JP2005194456A - Preform forming binder composition, reinforcing fiber base material, method for producing preform and fiber reinforced composite material - Google Patents
Preform forming binder composition, reinforcing fiber base material, method for producing preform and fiber reinforced composite material Download PDFInfo
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- JP2005194456A JP2005194456A JP2004003956A JP2004003956A JP2005194456A JP 2005194456 A JP2005194456 A JP 2005194456A JP 2004003956 A JP2004003956 A JP 2004003956A JP 2004003956 A JP2004003956 A JP 2004003956A JP 2005194456 A JP2005194456 A JP 2005194456A
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- binder composition
- preform
- reinforcing fiber
- glass transition
- thermosetting resin
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- 239000011230 binding agent Substances 0.000 title claims abstract description 110
- 239000000203 mixture Substances 0.000 title claims abstract description 102
- 239000012783 reinforcing fiber Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 31
- 239000003733 fiber-reinforced composite Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 230000009477 glass transition Effects 0.000 claims abstract description 34
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 239000011342 resin composition Substances 0.000 claims abstract description 20
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 15
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 43
- 239000000758 substrate Substances 0.000 claims description 32
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 45
- 238000003860 storage Methods 0.000 abstract description 15
- 239000002904 solvent Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 16
- 238000001723 curing Methods 0.000 description 15
- 239000000835 fiber Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229920000049 Carbon (fiber) Polymers 0.000 description 8
- 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 8
- 239000004917 carbon fiber Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000013007 heat curing Methods 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002759 woven fabric Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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
- 230000007423 decrease Effects 0.000 description 4
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- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 2
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 2
- ZJRAAAWYHORFHN-UHFFFAOYSA-N 2-[[2,6-dibromo-4-[2-[3,5-dibromo-4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenoxy]methyl]oxirane Chemical compound C=1C(Br)=C(OCC2OC2)C(Br)=CC=1C(C)(C)C(C=C1Br)=CC(Br)=C1OCC1CO1 ZJRAAAWYHORFHN-UHFFFAOYSA-N 0.000 description 2
- IWRZKNMUSBNOOD-UHFFFAOYSA-N 2-methyl-4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C=1C=C(N(CC2OC2)CC2OC2)C(C)=CC=1OCC1CO1 IWRZKNMUSBNOOD-UHFFFAOYSA-N 0.000 description 2
- OVEUFHOBGCSKSH-UHFFFAOYSA-N 2-methyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound CC1=CC=CC=C1N(CC1OC1)CC1OC1 OVEUFHOBGCSKSH-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- VAGOJLCWTUPBKD-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=1)=CC=CC=1N(CC1OC1)CC1CO1 VAGOJLCWTUPBKD-UHFFFAOYSA-N 0.000 description 2
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 description 2
- UHUUGQDYCYKQTC-UHFFFAOYSA-N 4-[2,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1CC(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 UHUUGQDYCYKQTC-UHFFFAOYSA-N 0.000 description 2
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 2
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 2
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 2
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 2
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
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- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 2
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- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 2
- FZZQNEVOYIYFPF-UHFFFAOYSA-N naphthalene-1,6-diol Chemical compound OC1=CC=CC2=CC(O)=CC=C21 FZZQNEVOYIYFPF-UHFFFAOYSA-N 0.000 description 2
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- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- DUILGEYLVHGSEE-UHFFFAOYSA-N 2-(oxiran-2-ylmethyl)isoindole-1,3-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1CC1CO1 DUILGEYLVHGSEE-UHFFFAOYSA-N 0.000 description 1
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 1
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- LNNIPFBETXOKIA-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)-9h-fluoren-2-yl]phenol Chemical compound C1=CC(O)=CC=C1C1=CC=C(C=2C(=CC=CC=2)C2)C2=C1C1=CC=C(O)C=C1 LNNIPFBETXOKIA-UHFFFAOYSA-N 0.000 description 1
- PMPLQTWAQNSOSY-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]-3-ethylphenyl]methyl]-2-ethyl-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C=1C=C(N(CC2OC2)CC2OC2)C(CC)=CC=1CC(C=C1CC)=CC=C1N(CC1OC1)CC1CO1 PMPLQTWAQNSOSY-UHFFFAOYSA-N 0.000 description 1
- RZJKZTPKSRPUFJ-UHFFFAOYSA-N 5,5-dimethyl-1,3-bis(oxiran-2-ylmethyl)imidazolidine-2,4-dione Chemical compound O=C1N(CC2OC2)C(=O)C(C)(C)N1CC1CO1 RZJKZTPKSRPUFJ-UHFFFAOYSA-N 0.000 description 1
- OXQXGKNECHBVMO-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-4-carboxylic acid Chemical compound C1C(C(=O)O)CCC2OC21 OXQXGKNECHBVMO-UHFFFAOYSA-N 0.000 description 1
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
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- 239000004952 Polyamide Substances 0.000 description 1
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Abstract
Description
本発明は、繊維強化複合材料の製造方法、ならびにこの製造方法に用いるプリフォーム、該プリフォームの作成に用いる強化繊維基材およびバインダー組成物の改良に関する。 The present invention relates to a method for producing a fiber reinforced composite material, a preform used in the production method, and a reinforcing fiber substrate and a binder composition used for producing the preform.
従来より、ガラス繊維、炭素繊維、アラミド繊維などの強化繊維と不飽和ポリエステル樹脂、ビニルエステル樹脂、エポキシ樹脂、フェノール樹脂、シアネート樹脂、ビスマレイミド樹脂などの熱硬化性樹脂からなる繊維強化複合材料は、軽量でありながら、強度、剛性、耐衝撃性、耐疲労性などの機械物性や耐熱性、更には耐食性に優れるため、航空機、宇宙機、自動車、鉄道車両、船舶、土木建築、スポーツ用品などの数多くの分野に応用されてきた。特に高性能が要求される用途では、連続した強化繊維を用いた繊維強化複合材料が用いられ、強化繊維としては炭素繊維が、マトリックス樹脂としては熱硬化性樹脂、なかんずくエポキシ樹脂が多く用いられている。 Conventionally, fiber reinforced composite materials consisting of reinforced fibers such as glass fiber, carbon fiber, and aramid fiber and thermosetting resins such as unsaturated polyester resin, vinyl ester resin, epoxy resin, phenol resin, cyanate resin, and bismaleimide resin have been Because it is lightweight, it has excellent mechanical properties and heat resistance such as strength, rigidity, impact resistance and fatigue resistance, as well as corrosion resistance, so it can be used in aircraft, spacecraft, automobiles, railway vehicles, ships, civil engineering, sports equipment, etc. Has been applied in many fields. In applications that require particularly high performance, fiber reinforced composite materials using continuous reinforcing fibers are used. Carbon fibers are used as reinforcing fibers, thermosetting resins are used as matrix resins, and epoxy resins are especially used. Yes.
また、繊維強化複合材料は様々な方法で製造されるが、型内に配置した強化繊維基材に液状の熱硬化性樹脂組成物を注入し、加熱硬化して繊維強化複合材料を得るレジン・トランスファー・モールディング（Ｒｅｓｉｎ Ｔｒａｎｓｆｅｒ Ｍｏｌｄｉｎｇ、以下ＲＴＭ法と略記する。）が、低コスト生産性にすぐれた方法として近年注目されている。 In addition, fiber reinforced composite materials are manufactured by various methods. A resin / resin is obtained by injecting a liquid thermosetting resin composition into a reinforced fiber base placed in a mold and heat-curing to obtain a fiber reinforced composite material. In recent years, transfer molding (resin transfer molding, hereinafter abbreviated as RTM method) has attracted attention as a method with excellent low-cost productivity.
ＲＴＭ法で繊維強化複合材料を製造する場合、強化繊維基材を所望の製品と近い形状に加工したプリフォームを予め作成し、このプリフォームを型内に設置して液状熱硬化性樹脂を注入することが多い。 When manufacturing fiber reinforced composite materials by the RTM method, a preform in which a reinforcing fiber substrate is processed into a shape close to the desired product is prepared in advance, and this preform is placed in a mold and a liquid thermosetting resin is injected. Often to do.
