TW201009008A - Toughness increased epoxy resin composition, composite material made from the same and laminate - Google Patents
Toughness increased epoxy resin composition, composite material made from the same and laminate Download PDFInfo
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- TW201009008A TW201009008A TW97133251A TW97133251A TW201009008A TW 201009008 A TW201009008 A TW 201009008A TW 97133251 A TW97133251 A TW 97133251A TW 97133251 A TW97133251 A TW 97133251A TW 201009008 A TW201009008 A TW 201009008A
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 99
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- 239000002131 composite material Substances 0.000 title claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 68
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- 229920005749 polyurethane resin Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims 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 claims description 7
- 239000012779 reinforcing material Substances 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
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- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- -1 amine modified carbon nanotube Chemical class 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000779 smoke Substances 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 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 claims 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- 229930003836 cresol Natural products 0.000 claims 1
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 42
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- 239000000463 material Substances 0.000 description 12
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- 239000011159 matrix material Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000005060 rubber Substances 0.000 description 7
- 229920000049 Carbon (fiber) Polymers 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000004917 carbon fiber Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000001066 destructive effect Effects 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920000768 polyamine Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
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- 239000002048 multi walled nanotube Substances 0.000 description 2
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- 235000021419 vinegar Nutrition 0.000 description 2
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- PONXTPCRRASWKW-UHFFFAOYSA-N 1,2-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1C(N)C(N)C1=CC=CC=C1 PONXTPCRRASWKW-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical group ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 241001343354 Halenia corniculata Species 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical class [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 1
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- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
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- 238000002347 injection Methods 0.000 description 1
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- 239000004816 latex Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000005906 menstruation Effects 0.000 description 1
- NCPHGZWGGANCAY-UHFFFAOYSA-N methane;ruthenium Chemical compound C.[Ru] NCPHGZWGGANCAY-UHFFFAOYSA-N 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
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- Reinforced Plastic Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
201009008 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種環氧樹脂組成物，特別是指一種 增章刃型環氧樹脂組成物，及應用其製得的_種複合材料及 一種積層板。 【先前技術】201009008 IX. Description of the invention: [Technical field of the invention] The present invention relates to an epoxy resin composition, in particular to an additive-edge type epoxy resin composition, and a composite material thereof obtained by using the same A laminated board. [Prior Art]
