JP2018167418A - Metal/fiber-reinforced plastic composite structure - Google Patents
Metal/fiber-reinforced plastic composite structure Download PDFInfo
- Publication number
- JP2018167418A JP2018167418A JP2017064706A JP2017064706A JP2018167418A JP 2018167418 A JP2018167418 A JP 2018167418A JP 2017064706 A JP2017064706 A JP 2017064706A JP 2017064706 A JP2017064706 A JP 2017064706A JP 2018167418 A JP2018167418 A JP 2018167418A
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- JP
- Japan
- Prior art keywords
- reinforced plastic
- metal
- fiber reinforced
- epoxy resin
- composite structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 143
- 239000002184 metal Substances 0.000 title claims abstract description 143
- 229920002430 Fibre-reinforced plastic Polymers 0.000 title claims abstract description 111
- 239000011151 fibre-reinforced plastic Substances 0.000 title claims abstract description 111
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000003822 epoxy resin Substances 0.000 claims abstract description 90
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 90
- 230000003746 surface roughness Effects 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 45
- 229910000838 Al alloy Inorganic materials 0.000 claims description 39
- 229920001187 thermosetting polymer Polymers 0.000 claims description 31
- 239000011342 resin composition Substances 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 125000003700 epoxy group Chemical group 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 35
- 238000000034 method Methods 0.000 description 35
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- 239000002253 acid Substances 0.000 description 31
- 238000001723 curing Methods 0.000 description 26
- 239000000853 adhesive Substances 0.000 description 24
- 230000001070 adhesive effect Effects 0.000 description 24
- 235000019592 roughness Nutrition 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 22
- 238000007788 roughening Methods 0.000 description 21
- 229910001447 ferric ion Inorganic materials 0.000 description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 16
- 239000012790 adhesive layer Substances 0.000 description 16
- 239000004918 carbon fiber reinforced polymer Substances 0.000 description 16
- 239000000835 fiber Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
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- 238000012360 testing method Methods 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
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- 229930185605 Bisphenol Natural products 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 206010040844 Skin exfoliation Diseases 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 229960003280 cupric chloride Drugs 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
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- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
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- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
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- 239000007769 metal material Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- 229920003023 plastic Polymers 0.000 description 1
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- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
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- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Landscapes
- Laminated Bodies (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Epoxy Resins (AREA)
Abstract
Description
本発明は金属／繊維強化プラスチック複合構造体に関する。 The present invention relates to a metal / fiber reinforced plastic composite structure.
炭素繊維強化プラスチック（以下、ＣＦＲＰとも呼ぶ。）等の繊維強化プラスチックを用いた軽量高剛性材料は軽量で高強度であるため航空・宇宙分野、スポーツ・レジャー分野、船舶分野、建築・土木分野、自動車分野等の幅広い分野で用いられている。しかしながら、繊維強化プラスチック単独では強度がやや不足であり、構造材料としてより高い強度が必要な場合には繊維強化プラスチック部材を金属部材と一体化した複合材料として用いられている。 Lightweight and high rigidity materials using fiber reinforced plastics such as carbon fiber reinforced plastics (hereinafter also referred to as CFRP) are lightweight and strong, so they are aerospace / sports, sports / leisure, ship, construction / civil engineering, Used in a wide range of fields such as the automobile field. However, the strength of the fiber reinforced plastic alone is slightly insufficient, and when a higher strength is required as a structural material, it is used as a composite material in which the fiber reinforced plastic member is integrated with the metal member.
繊維強化プラスチックを用いた軽量高剛性材料と金属部材との一体化手法としては、ボルトやナット等を用いた機械的な接合方法や、接着剤を用いる接合方法等が知られている。前者の機械的接合法は穴あけ等の加工工程が必要であるということ以外は軽量化に逆行するので、現在では後者の接着剤を用いた接合が適用される場合が多くなっている。
接着剤を用いた接合工程は常温あるいは加熱で実施され、接着剤としてはユリア樹脂系接着剤、メラミン樹脂系接着剤、フェノール樹脂系接着剤、α−オレフィン樹脂接着剤、エポキシ樹脂系接着剤、ホットメルト接着剤、ポリウレタン系接着剤、クロロプレンゴム系接着剤、ニトリルゴム系接着剤、ＳＢＲ系接着剤、エチレン共重合樹脂接着剤等が知られている。特にエポキシ樹脂系接着剤は硬化が速く、繊維強化プラスチック部材と金属との接合面の接着強度が高く、溶剤を含まず、硬化後の収縮も少ないことから、多用されている（例えば、特許文献１および２）。
As a method for integrating a lightweight high-rigidity material using fiber reinforced plastic and a metal member, a mechanical joining method using a bolt, a nut, or the like, a joining method using an adhesive, or the like is known. Since the former mechanical joining method goes against weight reduction except that a processing step such as drilling is required, at present, joining using the latter adhesive is often applied.
The bonding process using the adhesive is carried out at room temperature or heating. As the adhesive, a urea resin adhesive, a melamine resin adhesive, a phenol resin adhesive, an α-olefin resin adhesive, an epoxy resin adhesive, Hot melt adhesives, polyurethane adhesives, chloroprene rubber adhesives, nitrile rubber adhesives, SBR adhesives, ethylene copolymer resin adhesives, and the like are known. In particular, epoxy resin adhesives are frequently used because they are fast cured, have high adhesive strength at the joint surface between the fiber-reinforced plastic member and the metal, do not contain solvents, and have little shrinkage after curing (for example, patent documents). 1 and 2).
しかしながら、仮に公知エポキシ樹脂系接着剤を金属部材と繊維強化プラスチック部材との接合のために使用し、接着強度そのものが高い値を示した場合であっても、破断面の破壊形式が金属部材と接着剤層との界面剥離を伴う場合があった。このような界面剥離現象が起き、界面剥離部周辺の接合部分付近に、例えば電解質水溶液等の液体が接触した場合は、防錆処理されていない裸の金属面と繊維間のガルバニック反応に伴って金属の電気腐食が急速に進行し、金属材料そのものの破壊をもたらす二次被害を併発する可能性も否定できなかった。 However, even if a known epoxy resin adhesive is used for joining a metal member and a fiber reinforced plastic member, and the bond strength itself shows a high value, the fracture type of the fracture surface is the metal member. In some cases, there was interface peeling with the adhesive layer. When such an interfacial debonding phenomenon occurs and a liquid such as an aqueous electrolyte solution is in contact with the vicinity of the joint portion around the interfacial debonding portion, for example, a galvanic reaction between the bare metal surface that is not rust-proofed and the fiber It could not be denied that the electrical corrosion of the metal progressed rapidly, causing secondary damage that would cause destruction of the metal material itself.
本発明は上記事情に鑑みてなされたものであり、接着剤層と繊維強化プラスチック部材との間の界面剥離および金属部材と接着剤層との間の界面剥離が抑制され、接着剤層および／または繊維強化プラスチック部材の母材破壊が主に生じるものであり、かつ、繊維強化プラスチック部材と金属部材との間の接合性に優れた金属／繊維強化プラスチック複合構造体を提供することである。 The present invention has been made in view of the above circumstances, and interfacial delamination between the adhesive layer and the fiber-reinforced plastic member and interfacial delamination between the metal member and the adhesive layer are suppressed, and the adhesive layer and / or Another object of the present invention is to provide a metal / fiber reinforced plastic composite structure in which the base material destruction of the fiber reinforced plastic member is mainly caused and the bonding property between the fiber reinforced plastic member and the metal member is excellent.
本発明者らは、接着剤層を介して金属部材と繊維強化プラスチック部材が一体化された複合構造体において、接着剤層と繊維強化プラスチック部材との間の界面剥離および金属部材と接着剤層間との間の界面剥離の発生が抑制された金属／繊維強化プラスチック複合構造体を開発すべく鋭意検討した。その結果、表面に特定の微細凹凸形状を有する金属部材を使用し、特定の接着剤を金属部材と繊維強化プラスチック部材との間に介在させることによって、接着剤層と繊維強化プラスチック部材との間の界面剥離および金属部材と接着剤層との間の界面剥離が抑制され、接着剤層および／または繊維強化プラスチック部材の母材破壊が主に生じ、繊維強化プラスチック部材と金属部材との間の接合性に優れた金属／繊維強化プラスチック複合構造体が得られることを見出し、本発明に到達した。 In the composite structure in which the metal member and the fiber reinforced plastic member are integrated with each other through the adhesive layer, the present inventors have performed interfacial peeling between the adhesive layer and the fiber reinforced plastic member and the metal member and the adhesive layer. In order to develop a metal / fiber reinforced plastic composite structure in which the occurrence of interfacial delamination between the two is suppressed, the inventors have intensively studied. As a result, by using a metal member having a specific fine uneven shape on the surface and interposing a specific adhesive between the metal member and the fiber reinforced plastic member, the adhesive layer and the fiber reinforced plastic member are interposed. Interfacial delamination and interfacial delamination between the metal member and the adhesive layer are suppressed, and the base material destruction of the adhesive layer and / or the fiber reinforced plastic member mainly occurs. The inventors have found that a metal / fiber reinforced plastic composite structure excellent in bondability can be obtained, and have reached the present invention.
本発明によれば、以下に示す金属／繊維強化プラスチック複合構造体が提供される。 According to the present invention, the following metal / fiber reinforced plastic composite structure is provided.
［１］
金属部材と、
繊維強化プラスチック部材と、
上記金属部材と上記繊維強化プラスチック部材との間に設けられたエポキシ樹脂硬化体層と、
を備え、
上記金属部材は少なくとも上記繊維強化プラスチック部材との接合部表面にＪＩＳ Ｂ６０１（対応国際規格：ＩＳＯ４２８７）で規定される表面粗さパラメーターが下記要件ａ）〜ｃ）を同時に満たす微細凹凸形状を有し、
上記エポキシ樹脂硬化体層は上記金属部材の上記微細凹凸形状の一部または全部を覆うように形成されており、
上記金属部材と上記繊維強化プラスチック部材とは上記エポキシ樹脂硬化体層を介して接合している金属／繊維強化プラスチック複合構造体。
ａ）粗さ曲線の十点平均粗さ（Ｒｚ）が５μｍ超５０μｍ以下である
ｂ）粗さ曲線の算術平均粗さ（Ｒａ）が０．５μｍ以上３０μｍ以下である
ｃ）粗さ曲線要素の平均長さ（ＲＳｍ）が２０μｍ以上３００μｍ以下である
［２］
上記［１］に記載の金属／繊維強化プラスチック複合構造体において、
上記エポキシ樹脂硬化体層がエポキシ樹脂と硬化剤とを含む熱硬化性樹脂組成物の硬化物により構成される金属／繊維強化プラスチック複合構造体。
［３］
上記［２］に記載の金属／繊維強化プラスチック複合構造体において、
Ｂ型粘度計を用いて２３℃、回転数０．２ｒｐｍの条件で測定される、上記熱硬化性樹脂組成物の粘度が５０Ｐａ・ｓ以上５００Ｐａ・ｓ以下である金属／繊維強化プラスチック複合構造体。
［４］
上記［２］または［３］に記載の金属／繊維強化プラスチック複合構造体において、
上記熱硬化性樹脂組成物が、
分子内に２以上のエポキシ基を含むエポキシ樹脂と（メタ）アクリル酸との反応物である（メタ）アクリル変性エポキシ樹脂と、
潜在性硬化剤と、
を含む金属／繊維強化プラスチック複合構造体。
［５］
上記［１］乃至［４］のいずれか一つに記載の金属／繊維強化プラスチック複合構造体において、
上記金属部材が、鉄、ステンレス、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、銅、銅合金、チタンおよびチタン合金から選択される一種または二種以上を含む金属／繊維強化プラスチック複合構造体。
[1]
A metal member;
A fiber reinforced plastic member;
An epoxy resin cured body layer provided between the metal member and the fiber-reinforced plastic member;
With
The metal member has at least a fine concavo-convex shape in which the surface roughness parameter defined in JIS B601 (corresponding international standard: ISO4287) simultaneously satisfies the following requirements a) to c) on the surface of the joint portion with the fiber reinforced plastic member. ,
The epoxy resin cured body layer is formed so as to cover part or all of the fine uneven shape of the metal member,
The metal member and the fiber reinforced plastic member are metal / fiber reinforced plastic composite structures in which the cured epoxy resin layer is joined.