プリフォームの作成方法には、強化繊維から３次元ブレイドを作成する方法や、強化繊維織物を積層してステッチする方法など、いくつかの方法が知られているが、汎用性の高い方法として、ホットメルト性のバインダー（タッキファイアーとも呼ばれる）を用いて強化繊維織物などのシート状基材を積層、賦形する方法が知られている（例えば非特許文献１）。 There are several known methods for creating a preform, such as a method of creating a three-dimensional braid from reinforcing fibers and a method of stacking and stitching reinforcing fiber fabrics. A method of laminating and shaping a sheet-like substrate such as a reinforced fiber fabric using a hot-melt binder (also called a tackifier) is known (for example, Non-Patent Document 1).
バインダー成分としては、例えば特許文献１に示すような熱可塑性樹脂から成るバインダーがある。熱可塑性樹脂から成るバインダーは、熱を加えるホットメルトにより強化繊維基材へ接着させた場合、熱可塑性樹脂の溶融粘度が高いため強化繊維を充分に濡らすことができず、隣接する強化繊維基材を接着させる効果が小さいほか、バインダー自体が強化繊維基材に接着できず脱落するという問題があった。これらの問題を解決するためには熱可塑性樹脂のガラス転移温度を下げることが有効であるが、その場合、得られた繊維強化複合材料の耐熱性や機械物性を低下させるため好ましくはない。 As a binder component, there exists a binder which consists of a thermoplastic resin as shown, for example in patent document 1. FIG. When a binder made of a thermoplastic resin is bonded to a reinforcing fiber base by hot melt that applies heat, the thermoplastic fiber has a high melt viscosity, so that the reinforcing fiber cannot be sufficiently wetted. In addition to having a small effect of adhering, the binder itself cannot be adhered to the reinforcing fiber base and falls off. In order to solve these problems, it is effective to lower the glass transition temperature of the thermoplastic resin, but in that case, it is not preferable because the heat resistance and mechanical properties of the obtained fiber-reinforced composite material are lowered.
また、別成分のバインダーとして、特許文献２〜４に示すような熱硬化性樹脂から成るバインダーを用いた方法がある。熱硬化性樹脂は熱可塑性樹脂と比較すると溶融粘度が低いため、ホットメルトにより強化繊維を充分濡らすことができるが、熱硬化性樹脂は強化繊維との接着力が低く、また熱硬化性樹脂は脆性のため、プリフォームを取扱中に割れて脱落するといった問題があった。 Moreover, there exists the method of using the binder which consists of a thermosetting resin as shown to patent documents 2-4 as a binder of another component. The thermosetting resin has a low melt viscosity compared to the thermoplastic resin, so the hot fiber can sufficiently wet the reinforcing fiber. However, the thermosetting resin has a low adhesive force with the reinforcing fiber, and the thermosetting resin Due to the brittleness, there was a problem that the preform was broken and dropped during handling.
更に別成分のバインダーとして、特許文献５〜６に示すような熱可塑性樹脂と熱硬化性樹脂から成るバインダーを用いた方法がある。しかし、これらの特許文献に示されているバインダーは硬化剤成分が含まれており、自己硬化性が有るため保管中にバインダーのガラス転移温度が上昇し、ついには使用不可になる問題があった。
本発明は、かかる従来技術の背景に鑑み、熱硬化性樹脂、特にエポキシ樹脂を用いるＲＴＭ法に適し、溶剤を使わない加熱による固着方法を用いても、強化繊維との密着性が優れ、保存安定性の良いプリフォーム作成用のバインダー組成物およびこの組成物を用いたプリフォーム等を提供せんとするものである。 The present invention is suitable for the RTM method using a thermosetting resin, particularly an epoxy resin, in view of the background of such a prior art, and has excellent adhesion with a reinforcing fiber even when a fixing method by heating without using a solvent is used, and is preserved. It is an object of the present invention to provide a binder composition for producing a preform having good stability and a preform using the composition.
本発明は、かかる課題を解決するために、次のような手段を採用するものである。すなわち、本発明のバインダー組成物は、下記の構成要素（Ａ）および（Ｂ）から成り、該バインダー組成物は、そのガラス転移温度が７０〜１００℃の範囲であり、かつ、自己硬化性がないものであることを特徴とするものである。 The present invention employs the following means in order to solve such problems. That is, the binder composition of the present invention comprises the following components (A) and (B), the binder composition has a glass transition temperature in the range of 70 to 100 ° C., and has self-curing properties. It is characterized by not.
構成要素（Ａ）：１分子内にアルコール性水酸基またはアミド結合を２つ以上有する熱 可塑性樹脂
構成要素（Ｂ）：エポキシ樹脂
また、かかるバインダー組成物を構成する構成要素（Ａ）はガラス転移温度が１００〜１５０℃の熱可塑性樹脂であり、４０〜８０ｗｔ％含有することが好ましい。
Component (A): Thermoplastic resin having two or more alcoholic hydroxyl groups or amide bonds in the molecule Component (B): Epoxy resin The component (A) constituting the binder composition has a glass transition temperature. Is a thermoplastic resin having a temperature of 100 to 150 ° C., preferably 40 to 80 wt%.
本発明の強化繊維基材は、かかるバインダー組成物を含有する強化繊維基材で構成されていることを特徴とするものであり、好ましくはかかる強化繊維基材が、シート状またはテープ状の形状を有し、かつ、該バインダー組成物の含有量が目付で１〜３０ｇ／ｍ２の範囲であることを特徴とするものである。 The reinforcing fiber substrate of the present invention is characterized in that it is composed of a reinforcing fiber substrate containing such a binder composition, and preferably the reinforcing fiber substrate has a sheet-like or tape-like shape. And the content of the binder composition is in the range of 1 to 30 g / m 2 in weight per unit area.
また、本発明のプリフォームは、かかるシート状またはテープ状の強化繊維基材が積層されて成り、かつ、層間に、さらに該バインダー組成物を介在させることによって形態を固定してなることを特徴とするものである。 Further, the preform of the present invention is formed by laminating such a sheet-like or tape-like reinforcing fiber base material, and the form is fixed by further interposing the binder composition between layers. It is what.
さらに、本発明の繊維強化複合材料の製造方法は、かかるプリフォームに、さらに液状熱硬化性樹脂組成物を含浸させ、該バインダー組成物と該液状熱硬化性樹脂組成物を硬化させることを特徴とするものである。 Furthermore, the method for producing a fiber-reinforced composite material of the present invention is characterized in that the preform is further impregnated with a liquid thermosetting resin composition, and the binder composition and the liquid thermosetting resin composition are cured. It is what.
本発明のバインダー組成物を例えば繊維、フィルム、強化繊維ストランドあるいは強化繊維基材等に付与、含有させることにより、加熱により容易にプリフォーム化できるため、ＲＴＭ法による繊維強化複合材料製品の製造に適している。加えて本発明のバインダー組成物は熱安定性が良いため、調製や加工が容易であり、経済的および環境的に優れており、保存安定性が良い。 For example, by applying the binder composition of the present invention to a fiber, film, reinforcing fiber strand or reinforcing fiber base material, and the like, it can be easily preformed by heating. Are suitable. In addition, since the binder composition of the present invention has good thermal stability, it is easy to prepare and process, is economically and environmentally excellent, and has good storage stability.
また、上記バインダー組成物を含有した強化繊維基材にて作製したプリフォームを用いた繊維強化複合材料の製造方法については、プリフォームがかかるバインダー組成物にて形態が固定されているので取り扱いが容易であり、またプリフォーム端部において強化繊維の解れが生じにくく、成型品である繊維強化複合材料の端部処理量が少なくてすむことから低コスト化の効果を有する。 Moreover, about the manufacturing method of the fiber reinforced composite material using the preform produced with the reinforced fiber base material containing the said binder composition, since the form is fixed with the binder composition which preform requires, handling is possible. It is easy, and it is difficult for the reinforcing fibers to be unraveled at the end of the preform, and the amount of processing of the end of the fiber-reinforced composite material, which is a molded product, can be reduced.
まず、本発明のバインダー組成物は、下記の構成要素（Ａ）および（Ｂ）から成る。 First, the binder composition of the present invention comprises the following components (A) and (B).