、複合材料的種類很多且目前已廣泛地被運用於很多領 域上’其t ’以樹脂類複合材料的應用最為廣泛，而在眾 多的樹脂中’又以環氧樹脂因具有良好接著性、機械性質 、邑緣及加JL性質等優點而成為業界較常使用的樹脂材 料。但是’環氧樹脂在固化後，質地會變脆而易破損，並 降低抗衝擊性聽性，使得其應㈣®受到限制。 囚此 " 資便用％氧樹脂來製備複合材料時，勢必要對 環乳樹脂進行改質’而目前已研發並被使用之經改質的環 氧樹脂材料有橡膠增_氧樹脂（㈣⑽⑽㈣印㈣）、 剛性粒子填充環氧樹脂（_ particle_fmed ep〇xy)及熱塑性 4t m (thermoplastic resin-toughened ep〇xy) # ’以橡膠增_氧樹脂為例，此類型的環氧樹脂是藉由添 t橡膠粒子來增加其_，但是由於橡膠粒子與環氧樹脂 疋不相容的’所以還是可能會影響後續製作出的複合材料 的機械性質。 月經於此’發明人曾在 «一立vv A間现ZUU5 i 9495中揭示一 種異於以往的改質方式所製備出來的經改f之環氧樹脂組 成物其係包含-基質混合物，且該基質混合物具有—環 5 201009008 氧樹脂及一重量平均分子量是介於4000至6〇〇〇之間且具 有特殊結構的聚合物，此種經改質之環氧樹脂組成物具有 不錯之熱性質及機械性質，但是當要將其應用於製備需要 較南彳示準的機械性質的產品，例如運輸工具等時，其機械 性質仍有改善的空間。 在射出成型的塑膠製程中，曾有人藉由添加經改質的 奈米碳管來增強該塑膠的機械強度，但是其奈米碳管的添 加量以該塑膠總重量計都需要高達2 wt%才會有好的效果 產生，然，當將同樣添加量的奈米碳管添加至連續纖維補 強的環氧樹脂系複合材料中時，並沒有辦法產生如添加至 射出成型的塑膠中的效果，此長久以來，與此相關的 研究文獻並不多。直到2008年，M G. Kim et ^在 ”C〇mP〇sites: Part A 39 (2〇〇8)’ p 647 p 654，’上所發表的論文 才提到使環氧樹脂系複合材料中含有〇·2 wt%及〇·7 —的 多壁（multi-walled)的奈米碳管可以提昇其在低於零度c 的低溫下的破壞韌性，但並未提及其機械性質，也未提及 其在吊/皿下的情形’然’由於該環氧樹脂系複合材料是屬 於橡膠增㈣’所以可以推想的是，此等環氧樹脂系複合 材料於常溫或高溫下的機械性質及耐熱性並不佳。另，妖 塑性樹脂增㈣氧樹脂則是由於其分子鏈段相㈣長，且 經固，成型後的複合材料的模數較高，以至於即使添加奈 米碳官也無法顯著提升材料的破㈣性和破斷延伸率。 因此’想要將現有的橡踢增勒環氧樹脂或熱塑性樹脂 增動環氧㈣制於卫作環境溫度在常溫(25。〇或高溫環境 201009008 下的複材零件，例如引擎罩部分時，是有困難的。有鑑於 此，對於高性輯維_複合材料來說，仍是有*要發展 出-種能製備出兼顧有良好機械性質及破壞韌性的複合材 料的環氧樹脂組成物。 【發明内容】 本發明之第-目的，即在提供一種適用於製傷具有良 好機械ί生質及破壞勒性的複合材料的增動型環氧樹脂組成 物0 於是，本發明增韌型環氧樹脂組成物包含一經改質的 奈米妷管 '一環氧樹脂及一具有化學式（I)且重量平均分子 篁是介於40GG至6GGG之間的聚合物（以下簡稱聚合物⑼ ，其中的η值是由該重量平均分子量所決定：There are many types of composite materials and they have been widely used in many fields. 'The 't' is the most widely used resin composite material, and in many resins, it has good adhesion and mechanical properties. It has become a resin material commonly used in the industry due to its advantages such as properties, rim margin and JL properties. However, when the epoxy resin is cured, the texture becomes brittle and easily broken, and the impact resistance is lowered, so that it should be limited. In this case, when the composite material is prepared by using % oxygen resin, it is necessary to modify the ring-shaped latex resin. The modified epoxy resin material which has been developed and used now has rubber increase_Oxygen resin ((4)(10)(10)(4) Printing (4)), rigid particle-filled epoxy resin (_particle_fmed ep〇xy) and thermoplastic 4t m (thermoplastic resin-toughened ep〇xy) # 'in the case of rubber-enhanced oxy-resin, this type of epoxy resin is used Adding rubber particles to increase its _, but because rubber particles are incompatible with epoxy resin 所以, it may affect the mechanical properties of the subsequently produced composite. The menstruation here, the inventor has disclosed in the ZUU5 i 9495, a modified epoxy resin composition prepared by the invention, which comprises a matrix mixture, and The matrix mixture has - ring 5 201009008 oxygen resin and a polymer having a weight average molecular weight of between 4,000 and 6 Å and having a special structure, the modified epoxy resin composition has good thermal properties and Mechanical properties, but when it is to be applied to the preparation of products that require more mechanical properties, such as transportation tools, there is still room for improvement in mechanical properties. In the injection molding process, some people have enhanced the mechanical strength of the plastic by adding a modified carbon nanotube, but the amount of carbon nanotubes added is up to 2 wt% based on the total weight of the plastic. Good results will be produced. However, when the same amount of carbon nanotubes is added to the continuous fiber-reinforced epoxy resin composite, there is no way to produce the effect of adding to the injection molded plastic. There has been little research literature related to this for a long time. Until 2008, M G. Kim et ^ at the "C〇mP〇sites: Part A 39 (2〇〇8)' p 647 p 654,' published papers mentioned in the epoxy resin composites Multi-walled