a) The ten-point average roughness (Rz) of the roughness curve is more than 5 μm and not more than 50 μm. b) The arithmetic average roughness (Ra) of the roughness curve is not less than 0.5 μm and not more than 30 μm. c) The roughness curve element The average length (RSm) is 20 μm or more and 300 μm or less [2]
In the metal / fiber reinforced plastic composite structure according to the above [1],
A metal / fiber reinforced plastic composite structure in which the cured epoxy resin layer is composed of a cured product of a thermosetting resin composition containing an epoxy resin and a curing agent.
[3]
In the metal / fiber reinforced plastic composite structure according to the above [2],
A metal / fiber reinforced plastic composite structure in which the viscosity of the thermosetting resin composition is 50 Pa · s or more and 500 Pa · s or less as measured using a B-type viscometer at 23 ° C. and a rotational speed of 0.2 rpm. .
[4]
In the metal / fiber reinforced plastic composite structure according to the above [2] or [3],
The thermosetting resin composition is
A (meth) acryl-modified epoxy resin, which is a reaction product of an epoxy resin containing two or more epoxy groups in the molecule and (meth) acrylic acid,
A latent curing agent;
A metal / fiber reinforced plastic composite structure comprising:
[5]
In the metal / fiber reinforced plastic composite structure according to any one of the above [1] to [4],
A metal / fiber reinforced plastic composite structure in which the metal member includes one or more selected from iron, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, titanium, and titanium alloy.
本発明によれば、接着剤層と繊維強化プラスチック部材との間の界面剥離および金属部材と接着剤層との間の界面剥離が抑制され、接着剤層および／または繊維強化プラスチック部材の母材破壊が主に生じるものであり、かつ、繊維強化プラスチック部材と金属部材との間の接合性に優れた金属／繊維強化プラスチック複合構造体を提供することができる。 According to the present invention, the interfacial delamination between the adhesive layer and the fiber reinforced plastic member and the interfacial delamination between the metal member and the adhesive layer are suppressed, and the base material of the adhesive layer and / or the fiber reinforced plastic member is suppressed. It is possible to provide a metal / fiber reinforced plastic composite structure in which breakage mainly occurs and excellent bondability between the fiber reinforced plastic member and the metal member.
以下に、本発明の実施形態について、図面を用いて説明する。なお、すべての図面において、同様な構成要素には共通の符号を付し、適宜説明を省略する。また、図は概略図であり、実際の寸法比率とは一致していない。文中の数字の間にある「〜」は特に断りがなければ、以上から以下を表す。 Embodiments of the present invention will be described below with reference to the drawings. In all the drawings, similar constituent elements are denoted by common reference numerals, and description thereof is omitted as appropriate. Moreover, the figure is a schematic diagram and does not match the actual dimensional ratio. Unless otherwise specified, “˜” between numbers in the sentence represents the following.
＜金属／繊維強化プラスチック複合構造体＞
まず、本実施形態に係る金属／繊維強化プラスチック複合構造体１０６について説明する。
図１は、本発明に係る実施形態の金属／繊維強化プラスチック複合構造体１０６の構造の一例を示した外観図である。図２は、本発明に係る実施形態の金属／繊維強化プラスチック複合構造体１０６の接合部の構造の一例を概念的に示した断面図である。
本実施形態に係る金属／繊維強化プラスチック複合構造体１０６は、金属部材１０３と、繊維強化プラスチック部材１０５と、金属部材１０３と繊維強化プラスチック部材１０５との間に設けられたエポキシ樹脂硬化体層１０２と、を備える。
そして、金属部材１０３は少なくとも繊維強化プラスチック部材１０５との接合部表面１０４にＪＩＳ Ｂ６０１（対応国際規格：ＩＳＯ４２８７）で規定される表面粗さパラメーターが下記要件ａ）〜ｃ）を同時に満たす微細凹凸形状を有し、エポキシ樹脂硬化体層１０２は金属部材１０３の上記微細凹凸形状の一部または全部を覆うように形成されており、金属部材１０３と繊維強化プラスチック部材１０５とはエポキシ樹脂硬化体層１０２を介して接合している。
ａ）粗さ曲線の十点平均粗さ（Ｒｚ）が５μｍ超５０μｍ以下である
ｂ）粗さ曲線の算術平均粗さ（Ｒａ）が０．５μｍ以上３０μｍ以下である
ｃ）粗さ曲線要素の平均長さ（ＲＳｍ）が２０μｍ以上３００μｍ以下である
<Metal / fiber reinforced plastic composite structure>
First, the metal / fiber reinforced plastic composite structure 106 according to the present embodiment will be described.
FIG. 1 is an external view showing an example of the structure of a metal / fiber reinforced plastic composite structure 106 according to an embodiment of the present invention. FIG. 2 is a cross-sectional view conceptually showing an example of the structure of the joint portion of the metal / fiber reinforced plastic composite structure 106 according to the embodiment of the present invention.
The metal / fiber reinforced plastic composite structure 106 according to this embodiment includes a metal member 103, a fiber reinforced plastic member 105, and a cured epoxy resin layer 102 provided between the metal member 103 and the fiber reinforced plastic member 105. And comprising.
The metal member 103 has a fine uneven shape in which at least the surface roughness parameter defined by JIS B601 (corresponding international standard: ISO4287) satisfies the following requirements a) to c) at least on the joint surface 104 with the fiber reinforced plastic member 105. The cured epoxy resin layer 102 is formed so as to cover part or all of the fine uneven shape of the metal member 103, and the metal member 103 and the fiber reinforced plastic member 105 are composed of the cured epoxy resin layer 102. It is joined via.
a) The ten-point average roughness (Rz) of the roughness curve is more than 5 μm and not more than 50 μm. b) The arithmetic average roughness (Ra) of the roughness curve is not less than 0.5 μm and not more than 30 μm. c) The roughness curve element The average length (RSm) is 20 μm or more and 300 μm or less
また、本実施形態に係る金属／繊維強化プラスチック複合構造体１０６は、上記微細凹凸形状にエポキシ樹脂硬化体層１０２の一部分が浸入することにより金属部材１０３とエポキシ樹脂硬化体層１０２とが接合されていることが好ましい。 Further, in the metal / fiber reinforced plastic composite structure 106 according to the present embodiment, the metal member 103 and the epoxy resin cured body layer 102 are joined by part of the epoxy resin cured body layer 102 entering the fine concavo-convex shape. It is preferable.
本実施形態に係る金属部材１０３は、エポキシ樹脂硬化体層１０２との接合部表面１０４に微細凹凸形状を有している。上記微細凹凸形状に、エポキシ樹脂硬化体層１０２の加熱硬化前の熱硬化性エポキシ樹脂組成物を接触させることによって、該組成物の一部分を微細凹凸形状の凹部に十分に浸入させることが可能となる。次いで、熱硬化性エポキシ樹脂組成物からなる層の、金属部材１０３側の面とは対向する面側に繊維強化プラスチック部材１０５をセットし、熱硬化性エポキシ樹脂組成物を熱硬化（三次元架橋）することによって金属部材１０３とエポキシ樹脂硬化体層１０２、およびエポキシ樹脂硬化体層１０２と繊維強化プラスチック部材１０５と、が強固に接合した金属／繊維強化プラスチック複合構造体１０６を得ることができる。 The metal member 103 according to the present embodiment has a fine concavo-convex shape on the joint surface 104 with the cured epoxy resin layer 102. By bringing the thermosetting epoxy resin composition before the heat curing of the epoxy resin cured body layer 102 into contact with the fine concavo-convex shape, a part of the composition can be sufficiently infiltrated into the concave portions of the fine concavo-convex shape. Become. Next, the fiber reinforced plastic member 105 is set on the surface of the layer made of the thermosetting epoxy resin composition opposite to the surface on the metal member 103 side, and the thermosetting epoxy resin composition is thermoset (three-dimensionally crosslinked). ), A metal / fiber reinforced plastic composite structure 106 in which the metal member 103 and the epoxy resin cured body layer 102 and the epoxy resin cured body layer 102 and the fiber reinforced plastic member 105 are firmly bonded can be obtained.
本実施形態においては、金属部材１０３とエポキシ樹脂硬化体層１０２との間に物理的な抵抗力（アンカー効果）が効果的に発現し、金属部材１０３とエポキシ樹脂硬化体層１０２とが強固に接合している。本実施形態においては、アンカー効果を効果的に発現させるために、金属部材１０３の上に形成された微細凹凸形状の具体的構造は重要な要件となる。 In the present embodiment, physical resistance (anchor effect) is effectively expressed between the metal member 103 and the cured epoxy resin layer 102, and the metal member 103 and the cured epoxy resin layer 102 are firmly formed. It is joined. In the present embodiment, in order to effectively develop the anchor effect, the specific structure of the fine concavo-convex shape formed on the metal member 103 is an important requirement.