構成要素（Ａ）：１分子内にアルコール性水酸基またはアミド結合を２つ以上有する熱 可塑性樹脂
構成要素（Ｂ）:エポキシ樹脂
本発明のバインダー組成物を構成する構成要素（Ａ）のアルコール性水酸基またはアミド結合は、水素結合性官能基であり、酸素原子または窒素に結合した水素原子と強い水素結合を形成する。従って強化繊維表面に存在するカルボキシル基や水酸基などの水素原子と水素結合し接着力を向上するものである。構成要素（Ａ）のアルコール性水酸基またはアミド結合は分子内の末端に存在しても良いが、分子を構成する繰り返し単位内に側鎖の形で存在している方が、少ない添加量で官能基モル数を増やせるため好ましい。かかるアルコール性水酸基を有する熱可塑性樹脂としては、ポリビニルホルマールやポリビニルブチラールなどのポリビニルアセタール樹脂、ポリビニルアルコール、フェノキシ樹脂などを使用することができる。
Component (A): Thermoplastic resin having two or more alcoholic hydroxyl groups or amide bonds in the molecule Component (B): Epoxy resin Alcoholic hydroxyl group of component (A) constituting the binder composition of the present invention Alternatively, the amide bond is a hydrogen bonding functional group and forms a strong hydrogen bond with a hydrogen atom bonded to an oxygen atom or nitrogen. Accordingly, hydrogen bonding with hydrogen atoms such as carboxyl groups and hydroxyl groups present on the surface of the reinforcing fiber is carried out to improve the adhesive force. The alcoholic hydroxyl group or amide bond of the component (A) may exist at the terminal in the molecule, but if it exists in the form of a side chain in the repeating unit constituting the molecule, it can be functionalized with a small addition amount. This is preferable because the number of moles of the group can be increased. Examples of the thermoplastic resin having an alcoholic hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, and phenoxy resins.
アミド結合を有する熱可塑性樹脂としては、ポリアミド、ポリイミド、ポリアミドイミド、ポリウレタン、尿素樹脂などを使用することができる。 As the thermoplastic resin having an amide bond, polyamide, polyimide, polyamideimide, polyurethane, urea resin, or the like can be used.
かかる構成要素（Ａ）はガラス転移温度が１００〜１５０℃であることが好ましい。ガラス転移温度が１００℃より低い場合は、得られた繊維強化複合材料の耐熱性、機械物性が低下する傾向を示す。また、ガラス転移温度が１５０℃より高い場合は、バインダー組成物を調整する際、最も経済的な熱をかけて混練する方法、すなわちニーダや押出機などによる混練が難しくなり、有機溶剤を用いて混合し、後に有機溶媒を除去するなどの加工が必要になり、経済面および環境面で問題となる可能性がでてくる。 Such component (A) preferably has a glass transition temperature of 100 to 150 ° C. When the glass transition temperature is lower than 100 ° C., the heat resistance and mechanical properties of the obtained fiber-reinforced composite material tend to decrease. If the glass transition temperature is higher than 150 ° C., the most economical method of kneading when adjusting the binder composition, that is, kneading by a kneader or an extruder becomes difficult, and an organic solvent is used. Processing such as mixing and subsequent removal of the organic solvent is required, which may cause problems in terms of economy and environment.
上記範囲のガラス転移温度を有し、水素結合性官能基を持つ熱可塑性樹脂としては、ポリビニルホルマールが最も好ましく用いることができる。 As the thermoplastic resin having a glass transition temperature in the above range and having a hydrogen bonding functional group, polyvinyl formal can be most preferably used.
本発明のバインダー組成物は、該構成要素（Ａ）を３０〜８０ｗｔ％含有することが好ましく、より好ましくは４０〜７０ｗｔ％である。かかる含有量が３０ｗｔ％未満では、強化繊維基材との接着性が乏しくなり、逆に８０ｗｔ％を超えると、バインダー組成物のガラス転移温度が高くなりすぎて、低温加工性が低下する傾向を示す。 The binder composition of the present invention preferably contains 30 to 80 wt% of the component (A), more preferably 40 to 70 wt%. If the content is less than 30 wt%, the adhesion to the reinforcing fiber substrate becomes poor. Conversely, if the content exceeds 80 wt%, the glass transition temperature of the binder composition becomes too high, and the low-temperature processability tends to decrease. Show.
本発明のバインダー組成物を構成する構成要素（Ｂ）のエポキシ樹脂は、分子内にエポキシ基を複数有するエポキシ化合物から成る。かかるエポキシ樹脂はエポキシ化合物単体でも良く、複数種の混合物であっても良い。かかるエポキシ化合物としては、例えば、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、テトラブロモビスフェノールＡジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、２，２’，６，６’−テトラメチル−４，４’−ビフェノールジグリシジルエーテル、Ｎ，Ｎ，Ｏ−トリグリシジル−ｍ−アミノフェノール、Ｎ，Ｎ，Ｏ−トリグリシジル−ｐ−アミノフェノール、Ｎ，Ｎ，Ｏ−トリグリシジル−４−アミノ−３−メチルフェノール、Ｎ，Ｎ−ジグリシジルアニリン、Ｎ，Ｎ−ジグリシジル−ｏ−トルイジン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−４，４’−メチレンジアニリン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−２，２’−ジエチル−４，４’−メチレンジアニリン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミン、１，３−ビス(ジグリシジルアミノメチル)シクロヘキサン、エチレングリコールジグリジジルエーテル、プロピレングリコールジグリシジルエーテル、ヘキサメチレングリコールジグリシジルエーテル、ネオペンチレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、フタル酸ジグリシジル、テレフタル酸ジグリシジル、ビニルシクロヘキセンジエポキシド、３，４−エポキシシクロヘキサンカルボン酸−３，４−エポキシシクロヘキシルメチル、アジピン酸ビス−３，４−エポキシシクロヘキシルメチル、１,６-ジヒドロキシナフタレンのジグリシジルエーテル、９,９-ビス（4-ヒドロキシフェニル）フルオレンのジグリシジルエーテル、トリス(ｐ-ヒドロキシフェニル)メタンのトリグリシジルエーテル、テトラキス(ｐ-ヒドロキシフェニル)エタンのテトラグリシジルエーテル、フェノールノボラックグリシジルエーテル、クレゾールノボラックグリシジルエーテル、フェノールとジシクロペンタジエンの縮合物のグリシジルエーテル、フェノールアラルキル樹脂のグリシジルエーテルなどを使用することができる。 The epoxy resin of the component (B) which comprises the binder composition of this invention consists of an epoxy compound which has multiple epoxy groups in a molecule | numerator. Such an epoxy resin may be an epoxy compound alone or a mixture of plural kinds. Examples of the epoxy compound include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, 2,2 ′, 6,6′-tetramethyl-4,4. '-Biphenol diglycidyl ether, N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3- Methylphenol, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline, N, N, N ′, N′-tetraglycidyl-2,2′-diethyl-4,4′-methylenedianiline N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (diglycidylaminomethyl) cyclohexane, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether , Neopentylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate, vinylcyclohexene diepoxide, 3,4-epoxycyclohexanecarboxylic acid 3,4 -Epoxycyclohexylmethyl, bis-3,4-epoxycyclohexylmethyl adipate, 1,6-dihydroxynaphthalene diglycidyl ether Diglycidyl ether of 9,9-bis (4-hydroxyphenyl) fluorene, triglycidyl ether of tris (p-hydroxyphenyl) methane, tetraglycidyl ether of tetrakis (p-hydroxyphenyl) ethane, phenol novolac glycidyl ether, cresol novolac A glycidyl ether, a glycidyl ether of a condensation product of phenol and dicyclopentadiene, a glycidyl ether of a phenol aralkyl resin, or the like can be used.