carbon nanotubes containing 〇·2 wt% and 〇·7 — can improve their fracture toughness at low temperatures below zero c, but do not mention their mechanical properties, nor Mention that it is under the sling / dish, 'because' the epoxy resin composite is a rubber increase (four)', it is conceivable that the mechanical properties of these epoxy resin composites at normal temperature or high temperature and The heat resistance is not good. In addition, the deodorant plastic resin (4) oxygen resin is due to its molecular segment phase (four) long, and the solid modulus of the composite after molding is so high that even the addition of nano carbon official It is impossible to significantly improve the breakage and breaking elongation of the material. Therefore, 'I want to use the existing rubber rubber or thermoplastic resin to activate the epoxy (4) in the ambient temperature at room temperature (25. 〇 or high temperature). It is difficult to make a composite part under the environment 201009008, such as the hood part. Herein, for the high-performance series-composite material, there is still an epoxy resin composition capable of producing a composite material having both good mechanical properties and fracture toughness. The purpose of the present invention is to provide an actuated epoxy resin composition suitable for use in the manufacture of a composite material having good mechanical properties and destructive properties. Thus, the toughened epoxy resin composition of the present invention comprises a The modified nanotube 'an epoxy resin and a polymer having the formula (I) and having a weight average molecular weight of between 40 GG and 6 GGG (hereinafter referred to as polymer (9), wherein the η value is determined by the weight The average molecular weight is determined by:
’且以該組成物總重量計’該經改質的奈米碳管的含量不超 過 1 wt% 。 雖然發明人無法得知添加的經改質的奈米碳管與聚合 物（I)之間的確切作用機制為何，但是發明人驚奇地發現到 只需要在他先前所申請的TW公開號200819495中的環氧樹 脂組成物中添加不大於1 wt%的經改質的奈米碳管，則以 其所製得的纖維補強複合材料的破壞韌性，與未添加經改 201009008 質奈米碳管的環氧樹脂組成物所製得的複合材料相比，所 提昇的百分比是超乎預期得高，I高於現有的環氧樹脂系 複合材料。 本案發明人經由各項性質測試的數據結果推知，之所 以有如此出其意外的良好功效應是該增韌型環氧樹脂組成 物中除了該聚合物（I)和該經改質的奈米碳管會各自形成卉 米增韌機構外，該聚合物⑴和該經改質的奈米碳管之間亦 有作用存在。上述的奈米增韌機構包含：⑴該聚合物⑴以 塑性變形來鈍化裂紋尖端並吸收破壞能量；及（2)經改質的 奈米碳管扮演微觀上應力傳遞的功能，以提高形成塑性變 形所需能量，並利用可能形成的奈米碳管架橋（bHdge)及 拔出（pull-out)來吸收破壞能量，然，本發明增韌型環氧 樹脂組成物除了藉由上述方式吸收能量外，還因為其中的 聚合物（I)與經改質的奈米碳管之間具有強的介面結合強度 ，使得形成架橋及拔出所需的能量增加，進而能吸收更多 的破壞能量，因而大幅地提高以其製得的複合材料的破壞 韌性。 本發明之第二目的，即在提供一種具有良好機械性質 及破壞韌性的預浸材。 於是’本發明預浸材係藉由將一如上所述之增勒型環 氧樹脂組成物及至少一補強材結合而製得的。 本發明之第二目的，即在提供一種具有良好機械性質 及破壞韌性的複合材料。 於疋，本發明複合材料係對至少一如上所述之預浸材 201009008 施予一固化處理而製得的。 本發明之功效在於：本發明增韌型環氧樹脂組成物中 僅需含有以組成物總重量計，不大於1 wt%的經改質的齐 米碳管’就能使破壞韌性大大地被提昇，且同時兼顧到機 械性質，這是超乎現有技術所預期的結果；此外，使用者 . 藉由控制該組成物中的聚合物（I)及該經改質的奈米碳管的 用量’即可調配出符合不同機械性質及破壞·勃性要求的增 韌型環氧樹脂，故確實能達到本發明之目的。 φ 【實施方式】 本發明增韌型環氧樹脂組成物包含一經改質的奈米碳 管、一環氧樹脂及一具有化學式⑴且重量平均分子量是介 於4000至6000之間的聚合物，其中的n值是由該重量平 均分子量所決定：And the content of the modified carbon nanotubes is not more than 1 wt% based on the total weight of the composition. Although the inventors were unable to know the exact mechanism of action between the added modified carbon nanotubes and the polymer (I), the inventors were surprised to find that only in his previously filed TW Publication No. 200819495 Adding no more than 1 wt% of modified carbon nanotubes to the epoxy resin composition, the fracture toughness of the fiber-reinforced composite material prepared by the epoxy resin composition, and the non-added 201009008 carbon nanotubes Compared with the composite material prepared from the epoxy resin composition, the percentage increase is higher than expected, and I is higher than the existing epoxy resin composite material. The inventors of the present invention have inferred from the data of various property tests that the unexpected good effect is that the toughened epoxy resin composition except the polymer (I) and the modified nanometer. The carbon tubes will each form a toughening mechanism, and