本実施形態に係る金属部材１０３は、少なくとも繊維強化プラスチック部材１０５との接合部表面１０４に微細凹凸形状を有しており、該微細凹凸形状のＪＩＳ Ｂ６０１（対応国際規格：ＩＳＯ４２８７）で規定される表面粗さパラメーターが下記要件ａ）、ｂ）およびｃ）を同時に満たすことを特徴としている。
ａ）粗さ曲線の十点平均粗さ（Ｒｚ）が５μｍ超５０μｍ以下であり、好ましくは１０μｍ以上５０μｍ以下であり、より好ましくは１５μｍ以上４０μｍ以下である。
ｂ）粗さ曲線の算術平均粗さ（Ｒａ）が０．５μｍ以上３０μｍ以下であり、好ましくは２μｍ以上２０μｍ以下であり、より好ましくは３μｍ以上１５μｍ以下である。
ｃ）粗さ曲線要素の平均長さ（ＲＳｍ）が２０μｍ以上３００μｍ以下であり、好ましくは３０μｍ以上２５０μｍ以下であり、より好ましくは４０μｍ以上２００μｍ以下である。
金属部材１０３上に形成された微細凹凸形状が上記のような要件を満たすことによって、金属部材１０３と、接着層としてのエポキシ樹脂硬化体層１０２との間にアンカー効果が効果的に発現し、結果として接合強度に優れた金属／繊維強化プラスチック複合構造体１０６を実現できる。なお、表面にこのような形状特性を備えた金属部材１０３は、後述するように、金属部材１０３の表面に対する粗化処理の条件を適切に調整することによって制御が可能である。
The metal member 103 according to the present embodiment has a fine concavo-convex shape at least on the joint surface 104 with the fiber reinforced plastic member 105, and is defined by JIS B601 (corresponding international standard: ISO4287) having the fine concavo-convex shape. The surface roughness parameter satisfies the following requirements a), b) and c) simultaneously.
a) The ten-point average roughness (Rz) of the roughness curve is more than 5 μm and 50 μm or less, preferably 10 μm or more and 50 μm or less, more preferably 15 μm or more and 40 μm or less.
b) The arithmetic mean roughness (Ra) of the roughness curve is 0.5 μm or more and 30 μm or less, preferably 2 μm or more and 20 μm or less, more preferably 3 μm or more and 15 μm or less.
c) The average length (RSm) of the roughness curve element is 20 μm or more and 300 μm or less, preferably 30 μm or more and 250 μm or less, more preferably 40 μm or more and 200 μm or less.
When the fine concavo-convex shape formed on the metal member 103 satisfies the above requirements, an anchor effect is effectively expressed between the metal member 103 and the cured epoxy resin layer 102 as an adhesive layer, As a result, the metal / fiber reinforced plastic composite structure 106 having excellent bonding strength can be realized. Note that the metal member 103 having such shape characteristics on the surface can be controlled by appropriately adjusting the conditions of the roughening treatment on the surface of the metal member 103 as described later.
以下、本実施形態に係る金属／繊維強化プラスチック複合構造体１０６を構成する各部材について説明する。
＜繊維強化プラスチック部材＞
以下、本実施形態に係る繊維強化プラスチック部材１０５について説明する。
本実施形態に係る繊維強化プラスチック部材１０５は繊維強化プラスチックにより構成される部材であれば特に限定されないが、強化材料である繊維とマトリックス樹脂である熱硬化性樹脂とから得られる熱硬化体、強化材料である繊維とマトリックス樹脂である熱可塑性樹脂とから得られる部材等が挙げられる。
本実施形態に係る金属／繊維強化プラスチック複合構造体１０６においては、繊維強化プラスチック部材１０５と金属部材１０３がエポキシ樹脂硬化体層１０２を介して接合されるので、繊維強化プラスチック部材１０５を構成するマトリックス樹脂としてはエポキシ樹脂硬化体層１０２に近い物理特性を示す熱硬化性樹脂、特にエポキシ樹脂系の熱硬化性樹脂であることが好ましい。
Hereinafter, each member constituting the metal / fiber reinforced plastic composite structure 106 according to the present embodiment will be described.
<Fiber-reinforced plastic parts>
Hereinafter, the fiber reinforced plastic member 105 according to the present embodiment will be described.
The fiber-reinforced plastic member 105 according to the present embodiment is not particularly limited as long as it is a member made of fiber-reinforced plastic, but is a thermoset obtained from a fiber that is a reinforcing material and a thermosetting resin that is a matrix resin. Examples thereof include a member obtained from a fiber as a material and a thermoplastic resin as a matrix resin.
In the metal / fiber reinforced plastic composite structure 106 according to the present embodiment, since the fiber reinforced plastic member 105 and the metal member 103 are joined via the epoxy resin cured body layer 102, the matrix constituting the fiber reinforced plastic member 105. The resin is preferably a thermosetting resin exhibiting physical properties close to those of the cured epoxy resin layer 102, particularly an epoxy resin thermosetting resin.
繊維強化プラスチック部材１０５を構成する繊維としては繊維強化プラスチックに用いられる繊維であれば特に限定されないが、例えば、炭素繊維、ガラス繊維、ボロン繊維、アラミド繊維、ポリエチレン繊維、ポリ（パラフェニレンベンゾビスオキサゾール）繊維等が挙げられる。これらの中でも炭素繊維が好ましい。ここで、繊維強化プラスチック部材１０５を構成する繊維が炭素繊維の場合、繊維強化プラスチックは炭素繊維強化プラスチック（ＣＦＲＰ）とも呼ぶ。ＣＦＲＰを構成する炭素繊維としては、原料がアクリルニトリル樹脂であるＰＡＮ系、コールタール等の炭素が原料のピッチ系等が挙げられる。
また、繊維形状は長繊維、短繊維いずれも使用可能であり、繊維径は通常３〜３０μｍ程度である。また繊維強化プラスチックの形態としては、例えば、クロス、ステーブルヤーン、ストランドシート、トウ、トウプレート、フェルマット、プリプレグ、ＵＤプリプレグ、プリプレグ積層体、ブレード、ロービング等が挙げられる。
The fiber constituting the fiber reinforced plastic member 105 is not particularly limited as long as it is a fiber used for fiber reinforced plastic. For example, carbon fiber, glass fiber, boron fiber, aramid fiber, polyethylene fiber, poly (paraphenylenebenzobisoxazole) ) Fiber and the like. Among these, carbon fiber is preferable. Here, when the fiber constituting the fiber reinforced plastic member 105 is carbon fiber, the fiber reinforced plastic is also called carbon fiber reinforced plastic (CFRP). Examples of the carbon fiber constituting the CFRP include PAN-based materials whose raw material is acrylonitrile resin, pitch-based carbon materials such as coal tar, and the like.
Moreover, as for the fiber shape, both long fibers and short fibers can be used, and the fiber diameter is usually about 3 to 30 μm. Examples of the form of fiber reinforced plastic include cloth, stable yarn, strand sheet, tow, tow plate, fermat, prepreg, UD prepreg, prepreg laminate, blade, and roving.
＜金属部材＞
本実施形態に係る金属／繊維強化プラスチック複合構造体１０６を構成する金属部材１０３は特に限定されないが、例えば、鉄、ステンレス、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、銅、銅合金、チタンおよびチタン合金等を挙げることができる。これらは単独で使用してもよいし、二種以上組み合わせて使用してもよい。これらの中でも、軽量かつ高強度の点から、アルミニウム（アルミニウム単体）およびアルミニウム合金が好ましく、アルミニウム合金がより好ましい。
アルミニウム合金としては、これらの中でも展伸法に利用されるものである、日本工業規格（ＪＩＳ Ｈ４０００）で定義される合金種を示す４桁の数字が、２０００番台のアルミニウム／銅系合金、３０００番台のアルミニウム／マンガン系合金、４０００番台のアルミニウム／ケイ素系合金、５０００番台のアルミニウム／マグネシウム系合金、６０００番台のアルミニウム／マグネシウム／ケイ素系合金、７０００番台のアルミニウム／亜鉛／マグネシウム系合金、アルミニウム／亜鉛／マグネシウム／銅系合金等が好適に用いられる。これらの中でも、入手容易性や複合体とした場合の機械・熱特性の視点から５０００番台のアルミニウム／マグネシウム合金が特に好んで用いられる。
<Metal member>
The metal member 103 constituting the metal / fiber reinforced plastic composite structure 106 according to the present embodiment is not particularly limited. For example, iron, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, titanium, and titanium are used. An alloy etc. can be mentioned. These may be used alone or in combination of two or more. Among these, aluminum (aluminum simple substance) and aluminum alloy are preferable from the viewpoint of light weight and high strength, and aluminum alloy is more preferable.
Among these aluminum alloys, a 4-digit number indicating an alloy type defined in the Japanese Industrial Standard (JIS H4000), which is used for the extension method, is an aluminum / copper alloy in the 2000s, 3000 A series of aluminum / manganese alloys, 4000 series aluminum / silicon alloys, 5000 series aluminum / magnesium alloys, 6000 series aluminum / magnesium / silicon alloys, 7000 series aluminum / zinc / magnesium alloys, aluminum / Zinc / magnesium / copper alloys are preferably used. Among these, aluminum / magnesium alloys in the 5000s are particularly preferred from the viewpoint of availability and mechanical / thermal properties when composites are used.
金属部材１０３の形状は、エポキシ樹脂硬化体層１０２を介して繊維強化プラスチック部材１０５と接合できる形状であれば特に限定されず、例えば、平板状、曲板状、棒状、筒状、塊状等とすることができる。また、これらの組み合わせからなる構造体であってもよい。
また、繊維強化プラスチック部材１０５と接合する金属部材１０３の接合部表面１０４の形状は、特に限定されないが、平面、曲面等が挙げられる。
The shape of the metal member 103 is not particularly limited as long as it is a shape that can be bonded to the fiber reinforced plastic member 105 via the epoxy resin cured body layer 102. For example, a flat plate shape, a curved plate shape, a rod shape, a cylindrical shape, a lump shape, and the like can do. Moreover, the structure which consists of these combination may be sufficient.
Further, the shape of the joint surface 104 of the metal member 103 joined to the fiber reinforced plastic member 105 is not particularly limited, and examples thereof include a flat surface and a curved surface.
金属部材１０３は、金属材料を切断、プレス等による塑性加工、打ち抜き加工、切削、研磨、放電加工等の除肉加工によって上述した所定の形状に加工された後に、後述する粗化処理がなされたものが好ましい。要するに、種々の加工法により、必要な形状に加工されたものを用いることが好ましい。 The metal member 103 was processed into a predetermined shape as described above by metal removal such as cutting, pressing, etc., metal processing, punching, cutting, polishing, electric discharge processing, etc., and then the roughening process described later was performed. Those are preferred. In short, it is preferable to use a material processed into a necessary shape by various processing methods.
（金属部材表面の粗化処理方法）
金属部材１０３に設けられた微細凹凸形状は、金属部材１０３の全表面に設けられてもよいし、片面のみであってもよいし、片面の一部分のみであってもよし、エポキシ樹脂硬化体層１０２を介した繊維強化プラスチック部材１０５との接合面のみであってもよい。ここで微細凹凸形状を付与する方法は、本実施形態に係る微細凹凸形状が上記要件ａ）、ｂ）およびｃ）を同時に満たす限りは、公知の方法が制限なく用いられる。公知方法としては、得られる微細凹凸形状の三次元構造から大別して、侵食性水溶液または侵食性懸濁液に金属部材を浸漬する方法（エッチング剤法）、陽極酸化法、および機械的切削法が挙げられるが、これらの中では、大量処理の視点からエッチング剤法が好ましい。
(Roughening method of metal member surface)
The fine concavo-convex shape provided on the metal member 103 may be provided on the entire surface of the metal member 103, or may be only on one side or only on a part of one side. Only the joint surface with the fiber reinforced plastic member 105 via 102 may be sufficient. Here, as a method for providing the fine uneven shape, a known method can be used without limitation as long as the fine uneven shape according to the present embodiment satisfies the requirements a), b) and c) at the same time. Known methods are roughly classified from the obtained three-dimensional structure of fine irregularities, and include a method of immersing a metal member in an erosive aqueous solution or erosive suspension (etching method), an anodic oxidation method, and a mechanical cutting method. Among these, the etching method is preferable from the viewpoint of mass processing.