かかるエポキシ樹脂は、本発明のバインダー組成物のガラス転移温度を調整するために用いられる。そのためには、エポキシ樹脂のガラス転移温度は２０℃以下が好ましく、１０℃以下であればより好ましい。エポキシ樹脂のガラス転移温度が２０℃を超えると、可塑化効果が低いため配合量が多くなり、構成要素（Ａ）の配合量が少なくなるため強化繊維基材との接着性が悪くなる傾向がある。 Such an epoxy resin is used for adjusting the glass transition temperature of the binder composition of the present invention. For this purpose, the glass transition temperature of the epoxy resin is preferably 20 ° C. or lower, more preferably 10 ° C. or lower. If the glass transition temperature of the epoxy resin exceeds 20 ° C., the compounding amount increases because the plasticizing effect is low, and the adhesiveness to the reinforcing fiber base tends to deteriorate because the compounding amount of the component (A) decreases. is there.
本発明のバインダー組成物は、上記以外の他の成分をさらに含んでいても良い。例えば酸化防止剤、非溶解性の有機粒子、無機粒子等を使用することができる。特に有機粒子のうち、架橋ゴム粒子や非溶解性の熱可塑性樹脂粒子は、高靭性化効果を向上させるのに有効である。 The binder composition of the present invention may further contain components other than those described above. For example, antioxidants, insoluble organic particles, inorganic particles, and the like can be used. In particular, among organic particles, crosslinked rubber particles and non-soluble thermoplastic resin particles are effective in improving the toughening effect.
本発明のバインダー組成物は、ガラス転移温度が７０〜１００℃であることが必要である。ガラス転移温度が７０℃より低いと、保管中に粒子状等のバインダー組成物同士が融着するなどの不都合が起こる恐れがあり、１００℃よりも高いと、ホットメルトにより強化繊維基材へ接着させるのが困難になる。 The binder composition of the present invention needs to have a glass transition temperature of 70 to 100 ° C. If the glass transition temperature is lower than 70 ° C., there is a risk of inconveniences such as particulate binder compositions fusing together during storage. If the glass transition temperature is higher than 100 ° C., the glass transition temperature adheres to the reinforcing fiber substrate by hot melt. It becomes difficult to let you.
また、本発明のバインダー組成物は、構成要素（Ｂ）の硬化剤あるいは硬化触媒を配合しないため、自己硬化性がないことが特徴である。自己硬化性がある場合は保管中にバインダー組成物のガラス転移温度が上昇し、バインダーとしての機能が失われてしまうため好ましくない。 Moreover, since the binder composition of the present invention does not contain the curing agent or curing catalyst of the component (B), it is characterized by no self-curing property. If it is self-curing, the glass transition temperature of the binder composition increases during storage, and the function as a binder is lost, which is not preferable.
また、本発明のバインダー組成物のように自己硬化性がない場合は、熱的に安定なため様々な公知の方法で調製することができる。最も経済的な方法は、各成分を１５０〜２２０℃程度の比較的高温で、押出機やニーダなどを用いて混練する方法である。得られたバインダー組成物は、粉砕して粒子にしたり、口金から溶融押出することにより繊維やフィルムの形態に後加工したりすることもできる。 Moreover, when there is no self-hardening like the binder composition of this invention, since it is thermally stable, it can prepare by various well-known methods. The most economical method is a method of kneading each component at a relatively high temperature of about 150 to 220 ° C. using an extruder or a kneader. The obtained binder composition can be pulverized into particles, or post-processed into a fiber or film form by melt extrusion from a die.
もちろん、一度有機溶媒溶液を調製し、しかる後に有機溶媒を除去する方法も可能である。更に、有機溶剤溶液を水中に分散してエマルジョンとし、そのエマルジョンを加熱して有機溶媒を除去してディスパーションを調製する方法がある。ディスパーションはそのまま強化繊維の加工に用いることができ、また濾過して粒子を取り出し、その粒子を用いることもできる。 Of course, it is possible to prepare an organic solvent solution once and then remove the organic solvent. Further, there is a method of preparing a dispersion by dispersing an organic solvent solution in water to form an emulsion and heating the emulsion to remove the organic solvent. The dispersion can be used as it is for the processing of the reinforcing fiber, or the particles can be taken out by filtration and used.
本発明のバインダー組成物の形態としては、通孔を設けたフィルム、テープ、長繊維、短繊維、紡績糸、織物、ニット、不織布、網状体、粒子などを採用することができる。 As the form of the binder composition of the present invention, a film, tape, long fiber, short fiber, spun yarn, woven fabric, knit, non-woven fabric, net-like body, particle and the like provided with through holes can be employed.
例えば粒子形態を用いる場合、その平均粒径は０．１〜２００μｍが好ましく、１〜１５０μｍであれば更に好ましい。平均粒子径がこの範囲より小さい場合は製造することが困難であり、平均粒子径がこの範囲より大きい場合はプリフォームとしたときに強化繊維にうねりが生じて繊維強化複合材料の機械物性が低下したり、また、粒子が液状熱硬化樹脂に完全溶解あるいは膨潤しないため、系内に未反応エポキシ樹脂が残り、耐熱性、耐薬品性の低下と言った問題が生じる。 For example, when using a particle form, the average particle diameter is preferably 0.1 to 200 μm, more preferably 1 to 150 μm. When the average particle size is smaller than this range, it is difficult to produce, and when the average particle size is larger than this range, the reinforced fiber is swelled when preformed, and the mechanical properties of the fiber-reinforced composite material are reduced. In addition, since the particles do not completely dissolve or swell in the liquid thermosetting resin, an unreacted epoxy resin remains in the system, causing problems such as a decrease in heat resistance and chemical resistance.
本発明のバインダー組成物は強化繊維または強化繊維基材に付与して用いられる。強化繊維としては、炭素繊維、ガラス繊維、アラミド繊維、金属繊維など、あるいはこれらを組合せたものが好適に使用される。 The binder composition of the present invention is used by being applied to a reinforcing fiber or a reinforcing fiber substrate. As the reinforcing fiber, carbon fiber, glass fiber, aramid fiber, metal fiber, or a combination thereof is preferably used.
シート状基材への本発明のバインダー組成物の付与としては、基材の製造時に付与することも可能であり、既存の基材に後加工として付与することもできるし、後述のプリフォーム作成時に基材の積層と本発明のバインダー組成物の付与を交互に行うこともできる。 As the application of the binder composition of the present invention to a sheet-like substrate, it can also be applied during the production of the substrate, can also be applied as a post-processing to an existing substrate, and the preform creation described below Sometimes the lamination of the substrate and the application of the binder composition of the present invention can be performed alternately.
さらに別の方法として、強化繊維ストランドの表面に本発明のバインダー組成物を付与する方法も可能である。具体的には、強化繊維ストランドの表面に本発明のバインダー組成物の粒子を付着させ、加熱により固定する方法、強化繊維ストランドの表面に本発明のバインダー組成物の繊維を巻き付ける方法も使用することができる。 As another method, a method of applying the binder composition of the present invention to the surface of the reinforcing fiber strand is also possible. Specifically, the method of attaching the binder composition particles of the present invention to the surface of the reinforcing fiber strand and fixing by heating, and the method of winding the fibers of the binder composition of the present invention on the surface of the reinforcing fiber strand are also used. Can do.
本発明のバインダー組成物を織物、ニット、マット、扁平ストランド、扁平なブレイドなどのシートまたはテープ状基材の表面に付与する場合は、少なくとも片面に１〜３０ｇ／ｍ2の目付で付着していることが好ましい。目付が上記範囲より少ないと、形態固定や高靭性化の効果が少なく、目付が多いと、強化繊維ストランドあるいは強化繊維基材のみかけ体積が大きくなるため、強化繊維の体積含有率の大きい繊維強化複合材料の製造が困難になる、あるいは熱硬化性樹脂の含浸性が乏しくなるなどの不利が生じる。 When the binder composition of the present invention is applied to the surface of a woven fabric, knit, mat, flat strand, flat blade or other sheet or tape-like substrate, it adheres to at least one side with a basis weight of 1 to 30 g / m 2. Preferably it is. If the basis weight is less than the above range, the effect of fixing the form and increasing the toughness is small. There are disadvantages such as difficulty in manufacturing the composite material or poor impregnation of the thermosetting resin.