the polymer (1) and the modified carbon nanotubes also have a function. The above nano toughening mechanism comprises: (1) the polymer (1) is plastically deformed to passivate the crack tip and absorb the damage energy; and (2) the modified carbon nanotube acts as a microscopic stress transfer function to improve the formation of plasticity. Deforming the energy required, and utilizing the possible formation of a carbon nanotube bridge (bHdge) and pull-out to absorb the damage energy, however, the toughened epoxy resin composition of the present invention absorbs energy by the above means. In addition, because of the strong interfacial bonding strength between the polymer (I) and the modified carbon nanotubes, the energy required for bridging and pulling out is increased, and thus more energy is absorbed. Therefore, the fracture toughness of the composite material produced therefrom is greatly improved. A second object of the present invention is to provide a prepreg having good mechanical properties and fracture toughness. Thus, the prepreg of the present invention is obtained by combining an energizing epoxy resin composition as described above and at least one reinforcing material. A second object of the present invention is to provide a composite material having good mechanical properties and fracture toughness. In the present invention, the composite material of the present invention is obtained by subjecting at least one prepreg 201009008 as described above to a curing treatment. The effect of the present invention is that the toughened epoxy resin composition of the present invention only needs to contain not less than 1 wt% of the modified zirconium carbon tube based on the total weight of the composition, so that the fracture toughness can be greatly Lifting, and at the same time taking into account the mechanical properties, which is beyond the expectations of the prior art; in addition, the user controls the amount of polymer (I) and the modified carbon nanotubes in the composition. 'It is possible to formulate a toughened epoxy resin that meets the requirements of different mechanical properties and damage and boring properties, so that the object of the present invention can be achieved. Φ [Embodiment] The toughened epoxy resin composition of the present invention comprises a modified carbon nanotube, an epoxy resin and a polymer having the formula (1) and having a weight average molecular weight of between 4,000 and 6,000. The value of n is determined by the weight average molecular weight:
(I) ’且以該組成物總重量計’該經改質的奈米碳管的含量不超 過 1 wt%。 較佳地，該經改質的奈米碳管是選自於經胺改質（ amine-modified)的奈米碳管、經環氧改質（epoxy-modified )的奈米碳管，或此等之一組合。較佳地，該經胺改質的 奈米碳管為一經醢胺（amide-modified )改質的奈米碳管。 201009008 較佳地’該經改質的奈米碳管的分散率是介於3 wt%至5 wt°/e之間。較佳地，該經改質的奈米碳管是多壁的奈米碳 管。 本案之一具體實施例中，即是使用一由申請人自行製 造的經胺改質的奈米碳管，而本案之另一具體實施例中， 則是使用一由申請人自行製造的經環氧改質的奈米碳管， 但是適用於本案的經改質的奈米碳管不應以此為限，現有 的經改質的奈米碳管皆適用於本案，例如：US7,229,747中 所述的經環氧改質的奈米碳管，或是D PaugHa等人所發表❹ 的 Joural of Applied Polymer Science，vol. 88，p,452-458, 中所述的經胺改質的奈米碳管。 較佳地，以該組成物總重量計，該經改質的奈米碳管 的含量是介於0.1 wt%至〇_9 wt%之間，更佳地，該經改質 的奈米碳管的含量是介於〇.丨wt%至〇·7 wt%之間，最佳地 ，該經改質的奈米碳管的含量是介於〇 3 wt%至〇 7评伐之 間。 在本案之一具體例中，該聚合物⑴為一重量平均分子❹ 量為5130的奈米彈性體，其係由本案申請人自行研發之產 品且可與環氧樹脂之間具有良好的相容性。 較佳地，以該組成物總重量計，該聚合物⑴的含量是 · 介於5 wt%至90 wt%之間，更佳地，是介於1〇至％ wt%之間，最佳地，是介於15 wt%至3〇之間。(I) 'and the content of the modified carbon nanotubes is not more than 1 wt% based on the total weight of the composition. Preferably, the modified carbon nanotube is selected from an amine-modified carbon nanotube, an epoxy-modified carbon nanotube, or the like. One of the combinations. Preferably, the amine-modified carbon nanotube is an amide-modified carbon nanotube. 