ここで、エッチング剤を用いて金属部材の表面を粗化処理すること自体は従来技術においても盛んに行われてきた。しかし、本実施形態では、エッチング剤の種類および濃度、粗化処理の温度および時間、エッチング処理のタイミング等の因子を高度に制御している。本実施形態に係る金属部材１０３の接合部表面１０４を得るためには、これらの因子を高度に制御することが重要となる。
以下、本実施形態に係る金属部材表面の粗化処理方法の一例を示す。ただし、本実施形態に係る金属部材表面の粗化処理方法は、以下の例に限定されない。
Here, roughening the surface of the metal member using an etching agent has been actively performed in the prior art. However, in this embodiment, factors such as the type and concentration of the etching agent, the temperature and time of the roughening process, and the timing of the etching process are highly controlled. In order to obtain the joint surface 104 of the metal member 103 according to the present embodiment, it is important to highly control these factors.
Hereinafter, an example of the roughening method of the metal member surface which concerns on this embodiment is shown. However, the roughening method of the metal member surface which concerns on this embodiment is not limited to the following examples.
（１）前処理工程
まず、金属部材１０３は、繊維強化プラスチック部材１０５との接合側の表面に酸化膜や水酸化物等からなる厚い被膜がないことが望ましい。このような厚い被膜を除去するため、次のエッチング剤で処理する工程の前に、サンドブラスト加工、ショットブラスト加工、研削加工、バレル加工等の機械研磨や、化学研磨により表面層を研磨してもよい。また、繊維強化プラスチック部材１０５との接合側の表面に機械油等の著しい汚染がある場合は、水酸化ナトリウム水溶液や水酸化カリウム水溶液等のアルカリ性水溶液による処理や、脱脂を行なうことが好ましい。
(1) Pretreatment process First, it is desirable that the metal member 103 does not have a thick film made of an oxide film, a hydroxide, or the like on the surface on the joint side with the fiber reinforced plastic member 105. In order to remove such a thick film, the surface layer may be polished by mechanical polishing such as sand blasting, shot blasting, grinding, barrel processing, or chemical polishing before the next etching step. Good. Further, when there is significant contamination of machine oil or the like on the surface on the joint side with the fiber reinforced plastic member 105, it is preferable to perform treatment with an alkaline aqueous solution such as a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, or degreasing.
（２）表面粗化処理工程
本実施形態において金属部材の表面粗化処理方法としては、後述する酸系エッチング剤による処理を特定のタイミングで行うことが好ましい。具体的には、該酸系エッチング剤による処理を表面粗化処理工程の最終段階で行うことが好ましい。
上記酸系エッチング剤を用いて粗化処理する方法としては、浸漬、スプレー等による処理方法が挙げられる。処理温度は２０〜４０℃が好ましく、処理時間は５〜３５０秒程度が好ましく、金属部材表面をより均一に粗化できる観点から、２０〜３００秒がより好ましく、５０〜３００秒が特に好ましい。
(2) Surface roughening treatment process In this embodiment, as a surface roughening treatment method of a metal member, it is preferable to perform the process by the acid type etching agent mentioned later at a specific timing. Specifically, the treatment with the acid-based etching agent is preferably performed at the final stage of the surface roughening treatment step.
Examples of the roughening treatment using the acid-based etching agent include treatment methods such as immersion and spraying. The treatment temperature is preferably 20 to 40 ° C., the treatment time is preferably about 5 to 350 seconds, 20 to 300 seconds are more preferred, and 50 to 300 seconds are particularly preferred from the viewpoint that the surface of the metal member can be more uniformly roughened.
上記酸系エッチング剤を用いた粗化処理によって、金属部材１０３の表面が凹凸形状に粗化される。上記酸系エッチング剤を用いた際の金属部材１０３の深さ方向のエッチング量（溶解量）は、溶解した金属部材１０３の質量、比重および表面積から算出した場合、０．１〜５００μｍであることが好ましく、５〜５００μｍであることがより好ましく、５〜１００μｍであることがさらに好ましい。エッチング量が上記下限値以上であれば、金属部材１０３とエポキシ樹脂硬化体層１０２との間の接合強度をより向上させることができる。また、エッチング量が上記上限値以下であれば、処理コストの低減が可能となる。エッチング量は、処理温度や処理時間等により調整できる。
上記酸系エッチング剤は、第二鉄イオンおよび第二銅イオンの少なくとも一方と、酸と、を含み、必要に応じて、マンガンイオン、各種添加剤等を含むことができる。
By the roughening treatment using the acid-based etching agent, the surface of the metal member 103 is roughened into an uneven shape. The etching amount (dissolution amount) in the depth direction of the metal member 103 when using the acid-based etching agent is 0.1 to 500 μm when calculated from the mass, specific gravity and surface area of the dissolved metal member 103. Is more preferable, it is more preferable that it is 5-500 micrometers, and it is further more preferable that it is 5-100 micrometers. When the etching amount is equal to or higher than the lower limit, the bonding strength between the metal member 103 and the cured epoxy resin layer 102 can be further improved. Further, if the etching amount is equal to or less than the above upper limit value, the processing cost can be reduced. The etching amount can be adjusted by the processing temperature, processing time, and the like.
The acid-based etching agent contains at least one of ferric ions and cupric ions and an acid, and may contain manganese ions, various additives, and the like as necessary.
・第二鉄イオン
上記第二鉄イオンは、金属部材を酸化する成分であり、第二鉄イオン源を配合することによって、酸系エッチング剤中に該第二鉄イオンを含有させることができる。上記第二鉄イオン源としては、硝酸第二鉄、硫酸第二鉄、塩化第二鉄等が挙げられる。上記第二鉄イオン源のうちでは、塩化第二鉄が溶解性に優れ、安価であるという点から好ましい。
-Ferric ion The said ferric ion is a component which oxidizes a metal member, and this ferric ion can be contained in an acid type etching agent by mix | blending a ferric ion source. Examples of the ferric ion source include ferric nitrate, ferric sulfate, and ferric chloride. Among the ferric ion sources, ferric chloride is preferable because it has excellent solubility and is inexpensive.
本実施形態において、酸系エッチング剤中の上記第二鉄イオンの含有量は、好ましくは０．０１〜２０質量％、より好ましくは０．１〜１２質量％、さらに好ましくは０．５〜７質量％、さらにより好ましくは１〜６質量％、特に好ましくは１〜５質量％である。上記第二鉄イオンの含有量が上記下限値以上であれば、金属部材の粗化速度（溶解速度）の低下を防ぐことができる。一方、上記第二鉄イオンの含有量が上記上限値以下であれば、粗化速度を適正に維持することができるため、金属部材１０３と繊維強化プラスチック部材１０５との間の接合強度向上により適した均一な粗化が可能になる。 In this embodiment, content of the said ferric ion in an acid type etching agent becomes like this. Preferably it is 0.01-20 mass%, More preferably, it is 0.1-12 mass%, More preferably, it is 0.5-7 % By mass, still more preferably 1-6% by mass, particularly preferably 1-5% by mass. If content of the said ferric ion is more than the said lower limit, the fall of the roughening rate (dissolution rate) of a metal member can be prevented. On the other hand, if the content of the ferric ion is less than or equal to the above upper limit value, the roughening rate can be maintained appropriately, and thus more suitable for improving the bonding strength between the metal member 103 and the fiber reinforced plastic member 105. Uniform roughening becomes possible.
・第二銅イオン
上記第二銅イオンは金属部材を酸化する成分であり、第二銅イオン源を配合することによって、酸系エッチング剤中に該第二銅イオン含有させることができる。上記第二銅イオン源としては、硫酸第二銅、塩化第二銅、硝酸第二銅、水酸化第二銅等が挙げられる。上記第二銅イオン源のうちでは、硫酸第二銅、塩化第二銅が安価であるという点から好ましい。
-Cupric ion The said cupric ion is a component which oxidizes a metal member, and can mix | blend this cupric ion in an acid type etching agent by mix | blending a cupric ion source. Examples of the cupric ion source include cupric sulfate, cupric chloride, cupric nitrate, and cupric hydroxide. Of the cupric ion sources, cupric sulfate and cupric chloride are preferred because they are inexpensive.
本実施形態において、酸系エッチング剤中の上記第二銅イオンの含有量は、０．００１〜１０質量％であることが好ましく、より好ましくは０．０１〜７質量％、さらに好ましくは０．０５〜１質量％、さらにより好ましくは０．１〜０．８質量％、さらにより好ましくは０．１５〜０．７質量％、特に好ましくは０．１５〜０．４質量％である。上記第二銅イオンの含有量が上記下限値以上であれば、金属部材の粗化速度（溶解速度）の低下を防ぐことができる。一方、上記第二銅イオンの含有量が上記上限値以下であれば、粗化速度を適正に維持することができるため、金属部材１０３と繊維強化プラスチック部材１０５との間の接合強度向上により適した均一な粗化が可能になる。 In this embodiment, it is preferable that content of the said cupric ion in an acid type etching agent is 0.001-10 mass%, More preferably, it is 0.01-7 mass%, More preferably, it is 0.00. It is 05-1 mass%, More preferably, it is 0.1-0.8 mass%, More preferably, it is 0.15-0.7 mass%, Most preferably, it is 0.15-0.4 mass%. If content of the said cupric ion is more than the said lower limit, the fall of the roughening rate (dissolution rate) of a metal member can be prevented. On the other hand, if the content of the cupric ion is less than or equal to the above upper limit value, the roughening rate can be maintained appropriately, so that the bonding strength between the metal member 103 and the fiber reinforced plastic member 105 is improved. Uniform roughening becomes possible.
上記酸系エッチング剤は、第二鉄イオンおよび第二銅イオンの一方のみを含むものであってもよく、両方を含むものであってもよいが、第二鉄イオンおよび第二銅イオンの両方を含むことが好ましい。酸系エッチング剤が第二鉄イオンおよび第二銅イオンの両方を含むことで、金属部材１０３と繊維強化プラスチック部材１０５との間の接合強度向上により適した良好な粗化形状が容易に得られる。 The acid-based etching agent may contain only one of ferric ion and cupric ion, or may contain both, but both ferric ion and cupric ion It is preferable to contain. By including both the ferric ion and the cupric ion in the acid-based etching agent, a good roughened shape suitable for improving the bonding strength between the metal member 103 and the fiber reinforced plastic member 105 can be easily obtained. .