強化繊維のストランドに本発明のバインダー組成物を付与した後、これを用いて織物やブレイドなどの強化繊維基材を作製した後、プリフォームを作製することもできる。３次元ブレイドなどの基材を作成する場合は、そのままプリフォームとして用いることもできる。さらに本発明のバインダー組成物を付与したストランドは、マンドレルに捲回した後加熱して強化繊維ストランド同士を接着し、プリフォームを作製する方法にも用いられる。 After applying the binder composition of the present invention to the strands of reinforcing fibers, and using them to prepare reinforcing fiber substrates such as woven fabrics and braids, a preform can be prepared. When creating a substrate such as a three-dimensional blade, it can be used as a preform as it is. Furthermore, the strand provided with the binder composition of the present invention is also used in a method for producing a preform by winding the mandrel and then heating it to bond the reinforcing fiber strands together.
本発明のバインダー組成物を付与したシート状強化繊維基材は、所定の形状に切り出し、型の上で積層し、適切な熱と圧力を加えてプリフォームを作製するために用いることができる。加圧の手段はプレスを用いることもできるし、バギングして内部を−９０ｋＰａ以下まで真空ポンプで吸引して大気圧により加圧する方法を用いることもできる。プリフォームを作製するときの加熱の温度は、６０〜１５０℃であることが好ましい。プリフォームには、強化繊維と本発明のバインダー組成物の他にフォームコア、ハニカムコア、金属部品などを一体化させることも可能である。 The sheet-like reinforcing fiber substrate provided with the binder composition of the present invention can be cut into a predetermined shape, laminated on a mold, and used for producing a preform by applying appropriate heat and pressure. The pressurizing means can be a press, or a method of bagging and sucking the inside to −90 kPa or less with a vacuum pump and pressurizing with atmospheric pressure. The heating temperature for producing the preform is preferably 60 to 150 ° C. In addition to the reinforcing fiber and the binder composition of the present invention, a foam core, a honeycomb core, a metal part, and the like can be integrated into the preform.
上記のようにして得られた本発明のプリフォームは、ＲＴＭ法に好適に用いられる。 The preform of the present invention obtained as described above is suitably used for the RTM method.
すなわち、本発明の繊維強化複合材料の製造方法は、本発明のプリフォームに液状熱硬化性樹脂組成物を含浸させ、上記バインダー組成物と液状熱硬化性樹脂組成物を硬化させることを特徴とするものである。 That is, the method for producing a fiber-reinforced composite material of the present invention is characterized in that the preform of the present invention is impregnated with a liquid thermosetting resin composition, and the binder composition and the liquid thermosetting resin composition are cured. To do.
ＲＴＭ法においてプリフォームを設置する成形型としては、剛体からなるクローズドモールドを用いてもよいし、剛体のオープンモールドと可撓性のフィルム（バッグ）を用いてもよい。後者の場合、プリフォームは剛体オープンモールドと可撓性フィルムの間に設置する。剛体型の材料としては、金属（スチール、アルミニウムなど）、ＦＲＰ、木材、石膏などを用いることができる。可撓性のフィルムの材料としては、ナイロン、フッ素樹脂、シリコーン樹脂などを用いることができる。 As a mold for installing the preform in the RTM method, a closed mold made of a rigid body may be used, or a rigid open mold and a flexible film (bag) may be used. In the latter case, the preform is placed between the rigid open mold and the flexible film. As the rigid material, metal (steel, aluminum, etc.), FRP, wood, plaster, etc. can be used. As a material for the flexible film, nylon, fluorine resin, silicone resin, or the like can be used.
ＲＴＭの具体的な手順としては、剛体のクローズドモールドを用いる場合は、加圧して型締めし、液状熱硬化性樹脂組成物を加圧して注入すると良い。このとき、注入口とは別に吸引口を設け、真空ポンプに接続して吸引しても良い。あるいは、吸引を行いながら、加圧手段は特に用いず大気圧で液状熱硬化性樹脂組成物を注入しても良い。 As a specific procedure of RTM, when a rigid closed mold is used, it is preferable to pressurize and clamp and inject the liquid thermosetting resin composition under pressure. At this time, a suction port may be provided separately from the injection port, and suction may be performed by connecting to a vacuum pump. Or you may inject | pour a liquid thermosetting resin composition at atmospheric pressure, using especially a pressurizing means, performing suction.
また、剛体のオープンモールドと可撓性フィルムを用いる場合は、通常は、吸引と大気圧による注入を採用できる。大気圧による注入で、良好な含浸を実現するためには、樹脂拡散媒体を用いることが有効である。また、プリフォームの設置に先立って、剛体型の表面にゲルコートを塗布することも好ましい。プリフォームを設置した後、型締めあるいはバギングを行い、続いて液状熱硬化性樹脂組成物の注入を行う。 Moreover, when using a rigid open mold and a flexible film, suction and injection by atmospheric pressure can be usually employed. In order to achieve good impregnation by injection at atmospheric pressure, it is effective to use a resin diffusion medium. It is also preferable to apply a gel coat to the rigid surface prior to installation of the preform. After the preform is placed, mold clamping or bagging is performed, and then the liquid thermosetting resin composition is injected.
液状熱硬化性樹脂組成物は、主にモノマー成分からなる液状樹脂とモノマー成分を３次元架橋させてポリマー化する硬化剤あるいは硬化触媒とからなる。 The liquid thermosetting resin composition is mainly composed of a liquid resin composed of a monomer component and a curing agent or a curing catalyst for polymerizing the monomer component by three-dimensionally crosslinking the monomer component.
該液状樹脂としては、本発明のバインダー組成物との反応性や相溶性などの点からエポキシ樹脂が好ましい。 The liquid resin is preferably an epoxy resin from the viewpoint of reactivity and compatibility with the binder composition of the present invention.
かかる液状エポキシ樹脂としては、ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、テトラブロモビスフェノールＡジグリシジルエーテル、ビスフェノールＡＤジグリシジルエーテル、２，２’，６，６’−テトラメチル−４，４’−ビフェノールジグリシジルエーテル、Ｎ，Ｎ，Ｏ−トリグリシジル−ｍ−アミノフェノール、Ｎ，Ｎ，Ｏ−トリグリシジル−ｐ−アミノフェノール、Ｎ，Ｎ，Ｏ−トリグリシジル−４−アミノ−３−メチルフェノール、Ｎ，Ｎ−ジグリシジルアニリン、Ｎ，Ｎ−ジグリシジル−ｏ−トルイジン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−４，４’−メチレンジアニリン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−２，２’−ジエチル−４，４’−メチレンジアニリン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジル−ｍ−キシリレンジアミン、１，３−ビス(ジグリシジルアミノメチル)シクロヘキサン、エチレングリコールジグリジジルエーテル、プロピレングリコールジグリシジルエーテル、ヘキサメチレングリコールジグリシジルエーテル、ネオペンチレングリコールジグリシジルエーテル、ソルビトールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、フタル酸ジグリシジル、テレフタル酸ジグリシジル．、ビニルシクロヘキセンジエポキシド、３，４−エポキシシクロヘキサンカルボン酸−３，４−エポキシシクロヘキシルメチル、アジピン酸ビス−３，４−エポキシシクロヘキシルメチル、１,６-ジヒドロキシナフタレンのジグリシジルエーテル、９,９-ビス（4-ヒドロキシフェニル）フルオレンのジグリシジルエーテル、トリス(ｐ-ヒドロキシフェニル)メタンのトリグリシジルエーテル、テトラキス(ｐ-ヒドロキシフェニル)エタンのテトラグリシジルエーテル、フェノールノボラックグリシジルエーテル、クレゾールノボラックグリシジルエーテル、フェノールとジシクロペンタジエンの縮合物のグリシジルエーテル、フェノールアラルキル樹脂のグリシジルエーテル、トリグリシジルイソシアヌレート、Ｎ−グリシジルフタルイミド、５−エチル−１，３−ジグリシジル−５−メチルヒダントイン、１，３−ジグリシジル−５，５−ジメチルヒダントイン、ビスフェノールＡジグリシジルエーテルとトリレンイソシアネートの付加により得られるオキサゾリドン型エポキシ樹脂、フェノールアラルキル型エポキシなどを使用することができる。 Such liquid epoxy resins include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol AD diglycidyl ether, 2,2 ′, 6,6′-tetramethyl-4,4 ′. -Biphenol diglycidyl ether, N, N, O-triglycidyl-m-aminophenol, N, N, O-triglycidyl-p-aminophenol, N, N, O-triglycidyl-4-amino-3-methyl Phenol, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, N, N, N ′, N′-tetraglycidyl-4,4′-methylenedianiline, N, N, N ′, N '-Tetraglycidyl-2,2'-diethyl-4,4'-methylenedianiline, N, , N ′, N′-tetraglycidyl-m-xylylenediamine, 1,3-bis (diglycidylaminomethyl) cyclohexane, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, neopenty Lenglycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, diglycidyl phthalate, diglycidyl terephthalate. , Vinylcyclohexene diepoxide, 3,4-epoxycyclohexanecarboxylic acid-3,4-epoxycyclohexylmethyl, bis-3,4-epoxycyclohexylmethyl adipate, diglycidyl ether of 1,6-dihydroxynaphthalene, 9,9- Diglycidyl ether of bis (4-hydroxyphenyl) fluorene, triglycidyl ether of tris (p-hydroxyphenyl) methane, tetraglycidyl ether of tetrakis (p-hydroxyphenyl) ethane, phenol novolac glycidyl ether, cresol novolac glycidyl ether, phenol And glycidyl ether of condensate of dicyclopentadiene, glycidyl ether of phenol aralkyl resin, triglycidyl isocyanurate, N-glycidyl phthalimide, 5- Cyl-1,3-diglycidyl-5-methylhydantoin, 1,3-diglycidyl-5,5-dimethylhydantoin, oxazolidone type epoxy resin obtained by addition of bisphenol A diglycidyl ether and tolylene isocyanate, phenol aralkyl type epoxy, etc. Can be used.