201009008 Preferably, the dispersion of the modified carbon nanotubes is between 3 wt% and 5 wt/e. Preferably, the modified carbon nanotube is a multi-walled carbon nanotube. In one embodiment of the present invention, an amine-modified carbon nanotube manufactured by the applicant is used, and in another embodiment of the present invention, a ring manufactured by the applicant is used. Oxygen-modified carbon nanotubes, but the modified carbon nanotubes used in this case should not be limited to this. Existing modified carbon nanotubes are suitable for this case, for example: US7,229,747 The epoxy-modified carbon nanotubes, or the amine-modified naphthalene described in Joural of Applied Polymer Science, vol. 88, p, 452-458, by D Paug Ha et al. Carbon tube. Preferably, the content of the modified carbon nanotubes is between 0.1 wt% and 〇_9 wt%, based on the total weight of the composition, more preferably, the modified nanocarbon The content of the tube is between 〇.丨wt% and 〇·7 wt%, and optimally, the content of the modified carbon nanotube is between 〇3 wt% and 〇7. In one embodiment of the present invention, the polymer (1) is a nano-elastomer having a weight average molecular weight of 5130, which is developed by the applicant of the present invention and has good compatibility with the epoxy resin. Sex. Preferably, the content of the polymer (1) is from 5 wt% to 90 wt%, more preferably from 1 % to % wt%, based on the total weight of the composition. Ground is between 15 wt% and 3 。.
較佳地，該環氧樹脂是選自於雙酚A型環氧樹脂（ bisPhen〇1-A epoxy resin)、雙盼 F 型環氧樹脂（bisphen〇i F 10 201009008 epoxy resin)、紛酸·型環氧樹脂（phenolic epoxy resin)、曱 紛-齡搭型環氧樹脂（cresol-phenolic epoxy resin)、多官能 基胺型環氧樹脂（multifunctional amine type epoxy)，或此 等之一組合。在本案之一具體實施例中，該環氧樹脂為雙 酚A型環氧樹脂。 較佳地，本發明增韌型環氧樹脂組成物還包含一聚胺 醋樹脂。 該聚胺醋（polyurethane )樹脂可依據後續用途來選用 φ 適當的材料，較佳地，該聚胺酯樹脂是3-異氰酸基-5-異氰 酸基甲基-1，1,5-三甲基環己院(3-isocyanate-5-methyl isocyanate-1,1,5-trimethyl-cyclohexane )與聚丙二醇之反應 產物。更佳地，該聚胺酯樹脂的重量平均分子量是介於 7000至9000之間。 當本發明增韌型環氧樹脂組成物中含有上述的聚胺酯 樹脂時，較佳地，以該組成物總重量計，該環氧樹脂的含 量是介於10 wt%至70 wt%之間，該聚合物（I)的含量是介 Φ 於10 wt%至40 wt%之間，該聚胺酯樹脂的含量是介於15 wt%至50 wt%之間；更佳地，該環氧樹脂的含量是介於10 wt%至60 wt%之間，該聚合物（I)的含量是介於15 wt%至 40 wt%之間，該聚胺酯樹脂的含量是介於15 wt%至50 wt %之間；又更佳地，該環氧樹脂的含量是介於20 wt%至40 wt%之間，該聚合物（I)的含量是介於15 wt%至35 wt%之 間，該聚胺S旨樹脂的含量是介於1 5 wt%至45 wt%之間。 較佳地，該組成物還包含一添加物。較佳地，該添加 201009008 物包含但不限於硬化劑、促進劑、阻燃劑、抑煙劑、紫外 線吸收劑或此等之一組合。在本案之一具體實施例中，該 添加物是硬化劑及促進劑之一組合。 該硬化劑可選用目前市售之任何產品，較佳地，該硬 化劑是選自於雙氰胺（dicyanodiamide)、1，2-二苯基乙二胺 (1，2-diphenyl-1，2-ethanediamine )、4,4-二氨基二苯讽（4，4-diaminodiphenyl sulfone )、酸酐，或此等之一組合。在本案 之一具體實施例中，該硬化劑是雙氰胺。 該促進劑可選用目前市售之任何產品，較佳地，該促 進劑是選自於3-(3,4-二氣苯基二曱基 （3-(3,4- dichlorophenyl)-l，l-dimethylurea)、咪峻（imidazole)、三氟 化硼錯化合物，或此等之一組合。在本案之一具體實施例 中’該促進劑是3-(3,4-二氣苯基）-1,1-二甲基 。 該添加物的用量可依據所使用之試劑及後續的用途進 行調整變化’較佳地，以該組成物總重量計，該添加物的 含量是介於4 wt%至60 wt%之間，更佳地，該添加物的含 量是介於4 wt%至25 wt%之間。 當該添加物是硬化劑及促進劑之一組合時，較佳地， 該硬化劑及促進劑的比例是介於40 : 1至4 : 3之間。在本 案之一具體例中，該硬化劑及促進劑的比例為2 : 1。 本發明增韌型環氧樹脂組成物的製備方式可以是先依 據所需比例’將環氧樹脂、該聚合物（I)及其它添加物予以 摻混以形成一基質混合物，接著’將該基質混合物與適量的 硬化劑、促進劑及經改質的奈米碳管混合，進而製得本發明 201009008 增韌型環氧樹脂組成物。 本發明增韌型環氧樹脂組成物可直接被使用（例如作為 间溫接著劑等），或與其他材料併用而製作成各種產品，例 如複合材料等。 本發明預浸材係藉由將一如上所述之增韌型環氧樹脂 組成物及至少一補強材結合而製得的。該至少一補強材可 為譬如纖維。 本發明複合材料係對至少一如上所述之預浸材施予— ® 固化處理而製得的。在本案之-具體實施例中，該複合材料 為積層板，且係藉由將多個如上所述之預浸材層疊並經固 化成型而製得的。 較佳地，當後續欲將增韌型環氧樹脂組成物製作成複 &材料時，可利用含浸法（Dipping Pr〇cess)、滾筒纏繞法 (Drum Winding Process)及熱熔膠法（H〇t Meh pr〇cess)等方 法，將至少一補強材與本發明增韌型環氧樹脂組成物結合， 以獲得-預浸材’接著再依據後續用途，將—個或多個前述 • 預浸材層疊至所需厚度並加熱成型。 在本案之一具體實施例中，該至少一補強材為多條碳 ' 纖維，發明人製作複合材料的方式是先將製得的增韌型環氡 樹脂組成物溶於一有機溶劑中，以形成一樹脂溶液，並將該 樹脂溶液倒人-鼓式纖維纏繞預浸機（Dmm驗〜）的 樹脂槽内’同時亦將所欲添加的㈣維置人該鼓式纖維纏繞 預浸機内，再啟動該鼓式纖維纏繞預浸機，使碳纖維與該樹 脂溶液中的環氧樹脂結合，藉此製得多個片狀的預浸材，並 13 201009008Preferably, the epoxy resin is selected from the group consisting of bisPhen〇1-A epoxy resin, bisphen〇i F 10 201009008 epoxy resin, and acid A phenolic epoxy resin, a cresol-phenolic epoxy resin, a multifunctional amine type epoxy, or a combination thereof. In a specific embodiment of the present invention, the epoxy resin is a bisphenol A type epoxy resin. Preferably, the toughened epoxy resin composition of the present invention further comprises a polyamine vinegar resin. The polyurethane resin may be selected from φ appropriate materials