上記酸系エッチング剤が、第二鉄イオンおよび第二銅イオンの両方を含む場合、第二鉄イオンおよび第二銅イオンのそれぞれの含有量が、上記範囲であることが好ましい。また、酸系エッチング剤中の第二鉄イオンと第二銅イオンの含有量の合計は、０．０１１〜２０質量％であることが好ましく、より好ましくは０．１〜１５質量％、さらに好ましくは０．５〜１０質量％、特に好ましくは１〜５質量％である。 When the acid-based etching agent contains both ferric ions and cupric ions, the contents of ferric ions and cupric ions are preferably in the above ranges. The total content of ferric ions and cupric ions in the acid-based etching agent is preferably 0.011 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably. Is 0.5 to 10% by mass, particularly preferably 1 to 5% by mass.
・マンガンイオン
上記酸系エッチング剤には、金属部材表面をむらなく一様に粗化するために、マンガンイオンが含まれていてもよい。マンガンイオンは、マンガンイオン源を配合することによって、酸系エッチング剤中に該マンガンイオンを含有させることができる。上記マンガンイオン源としては、硫酸マンガン、塩化マンガン、酢酸マンガン、フッ化マンガン、硝酸マンガン等が挙げられる。上記マンガンイオン源の中でも、硫酸マンガン、塩化マンガンが安価である等の点から好ましい。本実施形態において、酸系エッチング剤中の上記マンガンイオンの含有量は、０〜１質量％であることが好ましく、より好ましくは０〜０．５質量％である。
Manganese ions The acid-based etching agent may contain manganese ions in order to uniformly roughen the surface of the metal member. Manganese ions can be contained in the acid-based etching agent by blending a manganese ion source. Examples of the manganese ion source include manganese sulfate, manganese chloride, manganese acetate, manganese fluoride, and manganese nitrate. Among the above manganese ion sources, manganese sulfate and manganese chloride are preferable because they are inexpensive. In this embodiment, it is preferable that content of the said manganese ion in an acid type etching agent is 0-1 mass%, More preferably, it is 0-0.5 mass%.
・酸
上記酸は、第二鉄イオンおよび／または第二銅イオンにより酸化された金属を溶解させる成分である。上記酸としては、塩酸、臭化水素酸、硫酸、硝酸、リン酸、過塩素酸、スルファミン酸等の無機酸や、スルホン酸、カルボン酸等の有機酸が挙げられる。上記カルボン酸としては、ギ酸、酢酸、クエン酸、シュウ酸、リンゴ酸等が挙げられる。上記酸系エッチング剤には、これらの酸を一種または二種以上配合することができる。上記無機酸のうちでは、臭気がほとんどなく、安価である点から硫酸が好ましい。また、上記有機酸のうちでは、粗化形状の均一性の観点から、カルボン酸が好ましい。
-Acid The acid is a component that dissolves a metal oxidized by ferric ions and / or cupric ions. Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, and sulfamic acid, and organic acids such as sulfonic acid and carboxylic acid. Examples of the carboxylic acid include formic acid, acetic acid, citric acid, oxalic acid, malic acid and the like. One or more of these acids can be added to the acid-based etching agent. Of the inorganic acids, sulfuric acid is preferred because it has almost no odor and is inexpensive. Among the organic acids, carboxylic acid is preferable from the viewpoint of uniformity of the roughened shape.
本実施形態において、酸系エッチング剤中の上記酸の含有量は、０．１〜５０質量％であることが好ましく、０．５〜５０質量％であることがより好ましく、１〜５０質量％であることがさらに好ましく、１〜３０質量％であることがさらにより好ましく、１〜２５質量％であることがさらにより好ましく、２〜１８質量％であることがさらにより好ましい。上記酸の含有量が上記下限値以上であれば、金属の粗化速度（溶解速度）の低下を防止できる。一方、上記酸の含有量が上記上限値以下であれば、液温が低下した際の金属塩の結晶析出を防止できるため、作業性を向上できる。 In the present embodiment, the acid content in the acid-based etching agent is preferably 0.1 to 50% by mass, more preferably 0.5 to 50% by mass, and 1 to 50% by mass. It is still more preferable, it is still more preferable that it is 1-30 mass%, it is still more preferable that it is 1-25 mass%, and it is still more preferable that it is 2-18 mass%. If content of the said acid is more than the said lower limit, the fall of the metal roughening rate (dissolution rate) can be prevented. On the other hand, if the content of the acid is not more than the upper limit, it is possible to prevent crystal precipitation of the metal salt when the liquid temperature is lowered, so that workability can be improved.
・他の成分
本実施形態において使用できる酸系エッチング剤には、指紋等の表面汚染物による粗化のむらを防ぐために界面活性剤を添加してもよく、必要に応じて他の添加剤を添加してもよい。他の添加剤としては、深い凹凸を形成するために添加されるハロゲン化物イオン源、例えば、塩化ナトリウム、塩化カリウム、臭化ナトリウム、臭化カリウム等を例示できる。あるいは、粗化処理速度を上げるために添加されるチオ硫酸イオン、チオ尿素等のチオ化合物や、より均一な粗化形状を得るために添加されるイミダゾール、トリアゾール、テトラゾール等のアゾール類や、粗化反応を制御するために添加されるｐＨ調整剤等も例示できる。これら他の成分を添加する場合、その合計含有量は、酸系エッチング剤中に０．０１〜１０質量％程度であることが好ましい。本実施形態の酸系エッチング剤は、上記の各成分をイオン交換水等に溶解させることにより容易に調製することができる。
Other components To the acid-based etching agent that can be used in the present embodiment, a surfactant may be added to prevent unevenness due to surface contaminants such as fingerprints, and other additives may be added as necessary. May be. Other additives include halide ion sources added to form deep irregularities, such as sodium chloride, potassium chloride, sodium bromide, potassium bromide and the like. Alternatively, thio compounds such as thiosulfate ions and thiourea added to increase the roughening treatment speed, azoles such as imidazole, triazole and tetrazole added to obtain a more uniform roughened shape, Examples thereof include a pH adjuster added to control the oxidization reaction. When these other components are added, the total content is preferably about 0.01 to 10% by mass in the acid-based etching agent. The acid-based etching agent of this embodiment can be easily prepared by dissolving each of the above components in ion-exchanged water or the like.
（３）後処理工程
本実施形態では、上記表面粗化処理工程の後、通常、水洗および乾燥を行うことが好ましい。水洗の方法については特に制限はないが浸漬または流水にて所定時間洗浄することが好ましい。
(3) Post-treatment step In this embodiment, it is usually preferable to perform washing and drying after the surface roughening treatment step. Although there is no restriction | limiting in particular about the method of water washing, It is preferable to wash | clean for predetermined time with immersion or flowing water.
さらに、後処理工程としては、上記酸系エッチング剤を用いた処理により生じたスマット等を除去するため、超音波洗浄を施すことが好ましい。超音波洗浄の条件は、生じたスマット等を除去することができる条件であれば特に限定されないが、用いる溶媒としては水が好ましく、また、処理時間としては、好ましくは１〜２０分間である。 Furthermore, as a post-treatment step, it is preferable to perform ultrasonic cleaning in order to remove smut and the like generated by the treatment using the acid-based etching agent. The ultrasonic cleaning conditions are not particularly limited as long as the generated smut and the like can be removed, but the solvent used is preferably water, and the treatment time is preferably 1 to 20 minutes.
＜エポキシ樹脂硬化体層＞
本実施形態に係るエポキシ樹脂硬化体層１０２は、例えば、エポキシ樹脂と硬化剤とを含む熱硬化性樹脂組成物を熱硬化することにより得ることができる。すなわち、本実施形態に係るエポキシ樹脂硬化体層１０２は、例えば、エポキシ樹脂と硬化剤とを含む熱硬化性樹脂組成物の硬化物により構成される。
エポキシ樹脂硬化体層１０２の厚みは特に限定されないが、１０μｍ以上１０００μｍ以下が好ましく、５０μｍ以上８００μｍ以下がより好ましい。
エポキシ樹脂としては特に限定されないが、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、２，２’−ジアリルビスフェノールＡ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂および水添ビスフェノール型等のビスフェノール型エポキシ樹脂；ジフェニルエーテル型エポキシ樹脂；フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ビフェニルノボラック型エポキシ樹脂、ビスフェノールノボラック型エポキシ樹脂、ナフトールノボラック型エポキシ樹脂、トリスフェノールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；ビフェニル型エポキシ樹脂；ナフチル型エポキシ樹脂；トリフェノールメタン型エポキシ樹脂、トリフェノールエタン型エポキシ樹脂、トリフェノールプロパン型エポキシ樹脂等のトリフェノールアルカン型エポキシ樹脂；脂環型エポキシ樹脂等が含まれる。
<Hardened epoxy resin layer>
The cured epoxy resin layer 102 according to the present embodiment can be obtained, for example, by thermally curing a thermosetting resin composition containing an epoxy resin and a curing agent. That is, the epoxy resin cured body layer 102 according to the present embodiment is constituted by a cured product of a thermosetting resin composition including, for example, an epoxy resin and a curing agent.
The thickness of the cured epoxy resin layer 102 is not particularly limited, but is preferably 10 μm or more and 1000 μm or less, and more preferably 50 μm or more and 800 μm or less.
Although it does not specifically limit as an epoxy resin, For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, 2,2'-diallyl bisphenol A type epoxy resin, bisphenol AD type epoxy resin, and hydrogenated bisphenol Type bisphenol type epoxy resin; diphenyl ether type epoxy resin; phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthol novolak type epoxy resin, trisphenol novolak type epoxy resin, Novolak epoxy resin such as dicyclopentadiene novolac epoxy resin; biphenyl epoxy resin; naphthyl epoxy resin A triphenolalkane type epoxy resin such as a triphenolmethane type epoxy resin, a triphenolethane type epoxy resin, or a triphenolpropane type epoxy resin; and an alicyclic epoxy resin.
これらの中でも、分子内に２以上のエポキシ基を含むエポキシ樹脂が好ましく、ビスフェノールＡ型エポキシ樹脂およびビスフェノールＦ型エポキシ樹脂等のビスフェノール型エポキシ樹脂がより好ましい。これらのビスフェノール型エポキシ樹脂は、ジフェニルエーテル型エポキシ樹脂等と比べて結晶性が低いため、塗布性や粘度安定性に優れる等の利点があるからである。 Among these, epoxy resins containing two or more epoxy groups in the molecule are preferable, and bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin are more preferable. This is because these bisphenol-type epoxy resins have advantages such as excellent applicability and viscosity stability because they have lower crystallinity than diphenyl ether-type epoxy resins and the like.
また、上記エポキシ樹脂は、例えば、活性水素含有化合物によってエポキシ環の一部が開環、すなわち部分変性されていてもよい。変性されている場合は、その変性率は、変性前のエポキシ基量の例えば５０モル％〜１００モル％、好ましくは６０モル％〜９９モル％である。変性剤としての活性水素化合物としては、カルボキシル基含有化合物、フェノール性水酸基含有化合物、アンモニア、一級アミノ基含有化合物、二級アミノ基含有化合物、メルカプト基含有化合物を例示できる。 Further, in the epoxy resin, for example, a part of the epoxy ring may be opened, that is, partially modified by an active hydrogen-containing compound. In the case of modification, the modification rate is, for example, 50 mol% to 100 mol%, preferably 60 mol% to 99 mol% of the amount of epoxy groups before modification. Examples of the active hydrogen compound as the modifier include a carboxyl group-containing compound, a phenolic hydroxyl group-containing compound, ammonia, a primary amino group-containing compound, a secondary amino group-containing compound, and a mercapto group-containing compound.