硬化剤としては、脂肪族ポリアミン、芳香族ポリアミン、酸無水物、イミダゾール、ルイス酸錯体等が適しており、目的用途により適宜選択して用いる。 As the curing agent, aliphatic polyamines, aromatic polyamines, acid anhydrides, imidazoles, Lewis acid complexes and the like are suitable, and they are appropriately selected and used depending on the intended use.
液状熱硬化性樹脂組成物の注入の際、バインダー組成物の溶解やその後の硬化が円滑に行われるよう、３０〜９０℃程度に型を加熱しながら注入を行うと良い。 When injecting the liquid thermosetting resin composition, the injection is preferably performed while heating the mold at about 30 to 90 ° C. so that the binder composition can be dissolved and then cured smoothly.
液状熱硬化性樹脂組成物の注入の後に、加熱硬化を行う。加熱硬化時の型の温度は、液状熱硬化性樹脂組成物の注入時における型の温度と同じでも良いが、低温での硬化の場合、脱型の際に繊維強化複合材料が変形しない程度の剛性が得られるまで硬化を進めるのに時間がかかる場合があるため、注入時の型の温度より高い温度を選ぶことが好ましく、例えば６０〜１８０℃の範囲が好ましい。また、加熱硬化の時間は１〜２０時間が好ましい。 Heat-curing is performed after injection | pouring of a liquid thermosetting resin composition. The temperature of the mold at the time of heat curing may be the same as the temperature of the mold at the time of injection of the liquid thermosetting resin composition, but in the case of curing at a low temperature, the fiber reinforced composite material is not deformed at the time of demolding. Since it may take time to advance curing until rigidity is obtained, it is preferable to select a temperature higher than the temperature of the mold at the time of injection, for example, a range of 60 to 180 ° C is preferable. The time for heat curing is preferably 1 to 20 hours.
加熱硬化の過程において、本発明のバインダー組成物は、一旦、液状熱硬化性樹脂組成物に溶解させるか、あるいは液状熱硬化性樹脂組成物により膨潤させることが好ましい。そうすることで、バインダー組成物の構成要素（Ｂ）であるエポキシ樹脂と熱硬化性樹脂組成物中の硬化剤が接触し、硬化反応を開始するため加熱硬化後に未反応のエポキシ樹脂を残存させず、繊維強化複合材料の靭性等の機械物性や、耐熱性、耐薬品性等を良好なものとすることができる。 In the process of heat curing, the binder composition of the present invention is preferably once dissolved in the liquid thermosetting resin composition or swollen with the liquid thermosetting resin composition. By doing so, the epoxy resin which is the component (B) of the binder composition comes into contact with the curing agent in the thermosetting resin composition, and the unreacted epoxy resin remains after heat curing in order to start the curing reaction. In addition, mechanical properties such as toughness, heat resistance, chemical resistance, and the like of the fiber reinforced composite material can be improved.
このように硬化の前に、一旦、バインダー組成物を溶解させるか、あるいは膨潤させるといった態様は、バインダー組成物の形状や、バインダー組成物と液状熱硬化性樹脂組成物の樹脂の組み合わせや、バインダー組成物中の熱可塑性樹脂、また加熱温度条件を適宜選択することにより達成される。 As described above, before curing, the mode in which the binder composition is once dissolved or swollen depends on the shape of the binder composition, the combination of the binder composition and the resin of the liquid thermosetting resin composition, the binder, This is achieved by appropriately selecting the thermoplastic resin in the composition and the heating temperature condition.
加熱硬化の後、脱型して繊維強化複合材料を取り出す。 After heat curing, the mold is removed and the fiber reinforced composite material is taken out.
その後、繊維強化複合材料を硬化温度よりも高い温度で加熱する、後硬化を行ってもよい。後硬化の温度は９０〜２００℃が好ましく、時間は１〜４時間が好ましい。 Thereafter, post-curing may be performed in which the fiber-reinforced composite material is heated at a temperature higher than the curing temperature. The post-curing temperature is preferably 90 to 200 ° C., and the time is preferably 1 to 4 hours.
前述の様に本発明のバインダー組成物等はＲＴＭ法に特に適したものであるが、ＲＴＭ法以外の成形法にも好適に用いることができる。 As described above, the binder composition of the present invention is particularly suitable for the RTM method, but can also be suitably used for molding methods other than the RTM method.
例えば、本発明のバインダー組成物を付与した強化繊維基材の形状がストランドやテープ状の場合にはフィラメントワインディング法、プルトルージョン法、プリプレグ法等にも適しており、シート状の場合にはハンドレイアップ法、プリプレグ法等にも適している。 For example, when the reinforcing fiber substrate to which the binder composition of the present invention is applied is in the form of a strand or a tape, it is suitable for the filament winding method, the pultrusion method, the prepreg method, etc. Suitable for lay-up method, prepreg method, etc.
本発明のバインダー組成物等を用いて製造した繊維強化複合材料は、生産性がよく、靭性に優れるため、宇宙機、航空機、鉄道車両、自動車、船舶などの構造材料に好適に用いることができる。 The fiber-reinforced composite material produced using the binder composition of the present invention has good productivity and excellent toughness, and therefore can be suitably used for structural materials such as spacecraft, aircraft, railway vehicles, automobiles and ships. .
以下、実施例によって本発明をさらに具体的に説明する。尚、組成比の単位「部」は、特に注釈のない限り重量部を意味する。 Hereinafter, the present invention will be described more specifically with reference to examples. The unit “part” of the composition ratio means part by weight unless otherwise specified.
＜炭素繊維織物の製造＞
実施例で用いた炭素繊維織物は以下のように作成した。
<Manufacture of carbon fiber fabrics>
The carbon fiber fabric used in the examples was prepared as follows.
炭素繊維Ｔ３００Ｂ−３Ｋ−４０Ｂ（東レ（株）製）を経糸および緯糸に用いて平織の織物を作成した。 A plain woven fabric was prepared using carbon fibers T300B-3K-40B (manufactured by Toray Industries, Inc.) as warps and wefts.
経糸密度および緯糸密度はそれぞれ５本／１０ｍｍとした。 The warp density and the weft density were 5/10 mm each.
織物の炭素繊維目付は２００ｇ／ｍ2であった。 The carbon fiber basis weight of the woven fabric was 200 g / m 2 .
＜バインダー樹脂のガラス転移温度測定方法＞
ＪＩＳ−Ｋ７１２１に従い、ＤＳＣ法で中間点ガラス転移温度を求めた。測定装置にはＰｙｒｉｓ１ ＤＳＣ（Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）を用いて窒素雰囲気下において昇温速度４０℃／分で測定した。
<Method for measuring glass transition temperature of binder resin>
In accordance with JIS-K7121, the midpoint glass transition temperature was determined by DSC method. A Pyris1 DSC (manufactured by Perkin Elmer) was used as a measuring apparatus, and measurement was performed at a temperature rising rate of 40 ° C./min in a nitrogen atmosphere.
