate (A5052) were used. The ratio of the yield stress to the Young's modulus of the steel sheet used was 5.5 × 10 ⁻³ , and the thickness of the steel sheet was 1.5 mm. The ratio of yield stress to Young's modulus of the aluminum plate used was 1.0 × 10 ⁻³ , and the thickness of the aluminum plate was 0.5 mm. The ratio of yield stress to Young's modulus of the used aluminum alloy was 3.56 × 10 ⁻³ , and the thickness of the aluminum alloy was 0.6 mm. Carbon fiber cloth (PAN-based carbon fiber STS60 manufactured by Toho Tenax Co., Ltd.) and unidirectional glass fiber were used as the reinforcing fibers 102 contained in FRTP12. Polypropylene and nylon were used as the crystalline thermoplastic resin contained in the matrix resin 101. Further, as an additive in the matrix resin 101, an olefin elastomer (manufactured by Sumitomo Chemical Co., Ltd., Espolex TPE series) was used. As FRTP12 containing a unidirectional glass fiber, a glass fiber prepreg: CETEX TC920 manufactured by TENCATE using polycarbonate as a matrix resin 101 was used. The laminate obtained by laminating a FRTP12A on top of the metal member 11 is heated at a heating temperature _{T 1} of the described in Table 2-1 to 2-3, set strain rate ^{1s -1,} a press load to 50 kN, The laminate was processed for a press time of 5 minutes. Thereafter, it was released from the mold m with a mold release temperature _{T 2} shown in Table 2-1 to 2-3 to obtain a complex. At this time, Daikin Industries, Ltd. die-free was spray-coated on the mold as a release agent.

  About the sample obtained by the said method, the presence or absence of the interface peeling of the metal member 11 and FRTP12A and the shear deviation of FRTP12A were confirmed. Regarding the interface peeling between the metal member 11 and FRTP12A, the interface between the metal member 11 and FRTP12A was observed using an optical microscope (manufactured by Keyence Corporation, VH-5500), and no interface peeling of 50 μm or more was observed. Was very good (◎), a case where peeling of 100 μm or more was not confirmed was good (◯), and a case where peeling of 100 μm or more was confirmed was rejected (x).

  Regarding the shear deviation of FRTP12A, the surface of FRTP12A of the sample obtained by processing was observed, and when no protrusions of 100 μm or more were observed, the result was very good (A), and when no protrusions of 500 μm or more were confirmed (good) (Circle)) and the thing by which the protrusion of 500 micrometers or more was confirmed was made disqualified (x).

  Moreover, the peeling strength test was done with the following method. A test piece having a width of 15 mm and a length of 90 mm is cut out from the prepared sample, the metal member 11 of the test piece is peeled off from the FRTP 12A by 30 mm, and only the metal part is bent at 90 degrees. A metal member bent at 90 degrees using a room temperature curable adhesive is bonded to the surface of the FRTP 12A opposite to the surface to which the metal member 11 is bonded. The test piece produced as described above can be used for the peel strength test. In addition, when the adhesive strength between the room temperature curable adhesive used and FRTP12 was separately examined, it was 200 N or more, and thus the peel strength test result reflects the peel strength between the metal member 11 and FRTP12. It becomes.

As shown in Tables 2-1 to 2-3, the heating temperature T ₁ is set to a temperature range of less than 400 ° C. and (Tg + 50) ° C. to (Tg + 200) ° C. after integrally processed FRTP12A, the releasing temperature _{T 2,} below 400 ° C., and, (Tg + 20) ℃ or higher (Tg + 200) release the ° C. was set within a temperature range of metal -FRTP composite member 1A from the mold By doing, it turned out that 1A of metal-FRTP composite members excellent in the moldability and workability are obtained. Moreover, it turned out that 1 A of metal-FRTP composite members obtained by the processing method which concerns on this embodiment show 20 N or more of peeling strength.

  The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited to such examples. It is obvious that a person having ordinary knowledge in the technical field to which the present invention pertains can come up with various changes or modifications within the scope of the technical idea described in the claims. Of course, it is understood that these also belong to the technical scope of the present invention.