本実施形態に係る熱硬化性樹脂組成物においては、熱硬化によって得られる硬化体に靱性が付与できること、部分変性時の反応制御が相対的に容易であること、および部分変性エポキシ樹脂がビニル系ポリマーへのグラフト鎖として活用できるという変性自由度が格段に向上できる等の理由によってカルボキシル基含有化合物としての（メタ）アクリル酸を変性剤として用いることが好ましい。
（メタ）アクリル酸を変性剤として用いて得られる（メタ）アクリル変性エポキシ樹脂の（メタ）アクリレート基の二重結合部分は、必要に応じて他のビニルモノマーがグラフト重合されていてもよい。他のビニルモノマーとしては、スチレン等のアルケニル芳香族類、メチルメタクリレート（ＭＭＡ）等のアクリルエステル類、アクリル酸等のエステル基不含のアクリル化合物、ビニリアセテート等の非共役性ビニル化合物、ブタジエン等の共役ジエン化合物を例示することができる。この際のグラフト重合においては、触媒として公知のラジカル開始剤が用いられる。
In the thermosetting resin composition according to the present embodiment, toughness can be imparted to a cured product obtained by thermosetting, reaction control during partial modification is relatively easy, and the partially modified epoxy resin is a vinyl-based resin. It is preferable to use (meth) acrylic acid as a carboxyl group-containing compound as a modifying agent for the reason that the degree of modification freedom that can be utilized as a graft chain to a polymer can be remarkably improved.
If necessary, the double bond portion of the (meth) acrylate group of the (meth) acryl-modified epoxy resin obtained by using (meth) acrylic acid as a modifier may be graft-polymerized with another vinyl monomer as necessary. Other vinyl monomers include alkenyl aromatics such as styrene, acrylic esters such as methyl methacrylate (MMA), acrylic compounds containing no ester groups such as acrylic acid, non-conjugated vinyl compounds such as vinyl acetate, butadiene Examples thereof include conjugated diene compounds. In this graft polymerization, a known radical initiator is used as a catalyst.
本実施形態に係る熱硬化性樹脂組成物は、硬化剤を含むことが好ましい。硬化剤は組成物中に存在する場合であっても常温時には硬化反応を生起させず、熱が与えられると直ちにエポキシ樹脂を硬化させる潜在性硬化剤が好んで用いられる。潜在性硬化剤の融点は好ましくは５０℃以上、より好ましくは５０℃以上２５０℃以下である。 The thermosetting resin composition according to this embodiment preferably contains a curing agent. Even when the curing agent is present in the composition, a latent curing agent that does not cause a curing reaction at normal temperature and cures the epoxy resin immediately upon application of heat is preferably used. The melting point of the latent curing agent is preferably 50 ° C. or higher, more preferably 50 ° C. or higher and 250 ° C. or lower.
潜在性硬化剤は、窒素含有化合物であることが好ましく、有機酸ジヒドラジド化合物、イミダゾール変性化合物、ポリアミン化合物、ジシアンジアミド等のシアノ基とアミド基とを有する化合物およびポリアミノウレア化合物からなる群より選ばれる少なくとも一種の化合物であることがより好ましい。これらの潜在性硬化剤は、単独で用いてもよいし、二種以上を組み合わせて用いてもよい。 The latent curing agent is preferably a nitrogen-containing compound, at least selected from the group consisting of a compound having a cyano group and an amide group such as an organic acid dihydrazide compound, an imidazole-modified compound, a polyamine compound, dicyandiamide, and a polyaminourea compound. More preferably, it is a kind of compound. These latent curing agents may be used alone or in combination of two or more.
有機酸ジヒドラジド化合物としては、アジピン酸ジヒドラジド、ドデカン二酸ジヒドラジド）、イソフタル酸ジヒドラジド、およびセバシン酸ジヒドラジド等の融点が１５０℃を超えるような化合物を好ましい例として挙げることができる。このように、一定以上の融点を有する有機酸ジヒドラジド化合物は、１，３−ビス（ヒドラジノカルボエチル）−５−イソプロピルヒダントイン（ＶＤＨ）等の融点が低い有機酸ジヒドラジド化合物と比べて熱的に安定であるため、加温下における粘度安定性に優れる。 Preferred examples of the organic acid dihydrazide compound include compounds having a melting point exceeding 150 ° C. such as adipic acid dihydrazide, dodecanedioic acid dihydrazide), isophthalic acid dihydrazide, and sebacic acid dihydrazide. Thus, an organic acid dihydrazide compound having a melting point of a certain level or more is thermally compared with an organic acid dihydrazide compound having a low melting point such as 1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin (VDH). Since it is stable, it has excellent viscosity stability under heating.
融点が１３０℃以下のイミダゾール変性化合物としては、例えば、味の素ファインテクノ社製ＰＮ-２３、ＰＮ−４０Ｊ、ＭＹ−Ｈ、ＭＹ−２４、およびＡＤＥＫＡ社製ＥＨ-４３４４Ｓ等が挙げられる。融点が１３０℃以下のポリアミン化合物としては、例えば、ＡＤＥＫＡ社製ＥＨ−５０５７（８０℃）等が挙げられる。融点が１３０℃以下のポリアミノウレア化合物としては、例えば、Ｔ＆Ｋ ＴＯＫＡ社製フジキュアＦＸＲ−１０８１（融点１２１℃）、およびフジキュアＦＸＲ−１０２０（融点１２４℃）等が挙げられる。ポリアミノウレア化合物とは、アミンと尿素を加熱硬化させて得られる化合物である。 Examples of the imidazole-modified compound having a melting point of 130 ° C. or lower include PN-23, PN-40J, MY-H, MY-24, and Adeka EH-4344S manufactured by Ajinomoto Fine Techno Co., Ltd. Examples of the polyamine compound having a melting point of 130 ° C. or less include EH-5057 (80 ° C.) manufactured by ADEKA. Examples of the polyaminourea compound having a melting point of 130 ° C. or lower include Fujicure FXR-1081 (melting point 121 ° C.) and Fujicure FXR-1020 (melting point 124 ° C.) manufactured by T & K TOKA. A polyaminourea compound is a compound obtained by heat-curing an amine and urea.
潜在性硬化剤は、前述の通り固形物であることが好ましく、その数平均粒子径は４μｍ以下であることが好ましく、０．５〜４μｍであることがより好ましく、１〜３μｍであることがさらに好ましい。潜在性硬化剤の数平均粒子径が上記下限値以上であると、粘度安定性がより向上し、数平均粒子径が上記上限値以下であると、分散性がより良好になる。潜在性硬化剤の粒子径は、ビーズミル、ボールミル等により粉砕することで調整できる。上記の硬化剤は、単独で用いても複数種を併用することもできる。潜在性硬化剤の含有量は、エポキシ樹脂１００重量部に対して、好ましくは１〜２０重量部であり、より好ましくは３〜１５重量部である。 The latent curing agent is preferably a solid as described above, and its number average particle diameter is preferably 4 μm or less, more preferably 0.5 to 4 μm, and preferably 1 to 3 μm. Further preferred. When the number average particle diameter of the latent curing agent is not less than the above lower limit, the viscosity stability is further improved, and when the number average particle diameter is not more than the above upper limit, dispersibility becomes better. The particle size of the latent curing agent can be adjusted by pulverizing with a bead mill, a ball mill or the like. The above curing agents can be used alone or in combination. The content of the latent curing agent is preferably 1 to 20 parts by weight and more preferably 3 to 15 parts by weight with respect to 100 parts by weight of the epoxy resin.
本実施形態に係る熱硬化性樹脂組成物は、必要に応じて、さらに炭酸カルシウムや二酸化ケイ素、アルミナ等の無機フィラー、シランカップリング剤等のカップリング剤、カーボンブラック等の顔料、染料、可塑剤、消泡剤等を含んでいてもよい。 If necessary, the thermosetting resin composition according to the present embodiment further includes inorganic fillers such as calcium carbonate, silicon dioxide, and alumina, coupling agents such as silane coupling agents, pigments such as carbon black, dyes, plastics, and the like. An agent, an antifoaming agent, etc. may be included.
本実施形態において、金属部材１０３とエポキシ樹脂硬化体層１０２との間に物理的な抵抗力（アンカー効果）を効果的に発現させために、エポキシ樹脂硬化体層１０２の硬化前ステージにある熱硬化性樹脂組成物の粘度（Ｂ型粘度計を用いて２３℃、回転数０．２ｒｐｍの条件で測定した値）は、好ましくは５０Ｐａ・ｓ〜５００Ｐａ・ｓ、より好ましくは１００Ｐａ・ｓ〜４００Ｐａ・ｓである。このような要件を満たすことによって、金属部材１０３と、接着層としてのエポキシ樹脂硬化体層１０２との間にアンカー効果が効果的に発現し、結果として接合強度により一層優れた金属／繊維強化プラスチック複合構造体１０６を得ることができる。また、このような流動変形特性は、塗布性を向上させるので好ましい。 In this embodiment, in order to effectively develop a physical resistance (anchor effect) between the metal member 103 and the cured epoxy resin layer 102, the heat in the stage before curing of the cured epoxy resin layer 102 is obtained. The viscosity of the curable resin composition (a value measured using a B-type viscometer at 23 ° C. and a rotational speed of 0.2 rpm) is preferably 50 Pa · s to 500 Pa · s, more preferably 100 Pa · s to 400 Pa. -S. By satisfying such requirements, an anchor effect is effectively expressed between the metal member 103 and the cured epoxy resin layer 102 as the adhesive layer, and as a result, the metal / fiber reinforced plastic is more excellent in bonding strength. A composite structure 106 can be obtained. Moreover, such a flow deformation characteristic is preferable because it improves applicability.