＜バインダーの保存安定性評価＞
バインダー組成物をＤＳＣ（Ｐｙｒｉｓ１ ＤＳＣ、Ｐｅｒｋｉｎ Ｅｌｍｅｒ社製）用アルミサンプルパンに５−１０ｍｇ採取し、１８０℃の熱風乾燥機中で５時間エージングを行った後、前記ガラス転移温度測定方法に従ってガラス転移温度を測定し、エージング前と比較を行った。
<Evaluation of storage stability of binder>
5-10 mg of the binder composition was sampled in an aluminum sample pan for DSC (Pyris1 DSC, manufactured by Perkin Elmer), aged in a hot air dryer at 180 ° C. for 5 hours, and then subjected to the glass transition temperature measurement method. The temperature was measured and compared with that before aging.
＜平均粒子径の測定方法＞
レーザー解析・散乱式粒度分布測定機ＬＭＳ−２４（（株）セイシン企業製）を用い、取り込み回数５００回で測定した。
<Measurement method of average particle diameter>
Using a laser analysis / scattering type particle size distribution analyzer LMS-24 (manufactured by Seishin Enterprise Co., Ltd.), the number of uptakes was 500 times.
実施例１
以下の処方により、樹脂等を混合してスラリーとし、２軸押出機により１８０℃で混練して、本発明のバインダー組成物のペレットを得た。
・ポリビニルホルマール（“ビニレック”Ｋタイプ、窒素（株）製）
：６０部。
・液状ビスフェノールＡ型エポキシ樹脂（“エピコート”８２８、ジャパンエポキシレジン（株）製）
：１０部。
・固形ビスフェノールＡ型エポキシ樹脂（“エピコート”１００１、ジャパンエポキシレジ ン（株）製）
：３０部。
Example 1
According to the following formulation, resin or the like was mixed to form a slurry, and kneaded at 180 ° C. by a twin-screw extruder to obtain pellets of the binder composition of the present invention.
・ Polyvinyl formal ("Vinylec" K type, manufactured by Nitrogen Corporation)
: 60 parts.
・ Liquid bisphenol A epoxy resin ("Epicoat" 828, manufactured by Japan Epoxy Resin Co., Ltd.)
: 10 parts.
・ Solid bisphenol A type epoxy resin ("Epicoat" 1001, manufactured by Japan Epoxy Resin Co., Ltd.)
: 30 parts.
バインダー組成物のガラス転移温度を前記測定方法にて測定したところ、７１℃であった。バインダー組成物の保存安定性を前記測定方法にて測定したところ、７２℃であり、ガラス転移温度はほとんど変化しておらず保存安定性は良好であった。このペレットをハンマーミル（ＰＵＬＶＥＲＩＺＥＲ、ホソカワミクロン（株）製）にて液体窒素を用いて凍結粉砕して粒子状バインダー組成物を得た。バインダー組成物の平均粒子径を前記測定方法にて測定したところ、平均粒径約１２０μｍの粒子であった。この粒子を前記の炭素繊維織物の片面に１０g/ｍ2の散布量で散布した後、表面温度が１６０℃になるように遠赤ヒーターを用いて加熱してバインダー組成物を付与した本発明の強化繊維基材を得た。この基材の粒子付着面を指で擦っても、粒子の脱落は起こらなかった。 It was 71 degreeC when the glass transition temperature of the binder composition was measured by the said measuring method. When the storage stability of the binder composition was measured by the above measuring method, it was 72 ° C., and the glass transition temperature was hardly changed and the storage stability was good. This pellet was freeze-ground using liquid nitrogen with a hammer mill (PULVERIZER, manufactured by Hosokawa Micron Corporation) to obtain a particulate binder composition. When the average particle diameter of the binder composition was measured by the above measuring method, the average particle diameter was about 120 μm. The particles were dispersed on one side of the carbon fiber woven fabric at an application amount of 10 g / m 2 and then heated using a far-infrared heater so that the surface temperature was 160 ° C. to give a binder composition. A reinforcing fiber substrate was obtained. Even when the particle adhering surface of the substrate was rubbed with a finger, the particles did not fall off.
実施例２
以下の処方により、実施例１と同様にして本発明のバインダー組成物のペレットを得た。
・グリルアミド（“ＧＲＩＬＡＭＩＤ”ＴＲ−５５、三菱化学工業（株）製）
：６０部。
・液状ビスフェノールＦ型エポキシ樹脂（“エピコート”８０６、ジャパンエポキシレジン（株）製）
：１５部。
・固形ビスフェノールＡ型エポキシ樹脂（“エピコート”１００１、ジャパンエポキシレジン（株）製）
：２５部。
Example 2
With the following formulation, pellets of the binder composition of the present invention were obtained in the same manner as in Example 1.
・ Grill amide ("GRILAMID" TR-55, manufactured by Mitsubishi Chemical Corporation)
: 60 parts.
・ Liquid bisphenol F type epoxy resin ("Epicoat" 806, manufactured by Japan Epoxy Resin Co., Ltd.)
: 15 parts.
・ Solid bisphenol A type epoxy resin ("Epicoat" 1001, manufactured by Japan Epoxy Resin Co., Ltd.)
: 25 parts.
バインダー組成物のガラス転移温度を実施例１と同様に求めたところ、７８℃であった。 When the glass transition temperature of the binder composition was determined in the same manner as in Example 1, it was 78 ° C.
バインダー組成物の保存安定性を実施例１と同様に測定したところ、７７℃であり、ガラス転移温度はほとんど変化しておらず保存安定性は良好であった。このペレットを実施例１と同様に凍結粉砕して粒子状バインダー組成物を得た。バインダー組成物の平均粒子径を実施例１と同様に測定したところ、平均粒径約１２０μｍであった。この粒子を用いて、実施例１と同様の条件で本発明の強化繊維基材を作製した。この基材の粒子付着面を指で擦っても、粒子の脱落は起こらなかった。 When the storage stability of the binder composition was measured in the same manner as in Example 1, it was 77 ° C., and the glass transition temperature was hardly changed, and the storage stability was good. This pellet was freeze-ground in the same manner as in Example 1 to obtain a particulate binder composition. When the average particle size of the binder composition was measured in the same manner as in Example 1, the average particle size was about 120 μm. Using these particles, a reinforcing fiber substrate of the present invention was produced under the same conditions as in Example 1. Even when the particle adhering surface of the substrate was rubbed with a finger, the particles did not fall off.
比較例１
以下の成分をバインダー組成物とした。
・固形ビスフェノールＡ型エポキシ樹脂（“エピコート”１００３、ジャパンエポキシレジン（株）製）
：１００部。
Comparative Example 1
The following components were used as a binder composition.
・ Solid bisphenol A type epoxy resin ("Epicoat" 1003, manufactured by Japan Epoxy Resin Co., Ltd.)
: 100 parts.
バインダー組成物のガラス転移温度を前記測定方法にて測定したところ、５８℃であった。バインダー組成物の保存安定性を実施例１と同様に測定したところ、６１℃であり、ガラス転移温度はほとんど変化しておらず保存安定性は良好であった。 It was 58 degreeC when the glass transition temperature of the binder composition was measured by the said measuring method. When the storage stability of the binder composition was measured in the same manner as in Example 1, it was 61 ° C., and the glass transition temperature was hardly changed, and the storage stability was good.
バインダー組成物を実施例１と同様に凍結粉砕して粒子を得た。平均粒子径を実施例１と同様に測定したところ、平均粒径約８５μｍであった。この粒子を用いて、実施例１と同様の条件で強化繊維基材を作製した。この基材の粒子付着面を指で擦ったところ、粒子の脱落が起こった。 The binder composition was freeze-ground in the same manner as in Example 1 to obtain particles. When the average particle size was measured in the same manner as in Example 1, the average particle size was about 85 μm. Using these particles, a reinforcing fiber substrate was produced under the same conditions as in Example 1. When the particle adhering surface of the substrate was rubbed with a finger, the particles dropped out.