depending on the subsequent use. Preferably, the polyurethane resin is 3-isocyanato-5-isocyanatomethyl-1,1,5-tri The reaction product of 3-isocyanate-5-methyl isocyanate-1,1,5-trimethyl-cyclohexane with polypropylene glycol. More preferably, the polyurethane resin has a weight average molecular weight of between 7,000 and 9000. When the above-mentioned polyurethane resin is contained in the toughened epoxy resin composition of the present invention, preferably, the content of the epoxy resin is between 10% by weight and 70% by weight based on the total weight of the composition. The content of the polymer (I) is between 10 wt% and 40 wt%, and the content of the polyurethane resin is between 15 wt% and 50 wt%; more preferably, the epoxy resin content It is between 10 wt% and 60 wt%, the content of the polymer (I) is between 15 wt% and 40 wt%, and the content of the polyurethane resin is between 15 wt% and 50 wt%. Further preferably, the content of the epoxy resin is between 20 wt% and 40 wt%, and the content of the polymer (I) is between 15 wt% and 35 wt%, the polyamine The content of the S resin is between 15 wt% and 45 wt%. Preferably, the composition further comprises an additive. Preferably, the addition of 201009008 includes, but is not limited to, a hardener, an accelerator, a flame retardant, a smoke suppressant, an ultraviolet absorber, or a combination thereof. In one embodiment of the present invention, the additive is a combination of a hardener and a promoter. The hardener may be selected from any of the currently commercially available products. Preferably, the hardener is selected from the group consisting of dicyanodiamide and 1,2-diphenylethylenediamine (1,2-diphenyl-1,2). -ethanediamine ), 4,4-diaminodiphenyl sulfone, anhydride, or a combination of these. In a specific embodiment of the present invention, the hardener is dicyandiamide. The accelerator may be selected from any of the products currently commercially available. Preferably, the accelerator is selected from 3-(3,4-diphenylphenyl)-(3-(3,4-dichlorophenyl)-l. L-dimethylurea), imidazole, boron trifluoride compound, or a combination thereof. In one embodiment of the present invention, the promoter is 3-(3,4-diphenyl) -1,1-dimethyl. The amount of the additive can be adjusted depending on the reagent used and the subsequent use. Preferably, the additive is present in an amount of 4 wt% based on the total weight of the composition. Between 6 and 60 wt%, more preferably, the content of the additive is between 4 wt% and 25 wt%. When the additive is a combination of a hardener and a promoter, preferably, The ratio of the hardener and the accelerator is between 40:1 and 4: 3. In one embodiment of the present invention, the ratio of the hardener to the accelerator is 2: 1. The toughened epoxy resin composition of the present invention The preparation may be carried out by first blending the epoxy resin, the polymer (I) and other additives to form a matrix mixture according to the desired ratio, and then 'the substrate The mixture is mixed with an appropriate amount of a hardener, a promoter and a modified carbon nanotube to obtain the 201009008 toughened epoxy resin composition of the present invention. The toughened epoxy resin composition of the present invention can be directly used ( For example, as a temperature-temperature adhesive, etc., or in combination with other materials, various products, such as composite materials, etc. are produced. The prepreg of the present invention is obtained by using a toughened epoxy resin composition as described above and at least one The reinforcing material is obtained by combining the reinforcing materials. The at least one reinforcing material may be, for example, a fiber. The composite material of the present invention is obtained by applying at least one prepreg as described above to the curing treatment of the prepreg as described above. In