本実施形態においては、アンカー効果をより一層効果的に発現させ、金属部材１０３と繊維強化プラスチック部材１０５との間の接合強度がさらに強固になった金属／繊維強化プラスチック複合構造体１０６を得るためには、エポキシ樹脂硬化体層１０２の硬化前ステージにある熱硬化性樹脂組成物の粘度（Ｂ型粘度計を用いて２３℃、回転数０．２ｒｐｍの条件で測定した値）が、好ましくは１００Ｐａ・ｓ〜３００Ｐａ・ｓ、より好ましくは１１０Ｐａ・ｓ〜２５０Ｐａ・ｓを満たし、かつ、２３℃におけるチクソトロピックインデックス（回転数０．２ｒｐｍで測定した粘度を、回転数２．０ｒｐｍで測定した値で除した比）が好ましくは１．２〜１．８、より好ましくは１．３〜１．７の範囲を満たす。２３℃のＢ型回転粘度が上記下限値以上であると、接着面に特定量の熱硬化性樹脂組成物を特定厚みで保持しやすくなるため好ましい。一方で、２３℃のＢ型回転粘度が上記上限値以下であると、金属部材１０３の微細凹凸形状の凹部への熱硬化性樹脂組成物の浸透性をより一層向上できる点、あるいは金属部材１０３と繊維強化プラスチック部材１０５との間の接着すべき空間が三次元的に入り組んでいる場合や隙間が狭い場合に熱硬化性樹脂組成物を接着すべき空間に十分に流入させることができる点等から好ましい。このような流動変形特性を備えた熱硬化性樹脂組成物は、熱硬化性樹脂組成物の構成成分種と成分割合を調整することによって調製することが可能である。 In this embodiment, in order to obtain the metal / fiber reinforced plastic composite structure 106 in which the anchor effect is more effectively exhibited and the bonding strength between the metal member 103 and the fiber reinforced plastic member 105 is further strengthened. The viscosity of the thermosetting resin composition in the pre-curing stage of the cured epoxy resin layer 102 (value measured using a B-type viscometer at 23 ° C. and a rotational speed of 0.2 rpm) is preferably 100 Pa · s to 300 Pa · s, more preferably 110 Pa · s to 250 Pa · s, and a thixotropic index at 23 ° C (viscosity measured at 0.2 rpm) measured at 2.0 rpm Ratio) is preferably 1.2 to 1.8, more preferably 1.3 to 1.7. It is preferable for the B-type rotational viscosity at 23 ° C. to be equal to or higher than the lower limit because a specific amount of the thermosetting resin composition can be easily held at a specific thickness on the adhesive surface. On the other hand, if the B-type rotational viscosity at 23 ° C. is equal to or lower than the above upper limit, the penetrability of the thermosetting resin composition into the concave portions of the fine unevenness of the metal member 103 can be further improved, or the metal member 103. When the space to be bonded between the fiber reinforced plastic member 105 and the fiber reinforced plastic member 105 is three-dimensionally complicated or when the gap is narrow, the thermosetting resin composition can be sufficiently allowed to flow into the space to be bonded, etc. To preferred. A thermosetting resin composition having such fluid deformation characteristics can be prepared by adjusting the constituent component species and the component ratio of the thermosetting resin composition.
＜金属／繊維強化プラスチック複合構造体の製造方法＞
本実施形態に係る金属／繊維強化プラスチック複合構造体の製造方法については特段の制限はない。以下に製造方法の一例を説明する。まず、熱硬化性樹脂組成物を調製したのち、これを金属部材１０３の粗化面に塗布する。例えば、公知の刷毛やスプレー、ローラー等により粗化金属面に熱硬化性樹脂組成物を塗布した後、必要に応じて風乾する方法等が挙げられる。次いで、熱硬化性樹脂組成物が塗布された金属部材１０３上に、繊維強化プラスチック部材１０５を配置後、プレス成形、オートクレーブ成形等の適切な成形方法により、熱硬化性樹脂組成物の硬化条件、並びに繊維強化プラスチックが非繊維強化樹脂を含む場合は非繊維強化樹脂組成物の硬化条件の両者を勘案して加熱、加圧し、熱硬化性樹脂組成物の硬化と、エポキシ樹脂硬化体層１０２の金属部材１０３の表面および繊維強化プラスチック部材１０５の表面への接合と、を完結させる。次いで、得られた金属／繊維強化プラスチック複合構造体１０６を脱型して取り出す。このような方法によって、本実施形態に係る金属／繊維強化プラスチック複合構造体１０６を製造することができる。
<Method for producing metal / fiber reinforced plastic composite structure>
There is no particular limitation on the method for producing the metal / fiber reinforced plastic composite structure according to this embodiment. An example of the manufacturing method will be described below. First, after preparing a thermosetting resin composition, this is applied to the roughened surface of the metal member 103. For example, a method of applying a thermosetting resin composition to a roughened metal surface with a known brush, spray, roller, or the like, and then air-drying as necessary can be used. Next, after disposing the fiber reinforced plastic member 105 on the metal member 103 to which the thermosetting resin composition is applied, the curing conditions of the thermosetting resin composition by an appropriate molding method such as press molding or autoclave molding, In addition, when the fiber reinforced plastic contains a non-fiber reinforced resin, heating and pressurizing in consideration of both the curing conditions of the non-fiber reinforced resin composition, curing of the thermosetting resin composition, and the epoxy resin cured body layer 102 Bonding to the surface of the metal member 103 and the surface of the fiber reinforced plastic member 105 is completed. Next, the obtained metal / fiber reinforced plastic composite structure 106 is demolded and taken out. By such a method, the metal / fiber reinforced plastic composite structure 106 according to the present embodiment can be manufactured.
以上、本発明の実施形態について述べたが、これらは本発明の例示であり、上記以外の様々な構成を採用することもできる。 As mentioned above, although embodiment of this invention was described, these are illustrations of this invention and various structures other than the above are also employable.
以下、本実施形態を、実施例・比較例を参照して詳細に説明する。なお、本実施形態は、これらの実施例の記載に何ら限定されるものではない。 Hereinafter, the present embodiment will be described in detail with reference to examples and comparative examples. In addition, this embodiment is not limited to description of these Examples at all.
［実施例１］
以下の方法により、アルミニウム合金の表面処理、接着剤の塗布および硬化工程を順次実施することによりアルミニウム合金／ＣＦＲＰ複合構造体を作製した。
[Example 1]
The aluminum alloy / CFRP composite structure was produced by sequentially performing the surface treatment of the aluminum alloy, the application of the adhesive, and the curing step by the following method.
＜表面処理工程＞
ＪＩＳ Ｈ４０００に規定された合金番号５０５２のアルミニウム合金板（４５ｍｍ×１８ｍｍ×２．０ｍｍ）を脱脂処理した。次いで、脱脂処理したアルミニウム合金板を硫酸８．２質量％、塩化第二鉄７．８質量％、塩化第二銅０．４質量％が溶解した水溶液（３０℃）中に３７５秒間浸漬し、揺動させることによってエッチングした。次いで、流水で超音波洗浄（水中、１分間）を行い、乾燥させることにより表面処理済みアルミニウム合金板を得た。
<Surface treatment process>
An aluminum alloy plate (45 mm × 18 mm × 2.0 mm) having an alloy number of 5052 defined in JIS H4000 was degreased. Then, the degreased aluminum alloy plate was immersed in an aqueous solution (30 ° C.) in which 8.2% by mass of sulfuric acid, 7.8% by mass of ferric chloride, and 0.4% by mass of cupric chloride were dissolved, for 375 seconds. Etching was performed by rocking. Subsequently, ultrasonic cleaning was performed with running water (in water, for 1 minute), and dried to obtain a surface-treated aluminum alloy plate.
得られた表面処理済みのアルミニウム合金板の表面粗さを、光学顕微鏡「オプトデジタルマイクロスコープＤＳＸ５００（オリンパス株式会社製）」を使用し、ＪＩＳ Ｂ０６０１（対応国際規格：ＩＳＯ４２８７）に準拠して測定される表面粗さのうち、粗さ曲線の十点平均粗さ（Ｒｚ）、粗さ曲線の算術平均粗さ（Ｒａ）および粗さ曲線要素の平均長さ（ＲＳｍ）を任意の三点について測定し、その平均値を求めた。その結果、Ｒｚ；２３．０μｍ、Ｒａ；６．０μｍ、ＲＳｍ；９０．９μｍであった。また、表面処理済みのアルミニウム合金板の粗化面（微細凹凸形状が形成された面）を顕微鏡観察（３Ｄ画像、有効倍率；５５５倍）した結果を図３に示す。 The surface roughness of the obtained surface-treated aluminum alloy plate was measured according to JIS B0601 (corresponding international standard: ISO 4287) using an optical microscope “Opto Digital Microscope DSX500 (Olympus Co., Ltd.)”. Among the surface roughnesses, the ten-point average roughness (Rz) of the roughness curve, the arithmetic average roughness (Ra) of the roughness curve, and the average length (RSm) of the roughness curve elements are measured at three arbitrary points. The average value was obtained. As a result, Rz: 23.0 μm, Ra: 6.0 μm, RSm: 90.9 μm. Moreover, the result of having observed the roughened surface (surface in which the fine uneven | corrugated shape was formed) of the surface-treated aluminum alloy plate under a microscope (3D image, effective magnification: 555 times) is shown in FIG.
＜塗布工程＞
ＣＦＲＰ板（１０枚の東レ社製トレカＴ３００を直交積層して得られた板、４５ｍｍ×１８ｍｍ×２．０ｍｍ）の長手方向端部（５ｍｍ幅）について、ヤスリを用いた機械研磨を行うことによって表面に付着した離型剤を除去した。
次いで、上の表面処理工程で得られた表面処理済みアルミニウム合金板の長手方向の端部（５ｍｍ幅）および上記ＣＦＲＰ板の研磨面に、エポキシ樹脂接着剤（特公昭６０−２６４２７号の実施例３に従って調製したエポキシ基含有アクリル変性ゴムを主成分として含む三井化学製接着剤「ストラクトボンド」、Ｂ型粘度計を用いて２３℃、回転数０．２ｒｐｍの条件で測定した粘度；２００Ｐａ・ｓ）を１００μｍの厚みになるようにそれぞれ塗布し、塗布されたそれぞれのエポキシ樹脂接着層が完全に重なるように相対配置させた。
なお、この配置においてはアルミニウム合金板とＣＦＲＰ板の隙間が２００μｍに固定させるための治具およびスペーサーを用いた。
<Application process>
By performing mechanical polishing with a file on the longitudinal end (5 mm width) of a CFRP plate (a plate obtained by orthogonally laminating 10 TORAYCA T300 manufactured by Toray Industries, Inc., 45 mm × 18 mm × 2.0 mm) The release agent adhering to the surface was removed.
Next, an epoxy resin adhesive (Example of Japanese Examined Patent Publication No. 60-26427) is applied to the longitudinal end (5 mm width) of the surface-treated aluminum alloy plate obtained in the above surface treatment step and the polished surface of the CFRP plate. Viscosity measured at 23 ° C. and a rotation speed of 0.2 rpm using a B-type viscometer, Mitsui Chemicals adhesive “Struct Bond” containing epoxy group-containing acrylic modified rubber prepared according to 3 as a main component; 200 Pa · s ) Were applied so as to have a thickness of 100 μm, and each of the applied epoxy resin adhesive layers was relatively disposed so as to completely overlap each other.
In this arrangement, a jig and a spacer for fixing the gap between the aluminum alloy plate and the CFRP plate to 200 μm were used.
＜硬化工程＞
相対配置させた試験片を、室温で１０分間静置した後、１５０℃で３０分間硬化させることによって、図１に示す引っ張りせん断強度測定用の試験片を得た。
<Curing process>
The relative-positioned test piece was allowed to stand at room temperature for 10 minutes and then cured at 150 ° C. for 30 minutes to obtain a test piece for tensile shear strength measurement shown in FIG.