比較例２
以下の成分をバインダー組成物とした。
・ポリビニルホルマール（“ビニレック”Ｋタイプ、窒素（株）製）
：１００部。
Comparative Example 2
The following components were used as a binder composition.
・ Polyvinyl formal ("Vinylec" K type, manufactured by Nitrogen Corporation)
: 100 parts.
バインダー組成物のガラス転移温度を前記測定方法にて測定したところ、１１０℃であった。 It was 110 degreeC when the glass transition temperature of the binder composition was measured by the said measuring method.
バインダー組成物の保存安定性を実施例１と同様に測定したところ、１１０℃であり、ガラス転移温度はほとんど変化しておらず保存安定性は良好であった。バインダー組成物を実施例１と同様に凍結粉砕して粒子をえた。平均粒子径を実施例１と同様に測定したところ、平均粒径約９０μｍであった。この粒子を用いて、実施例１と同様の条件で強化繊維基材を作製した。この基材の粒子付着面を指で擦ったところ、粒子の脱落が起こった。 When the storage stability of the binder composition was measured in the same manner as in Example 1, it was 110 ° C., and the glass transition temperature was hardly changed, and the storage stability was good. The binder composition was freeze-ground in the same manner as in Example 1 to obtain particles. When the average particle size was measured in the same manner as in Example 1, the average particle size was about 90 μm. Using these particles, a reinforcing fiber substrate was produced under the same conditions as in Example 1. When the particle adhering surface of the substrate was rubbed with a finger, the particles dropped out.
比較例３
以下の処方を濃度が１０ｗｔ％になるように塩化メチレンに溶かした溶液を５００ｇ調製した。塩化メチレン溶液をドデシルベンゼンスルホン酸ナトリウム１ｗｔ％水溶液１０００ｇにホモミキサーを用いて分散させてエマルジョン溶液を得た。得られたエマルジョン溶液を６０℃に加熱して塩化メチレンを除去し、サスペンションとした。このサスペンションを濾過して粒子を取り出し、３０℃の真空乾燥機中で２４時間乾燥してバインダー組成物を得た。
・ポリエーテルスルホン（“スミカエクセル”ＰＥＳ５００３Ｐ、住友化学（株）製を凍結粉砕して得た粉末）
：６０部。
・液状ビスフェノールＦ型エポキシ樹脂（“エピコート”８０６、ジャパンエポキシレジン（株）製）
：３１．５部。
・液状芳香族ポリアミン（“エピキュア”Ｗ、ジャパンエポキシレジン（株）製）
：８．５部。
Comparative Example 3
500 g of a solution prepared by dissolving the following formulation in methylene chloride so as to have a concentration of 10 wt% was prepared. The methylene chloride solution was dispersed in 1000 g of a 1 wt% aqueous solution of sodium dodecylbenzenesulfonate using a homomixer to obtain an emulsion solution. The obtained emulsion solution was heated to 60 ° C. to remove methylene chloride to obtain a suspension. The suspension was filtered to take out particles and dried in a vacuum dryer at 30 ° C. for 24 hours to obtain a binder composition.
・ Polyethersulfone ("Sumika Excel" PES5003P, powder obtained by freeze-grinding Sumitomo Chemical Co., Ltd.)
: 60 parts.
・ Liquid bisphenol F type epoxy resin ("Epicoat" 806, manufactured by Japan Epoxy Resin Co., Ltd.)
: 31.5 parts.
・ Liquid aromatic polyamine ("Epicure" W, manufactured by Japan Epoxy Resin Co., Ltd.)
: 8.5 parts.
バインダー組成物のガラス転移温度を前記測定方法にて測定したところ、５３℃であった。バインダー組成物の保存安定性を実施例１と同様に測定したところ、１６３℃であり、ガラス転移温度はかなり上昇しておりホットメルト性は消失していた。バインダー組成物の平均粒子径を実施例１と同様に測定したところ、平均粒子径は３０μｍであった。この粒子を用いて、実施例１と同様の条件で強化繊維基材を作製した。この基材の粒子付着面を指で擦ったところ、粒子の脱落が起こった。 It was 53 degreeC when the glass transition temperature of the binder composition was measured by the said measuring method. The storage stability of the binder composition was measured in the same manner as in Example 1. As a result, it was 163 ° C., the glass transition temperature was considerably increased, and the hot melt property was lost. When the average particle diameter of the binder composition was measured in the same manner as in Example 1, the average particle diameter was 30 μm. Using these particles, a reinforcing fiber substrate was produced under the same conditions as in Example 1. When the particle adhering surface of the substrate was rubbed with a finger, the particles dropped out.
本発明は、上述したように宇宙機、航空機、鉄道車両、自動車、船舶などの構造材料に好適に用いることができるが、その他テニスラケット、ゴルフシャフト、釣り竿などのレジャー産業や建築等の分野にも適用することが出来る。 As described above, the present invention can be suitably used for structural materials such as spacecrafts, aircrafts, railway vehicles, automobiles, ships, etc., but also in the fields of leisure industries such as tennis rackets, golf shafts, fishing rods, and construction. Can also be applied.
Claims (11)
構成要素（Ａ）：１分子内にアルコール性水酸基またはアミド結合を２つ以上有する 熱可塑性樹脂
構成要素（Ｂ）：エポキシ樹脂 A binder composition for producing a preform, comprising the following components (A) and (B), the binder composition having a glass transition temperature in the range of 70 to 100 ° C., and self A binder composition characterized by having no curability.
Component (A): Thermoplastic resin having two or more alcoholic hydroxyl groups or amide bonds in the molecule Component (B): Epoxy resin
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| WO2014007288A1 (en) | 2012-07-05 | 2014-01-09 | 東レ株式会社 | Binder resin composition for preform, binder particle, preform, and fiber-reinforced composite material |
| WO2015079917A1 (en) | 2013-11-29 | 2015-06-04 | 東レ株式会社 | Reinforcing fiber fabric substrate, preform, and fiber-reinforced composite material |
| US9062203B2 (en) | 2009-09-16 | 2015-06-23 | Tory Industries Inc. | Binder composition, reinforcing-fiber base material, preform, fiber-reinforced composite material, and manufacturing method therefor |
| WO2017104445A1 (en) | 2015-12-17 | 2017-06-22 | 東レ株式会社 | Binder resin composition for preform, binder particles, reinforced fiber substrate, preform, and fiber-reinforced composite material |
| WO2017104771A1 (en) * | 2015-12-16 | 2017-06-22 | Jnc株式会社 | Composite sheet and electronic device |
| KR101790976B1 (en) * | 2015-11-17 | 2017-10-27 | 주식회사 성우하이텍 | Binder spray device for preform of complex materials |
| JP2020506091A (en) * | 2017-02-02 | 2020-02-27 | サフラン セラミクス | Manufacturing method of composite material parts |
| US10792869B2 (en) | 2015-02-05 | 2020-10-06 | Toray Industries, Inc. | Preform, fiber-reinforced composite material, and method of manufacturing fiber-reinforced composite material |
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| JPH0820654A (en) * | 1994-07-06 | 1996-01-23 | Mitsubishi Chem Corp | Epoxy resin composition and prepreg using the same |
| JPH11302411A (en) * | 1998-02-19 | 1999-11-02 | Sumitomo Bakelite Co Ltd | Preparation of prepreg and laminate |
| JP2003055534A (en) * | 2001-08-14 | 2003-02-26 | Nippon Oil Corp | Resin composition for composite material, intermediate material for composite material, and composite material |
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| WO2014007288A1 (en) | 2012-07-05 | 2014-01-09 | 東レ株式会社 | Binder resin composition for preform, binder particle, preform, and fiber-reinforced composite material |
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| US10053575B2 (en) | 2012-07-05 | 2018-08-21 | Toray Industries, Inc. | Binder resin composition for preform, binder particle, preform, and fiber-reinforced composite material |
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| CN108350253A (en) * | 2015-12-17 | 2018-07-31 | 东丽株式会社 | Preform adhesive resin composition, binder particles, reinforcing-fiber substrate, preform and fibre reinforced composites |
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