1, 1A metal-FRTP composite member 11 metal member 12, 12A FRTP
101, 101A Matrix resin 102 Reinforcing fiber

Claims (13)

After heating a metal plate having a matrix resin containing a thermoplastic resin and a fiber reinforced resin material having a reinforced fiber material to a predetermined temperature at which at least one surface of the metal reinforced resin material alone cannot retain its shape An integrated processing step of applying a predetermined pressure through a mold having a predetermined shape and integrally processing;
A mold release step of releasing the integrally processed metal plate and the fiber reinforced resin material from the mold at a predetermined temperature at which the shape of the fiber reinforced resin material is not fixed.
A method for processing a metal-thermoplastic fiber reinforced resin material composite member. The thermoplastic resin is a crystalline resin having a melting point T _m,
The heating temperature in the integrated processing step is a temperature in the temperature range of (T _m −20) to (T _m +10) ° C.
The mold release temperature in the mold release step is a temperature in the temperature range of (T _m −30) to (T _m +10) ° C.
The processing method of the metal-thermoplastic fiber reinforced resin material composite member according to claim 1. The thermoplastic resin is a noncrystalline resin having a glass transition temperature T _g,
The heating temperature in the integrated processing step is lower than the decomposition temperature of the amorphous thermoplastic resin, and is a temperature in the temperature range of (Tg + 50) to (Tg + 200) ° C.
The mold release temperature in the mold release step is lower than the decomposition temperature of the amorphous thermoplastic resin and is a temperature in the temperature range of (Tg + 20) to (Tg + 200) ° C.
The processing method of the metal-thermoplastic fiber reinforced resin material composite member according to claim 1. The thermoplastic resin is contained in an amount of 20 to 80% by volume based on the total volume of the fiber reinforced resin material, and the total of the reinforced fiber material and the matrix resin is 100% by volume.
The processing method of the metal-thermoplastic fiber reinforced resin material composite member as described in any one of Claims 1-3. The reinforcing fiber material is contained in an amount of 20 to 70% by volume with respect to the total volume of the fiber reinforced resin material, and is contained so that the total of the reinforcing fiber material and the matrix resin is 100% by volume.
The processing method of the metal-thermoplastic fiber reinforced resin material composite member as described in any one of Claims 1-4. The thickness of the metal plate is 0.1 to 6.0 mm, and the ratio of the yield stress and Young's modulus of the metal plate is 0.8 × 10 ⁻³ or more.
The processing method of the metal-thermoplastic fiber reinforced resin material composite member as described in any one of Claims 1-5. The material of the metal plate is a steel material,
The processing method of the metal-thermoplastic fiber reinforced resin material composite member as described in any one of Claims 1-6. The reinforcing fiber material is a carbon fiber material.
The processing method of the metal-thermoplastic fiber reinforced resin material composite member as described in any one of Claims 1-7. A predetermined mold release treatment is performed on the surface of the mold,
The processing method of the metal-thermoplastic fiber reinforced resin material composite member as described in any one of Claims 1-8. As the amorphous thermoplastic resin, containing a phenoxy resin,
The processing method of the metal-thermoplastic fiber reinforced resin material composite member as described in any one of Claims 3-9. A metal plate having a thickness of 0.1 to 6.0 mm and a ratio of yield stress to Young's modulus of 0.8 × 10 ⁻³ or more;
A fiber reinforced resin material that is disposed on at least one surface of the metal plate, has a thickness of 2 to 12 mm, and includes a matrix resin containing a thermoplastic resin and a reinforced fiber material;
The fiber reinforced resin material contains at least 20 to 80% by volume of the thermoplastic resin,
The metal plate and the fiber reinforced resin material integrally have a predetermined shape,
Metal-thermoplastic fiber reinforced resin material composite. The peel strength of a test piece having a width of 15 mm, measured by a 90 ° peel adhesion strength test defined by a T-shaped peel test described in JIS K 6854-3, is 20 N or more.
The metal-thermoplastic fiber reinforced resin material composite member according to claim 11. A metal plate having a thickness of 0.1 to 6.0 mm and a ratio of Young's modulus and yield stress of 0.8 × 10 ⁻³ or more;
A fiber reinforced resin material that is disposed on at least one surface of the metal plate, has a thickness of 2 to 12 mm, and includes a matrix resin containing a thermoplastic resin and a reinforced fiber material;
The fiber reinforced resin material contains at least 20 to 80% by volume of the thermoplastic resin,
The metal plate and the fiber reinforced resin material have a predetermined shape integrally.
Automotive parts.

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