＜引っ張りせん断強度の測定および破断面観察＞
引っ張り試験機「モデル１３２３（アイコーエンジニヤリング社製）」を使用し、引張試験機に専用の治具を取り付け、室温（２３℃）にて、チャック間距離６０ｍｍ、引張速度１０ｍｍ／ｍｉｎの条件にて測定をおこなった。破断荷重（Ｎ）を金属／樹脂接合部分の面積で除することにより接合強度を求めた。その結果、接合強度は３９ＭＰａであった。接合部分の破断面を、アルミニウム合金側およびＣＦＲＰ側と並べて写真撮影した図面を図５に示す（左側はアルミニウム合金、右側はＣＦＲＰ、アルミニウム合金側の白色部分は合金部分に相当し、暗色部分はエポキシ樹脂硬化体層部分に相当する）。図５から明らかなように、アルミニウム合金側にはアルミニウム合金板−エポキシ樹脂硬化体層（接着剤）間の界面剥離はほとんど認められず、ＣＦＲＰ板の母材破壊が主なる破壊形態であることが理解できる。
<Measurement of tensile shear strength and observation of fracture surface>
Using a tensile tester “Model 1323 (manufactured by Aiko Engineering Co., Ltd.)”, a dedicated jig is attached to the tensile tester, and at room temperature (23 ° C.), the distance between chucks is 60 mm and the tensile speed is 10 mm / min. And measured. The joint strength was determined by dividing the breaking load (N) by the area of the metal / resin joint. As a result, the bonding strength was 39 MPa. FIG. 5 shows a photograph of the fracture surface of the joint portion taken side by side with the aluminum alloy side and the CFRP side (the left side is aluminum alloy, the right side is CFRP, the white portion on the aluminum alloy side is equivalent to the alloy portion, and the dark color portion is It corresponds to the epoxy resin cured body layer portion). As is clear from FIG. 5, almost no interfacial delamination between the aluminum alloy plate and the cured epoxy resin layer (adhesive) is observed on the aluminum alloy side, and the base material destruction of the CFRP plate is the main failure mode. Can understand.
［比較例１］
＜表面処理工程＞
ＪＩＳ Ｈ４０００に規定された合金番号５０５２のアルミニウム合金板（４５ｍｍ×１８ｍｍ×２．０ｍｍ）を脱脂処理した。次いで、脱脂処理したアルミニウム合金板を水洗し、４０℃の１質量％塩酸水溶液が入った槽に１分浸漬し水洗した。つづいて、４０℃の１．５質量％水酸化ナトリウム水溶液が入った槽に４分浸漬し水洗した。次いで４０℃の３質量％硝酸水溶液が入った槽に３分浸漬し水洗した。次いで６０℃の３．５質量％濃度の１水和ヒドラジン水溶液を入れたヒドラジン処理槽に２分浸漬し、４０℃の５質量％濃度の過酸化水素水溶液を入れた処理槽に５分浸漬し水洗した。これを乾燥させることにより表面処理済みアルミニウム合金板を得た。
[Comparative Example 1]
<Surface treatment process>
An aluminum alloy plate (45 mm × 18 mm × 2.0 mm) having an alloy number of 5052 defined in JIS H4000 was degreased. Next, the degreased aluminum alloy plate was washed with water, immersed in a tank containing a 1% by mass hydrochloric acid aqueous solution at 40 ° C. for 1 minute, and washed with water. Then, it was immersed in a tank containing a 1.5 mass% sodium hydroxide aqueous solution at 40 ° C. for 4 minutes and washed with water. Subsequently, it was immersed in a tank containing a 3% by mass nitric acid solution at 40 ° C. for 3 minutes and washed with water. Next, it was immersed in a hydrazine treatment tank containing a 3.5% by weight hydrated hydrazine aqueous solution at 60 ° C. for 2 minutes and immersed in a treatment tank containing a 5% by weight aqueous hydrogen peroxide solution at 40 ° C. for 5 minutes. Washed with water. This was dried to obtain a surface-treated aluminum alloy plate.
得られた表面処理済みのアルミニウム合金板の表面粗さを、実施例１に記載の方法と同様にして、粗さ曲線の十点平均粗さ（Ｒｚ）、粗さ曲線の算術平均粗さ（Ｒａ）および粗さ曲線要素の平均長さ（ＲＳｍ）を任意の三点について測定し、その平均値を求めた。その結果、Ｒｚ；３．２μｍ、Ｒａ；０．５μｍ、ＲＳｍ；１７．２μｍであった。また、表面処理済みのアルミニウム合金板の粗化面（微細凹凸形状が形成された面）を顕微鏡観察（３Ｄ画像、有効倍率；５５５倍）した結果を図４に示す。 The surface roughness of the obtained surface-treated aluminum alloy plate was determined in the same manner as in Example 1, except that the ten-point average roughness (Rz) of the roughness curve and the arithmetic average roughness ( Ra) and the average length (RSm) of the roughness curve element were measured at three arbitrary points, and the average value was obtained. As a result, Rz: 3.2 μm, Ra: 0.5 μm, RSm: 17.2 μm. Moreover, the result of having observed the roughened surface (surface in which the fine uneven | corrugated shape was formed) of the surface-treated aluminum alloy plate under a microscope (3D image, effective magnification: 555 times) is shown in FIG.
実施例１に記載した方法と全く同様にして、塗布工程、硬化工程、引っ張りせん断強度の測定および破断面観察を行った。その結果、接合強度は、３５ＭＰａであった。また、接合部分の破断面を、アルミニウム合金側およびＣＦＲＰ側と並べて写真撮影した図面を図６に示す（左側はアルミニウム合金、右側はＣＦＲＰ、アルミニウム合金側の白色部分は合金部分に相当し、暗色部分はエポキシ樹脂硬化体層部分に相当する）。図６から明らかなように、アルミニウム合金側にはアルミニウム合金板−エポキシ樹脂硬化体層（接着剤）間の界面剥離が多数認められる。 The coating process, the curing process, the tensile shear strength measurement, and the fracture surface observation were performed in exactly the same manner as described in Example 1. As a result, the bonding strength was 35 MPa. FIG. 6 shows a photograph of the fracture surface of the joint portion taken side by side with the aluminum alloy side and the CFRP side (the left side is aluminum alloy, the right side is CFRP, the white portion on the aluminum alloy side is equivalent to the alloy portion, and dark color) The part corresponds to the cured epoxy resin layer part). As is clear from FIG. 6, many interface peelings between the aluminum alloy plate and the cured epoxy resin layer (adhesive) are observed on the aluminum alloy side.
１０２ エポキシ樹脂硬化体層
１０３ 金属部材
１０４ 接合部表面
１０５ 繊維強化プラスチック部材
１０６ 金属／繊維強化プラスチック複合構造体
102 Hardened epoxy resin layer 103 Metal member 104 Joint surface 105 Fiber reinforced plastic member 106 Metal / fiber reinforced plastic composite structure
Claims (5)
繊維強化プラスチック部材と、
前記金属部材と前記繊維強化プラスチック部材との間に設けられたエポキシ樹脂硬化体層と、
を備え、
前記金属部材は少なくとも前記繊維強化プラスチック部材との接合部表面にＪＩＳ Ｂ６０１（対応国際規格：ＩＳＯ４２８７）で規定される表面粗さパラメーターが下記要件ａ）〜ｃ）を同時に満たす微細凹凸形状を有し、
前記エポキシ樹脂硬化体層は前記金属部材の前記微細凹凸形状の一部または全部を覆うように形成されており、
前記金属部材と前記繊維強化プラスチック部材とは前記エポキシ樹脂硬化体層を介して接合している金属／繊維強化プラスチック複合構造体。
ａ）粗さ曲線の十点平均粗さ（Ｒｚ）が５μｍ超５０μｍ以下である
ｂ）粗さ曲線の算術平均粗さ（Ｒａ）が０．５μｍ以上３０μｍ以下である
ｃ）粗さ曲線要素の平均長さ（ＲＳｍ）が２０μｍ以上３００μｍ以下である A metal member;
A fiber reinforced plastic member;
An epoxy resin cured body layer provided between the metal member and the fiber-reinforced plastic member;
With
The metal member has at least a fine concavo-convex shape in which the surface roughness parameter defined in JIS B601 (corresponding international standard: ISO4287) satisfies the following requirements a) to c) at least on the surface of the joint portion with the fiber reinforced plastic member ,
The epoxy resin cured body layer is formed so as to cover a part or all of the fine uneven shape of the metal member,
The metal member and the fiber reinforced plastic member are a metal / fiber reinforced plastic composite structure in which the cured epoxy resin layer is bonded to the metal member and the fiber reinforced plastic member.
a) The ten-point average roughness (Rz) of the roughness curve is more than 5 μm and not more than 50 μm. b) The arithmetic average roughness (Ra) of the roughness curve is not less than 0.5 μm and not more than 30 μm. c) The roughness curve element The average length (RSm) is 20 μm or more and 300 μm or less
前記エポキシ樹脂硬化体層がエポキシ樹脂と硬化剤とを含む熱硬化性樹脂組成物の硬化物により構成される金属／繊維強化プラスチック複合構造体。 The metal / fiber reinforced plastic composite structure according to claim 1,
A metal / fiber reinforced plastic composite structure in which the cured epoxy resin layer is composed of a cured product of a thermosetting resin composition containing an epoxy resin and a curing agent.
Ｂ型粘度計を用いて２３℃、回転数０．２ｒｐｍの条件で測定される、前記熱硬化性樹脂組成物の粘度が５０Ｐａ・ｓ以上５００Ｐａ・ｓ以下である金属／繊維強化プラスチック複合構造体。 The metal / fiber reinforced plastic composite structure according to claim 2,
A metal / fiber reinforced plastic composite structure in which the viscosity of the thermosetting resin composition is 50 Pa · s or more and 500 Pa · s or less as measured using a B-type viscometer at 23 ° C. and a rotational speed of 0.2 rpm. .
前記熱硬化性樹脂組成物が、
分子内に２以上のエポキシ基を含むエポキシ樹脂と（メタ）アクリル酸との反応物である（メタ）アクリル変性エポキシ樹脂と、
潜在性硬化剤と、
を含む金属／繊維強化プラスチック複合構造体。 The metal / fiber reinforced plastic composite structure according to claim 2 or 3,
The thermosetting resin composition is
A (meth) acryl-modified epoxy resin, which is a reaction product of an epoxy resin containing two or more epoxy groups in the molecule and (meth) acrylic acid,
A latent curing agent;
A metal / fiber reinforced plastic composite structure comprising:
前記金属部材が、鉄、ステンレス、アルミニウム、アルミニウム合金、マグネシウム、マグネシウム合金、銅、銅合金、チタンおよびチタン合金から選択される一種または二種以上を含む金属／繊維強化プラスチック複合構造体。 The metal / fiber reinforced plastic composite structure according to any one of claims 1 to 4,
A metal / fiber reinforced plastic composite structure in which the metal member includes one or more selected from iron, stainless steel, aluminum, aluminum alloy, magnesium, magnesium alloy, copper, copper alloy, titanium, and titanium alloy.
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