the example, the composite material is a laminate, and is obtained by laminating a plurality of prepregs as described above and solidifying and molding. Preferably, when the toughened epoxy resin composition is to be subsequently applied When making a composite & material, at least one reinforcing material can be used by a method such as Dipping Pr〇cess, Drum Winding Process, and hot melt adhesive method (H〇t Meh pr〇cess). Toughened ring of the invention The resin composition is combined to obtain a prepreg. Then, one or more of the foregoing prepregs are laminated to a desired thickness and thermoformed according to the subsequent use. In one embodiment of the present invention, the at least one The reinforcing material is a plurality of carbon 'fibers, and the inventors make the composite material by first dissolving the obtained toughened cyclic ruthenium resin composition in an organic solvent to form a resin solution, and smashing the resin solution. - the drum-type fiber-wound prepreg machine (Dmm test ~) in the resin tank 'at the same time, the desired (four) dimension is placed in the drum-type fiber-wound prepreg machine, and then the drum-type fiber-wound prepreg machine is activated, so that The carbon fiber is combined with the epoxy resin in the resin solution, thereby preparing a plurality of sheet-shaped prepregs, and 13 201009008
本發明將就以下實施例來作進—步說明，但應瞭解的 次材，以得到一具有一預定厚度的板 模具令以高溫高壓複材成型機進行熱 ’而不應被解釋為本發明 疋’該等實施例僅為例示說明之用， 實施之限制。 <化學品來源> 1 ·广紛A型環氧樹脂.由DOW Chemical公司所製造，型❹ 號為DER331 standard BPA，其環氧當量（—π equivalency)為 184〜190，黏度為 12000〜15000 cps(25〇c 下）。 2. 紛盤型環氧樹脂：由D〇w chemical公司所製造，型號 為 DER438。 3. 聚胺醋樹脂：由台灣莘茂複合材料股份有限公司所製造 ，係為3-異氰酸基-5-異氰酸基曱基-1，1，5_三曱基環己烧 與聚丙二醇之反應產物，其重量平均分子量為854〇。 ❹ 4. 奈米彈性體（增韌劑）：由台灣莘茂複合材料股份有限公 司所製造的，型號為Epolec®，其重量平均分子量為513〇 ’黏度為10000 Pa . S(30°C下）’以及玻璃轉移溫度為 90°C。 5. 硬化劑：為雙氰胺，由德國degussa公司所製造。 6. 促進劑：為3-(3,4-二氣苯基）-1，1-二甲基，由德國 degussa公司所製造。 14 201009008 7· 12 K碳纖維：購自於台麗，型號為Τ(：ΐ2κ35，^張強 度為侧Mpa ;抗張模數為247 Gpa ;密度為〔二3 ;直徑為7 // m。 8.經胺改質的奈米碳管：由台灣華茂複合材料股份有限公 司所製造的，型號為EP〇_A〇5,其直徑為ι〇〜2〇 ^長 度為3〜5以m ;密度為2 5〜2 6 g/cm3。The present invention will be further described with respect to the following examples, but it should be understood that the secondary material is obtained to obtain a plate mold having a predetermined thickness for heat treatment by a high temperature and high pressure composite material forming machine, and should not be construed as the invention. The examples are for illustrative purposes only and are not limited by the implementation. <Chemical Source> 1 · Widely A-type epoxy resin. Manufactured by DOW Chemical Co., Ltd., the model number is DER331 standard BPA, and its epoxy equivalent (-π equivalency) is 184 to 190, and the viscosity is 12000~ 15000 cps (under 25〇c). 2. Disc type epoxy resin: manufactured by D〇w Chemical Co., Ltd., model DER438. 3. Polyamine vinegar resin: manufactured by Taiwan Yumao Composite Materials Co., Ltd., which is 3-isocyanate-5-isocyanatodecyl-1,1,5-trimethylcyclohexane and The reaction product of polypropylene glycol has a weight average molecular weight of 854 Å. ❹ 4. Nano-elastomer (toughening agent): manufactured by Taiwan Minmao Composite Materials Co., Ltd., model Epolec®, with a weight average molecular weight of 513 〇 'viscosity of 10000 Pa. S (at 30 ° C )' and the glass transition temperature is 90 °C. 5. Hardener: dicyandiamide, manufactured by the German degussa company. 6. Accelerator: 3-(3,4-diphenyl)-1,1-dimethyl, manufactured by the German company degussa. 14 201009008 7· 12 K carbon fiber: purchased from Taili, model Τ(:ΐ2κ35, ^ tensile strength is side Mpa; tensile modulus is 247 Gpa; density is [2 3; diameter is 7 // m. 8 Amine-modified carbon nanotubes: manufactured by Taiwan Huamao Composite Materials Co., Ltd., model EP〇_A〇5, with a diameter of ι〇~2〇^3~5 to m; The density is 2 5 to 2 6 g/cm 3 .
製備本發明環氧樹脂組成物 9·經環氧改質的奈米碳管：&台灣莘茂複合材料股份有限 公司所製造的’型號為咖挪，其直徑為iq〜Mi 長度為3〜5 "m;密度為25〜26g/cm3。 <實施例1> 本實施例的製備步驟分為兩部分： ⑴基質混合物之製備：分別將以環氧樹脂組成物總重量 計，37.3 wt%的雙酚A型環氧樹脂、i8 67 的齡 酿型環氧樹脂、18.67 wt%的聚胺s旨樹脂及18 67⑽ 的奈米彈性體放入一高速均質攪拌機（出幼speed Dispersed Home Mixer，購自於台灣伸球企業有限公司 ;型號為HC0025 )中均勻混合，以製得一基質混合物 (2)增韌型環氧樹脂組成物之製備：將該基質混合物於8〇 C下授拌2小時’接著，加域環氧樹脂組成物總重 量計，〇.1 wt%的經胺改質的奈米碳管、3 73 wt%的硬 化劑及2.8 wt%的促進劑並均勻攪拌2()分鐘，進而製 得本發明增韌型環氧樹脂組成物。 15 201009008 <實施例2至4> 實施例2至4是以與實施例1相同的方式製備本發明 增勤型環氧樹脂組成物，不同之處僅在於：步謂的經胺 改質的奈米碳管的用量依序改為〇.4 wt% Wt% 。 0.7 _ wt% 及 1.0 <實施例5至8 >Preparation of the epoxy resin composition of the present invention 9. Epoxy-modified carbon nanotube: &Taiwan Yumao Composite Materials Co., Ltd. manufactured by the model of the company, its diameter is iq~Mi, the length is 3~ 5 "m; density is 25~26g/cm3. <Example 1> The preparation procedure of this example was divided into two parts: (1) Preparation of a matrix mixture: 37.3 wt% of bisphenol A type epoxy resin, i8 67 based on the total weight of the epoxy resin composition, respectively Age-growth epoxy resin, 18.67 wt% polyamine s resin and 18 67 (10) nano-elastomer were placed in a high-speed homomixer (young speed Dispersed Home Mixer, purchased from Taiwan Shenqiu Enterprise Co., Ltd.; Uniform mixing in HC0025) to prepare a matrix mixture (2) Preparation of toughened epoxy resin composition: the matrix mixture was mixed at 8 ° C for 2 hours 'then, adding the total epoxy resin composition重量.1 wt% of amine-modified carbon nanotubes, 373 wt% of hardener, and 2.8 wt% of accelerator and uniformly stirred for 2 () minutes to obtain the toughened ring of the present invention. Oxygen resin composition. 15 201009008 <Examples 2 to 4> Examples 2 to 4 were prepared in the same manner as in Example 1 to prepare the energizing epoxy resin composition of the present invention, except that the step was an amine-modified The amount of carbon nanotubes was changed to 〇.4 wt% Wt%. 0.7 _ wt% and 1.0 <Examples 5 to 8 >
實施例5至8分別是以與實施例^至*相同的方式製 備本發明增動型環氧樹脂組成物，不同之處僅在於：步驟 (2)的經胺改質的奈米碳管是以經環氧改質的奈米碳管取代 <比較例1 > 比較例1是以與實施例」相同的方式製備環氧樹脂組 成物，不同之處僅在於：比較例^並沒有加入任何奈米碳 管。 製備本發明複合材料—積層板 <應用例1 > 本應用例所要製備出的複合材料是一含有重量比為37❹ U :韌5L環氧樹脂組成物及63 wt%的丨碳纖維的積層 板。 本應用例的製備方式是先將秤好重量的實施例1之增 韌尘環氧樹脂組成物溶於適量的丁酮中，以形成一樹脂溶 液並將該樹脂溶液倒入一鼓式纖維纏繞預浸機（講自於 σ ^代理商金門化工有限公司；型號為BSD隐_49⑽55) 的樹月曰槽内’再將秤好量的12κ碳纖維置入該鼓式纖維纏 16 201009008 繞預浸機内，使碳纖維與樹脂溶液中環氧樹脂結合，進而 製得-呈片狀的預浸材，再將該預浸材裁切成2〇⑽2〇⑽ 的大小，而後以手積層法疊層至所需厚度，以得到一板材 ，再將該板材置人-模具中以高溫高壓複材成型機（構自 於台灣億幅實業公司）進行熱M，其製程條件為1〇分鐘升 溫至⑽’並於⑽下持溫持壓3〇分鐘，最後將該模 ㈣至室訂，待其自然降溫至室溫溫度，即可從該模且 中取出一積層板。 八 φ 〈應用例2至8 > 應用例2至8是以與應用们相同的方式製備本發明 積層板，不同之處僅在於：實施例1之增知型環氧樹脂组 成物分別是以實施例2至8之增物型環氧樹月旨組成物取代 〇 <應用比較例1 > 應用比較例1是以與應用例1相同的方式製備積層板 ，不同之處僅在於：實施例！之增勒型環氧樹脂組成物是 © 以比較例1之增韌型環氧樹脂組成物取代。 各項性質之測試 •纟進行各項機械性質之測試前，發明人先依據下述不 同測試的試片規格，將應用例！至8及應用比較例1之積層 板裁切成所需的試片大小，需特別說明的是，以下測試皆是 在常溫下進行的。 挽曲性質Γ flexural property )泪丨| f式. 發明人依據ASTM D79G規範以三點f曲方式對該等試 17 201009008 片進行撓曲強度、撓曲模數及破斷延伸率的測試，其中螺頭 下壓速度為6.3 mm/min，試片的長度、寬度及厚度分別為 120 mm、24 mm及2.4 mm，其測試結果如下表】所示。 撓曲強度的單位為奶；撓曲模數的單位&咖，換 曲強度、撓曲模數及破斷延伸率的數值越高代表挽曲性質越 佳，而表【中所述的90度方向和〇度方向是指受力方向與 碳纖维排列方_ .向.的夾角。 短樑強膚淛Μ 在進行強樑測試前，發明人必須先依據astm 〇3171 方法測試上述應用例及比較例丨所製得之積層板内之纖維重 量分率（w7)，並依據以下公式計算纖維體積分率（ν^: V/~ Wy/P/-f Wr/P, Xl〇〇% 於上式中，V/為纖維體積分率（％)，為纖維重量分率 (%)，Wr為樹脂重量分率（％)，P/為纖維密度（g/cm3)，以及 為樹脂密度（g/cm3)。接著，再依據ASTM D2344規範以 包樑形式對該等試片進行短樑強度（sh(m〜⑽）的測試， 其中螺頭下壓速度為L0 mm/min，試片的長度、寬度及厚〇 度分別為18 mm、6 mm及3 mm，而測試跨距為12 mm ( 亦即該:¾彳試跨距與該試#的厚度比為4 ·· 1}，其賴結果如 下表1所示。 短樑強度的單位為Mpa ,此數值代表層與層之間應力 於男切模式下的傳遞能力，因此其數值高代表層間剪切強度 越強。 性漭丨铽 18 201009008 1 ·模式 I (Mode I)—雙懸臂樑（Double Cantilever Beam ； DCB)測試 發明人依據ASTM D5528規範以雙懸臂樑的方式對該 等試片進行破壞性的測試，其中測試速度為2 mm/min，試 片的長度、寬度及厚度分別為125 mm、25 mm及3.3 mm， 並具有一長度為63 mm且裂缝寬度為0.08 mm的預裂縫， 而量測到的破壞韌性GIC值如下表1所示，測試數值越高代 表破壞韌性越佳。 ❿ 2.模式 II (Mode II)—端點刻痕彎曲（End Notched Flexure ; ENF)測試 發明人依據 Leif A Carlsson and R Byron Pipes 的 Experimental Characterization of Advanced Materials, p. 167-p. 176中所述的以三點彎曲的方式對該等試片進行破壞性的 測試，其中螺頭下壓速度為5 mm/min，試片的長度、寬度 及厚度分別為110 mm、25 mm及3.5 mm，並具有一長度為 25 mm且裂縫寬度為0.08 mm的預裂縫，且測試跨距為 Φ 100 mm，另，量測到的破壞韌性GIIC值如下表1中，測試 . 數值越高代表破壞韌性越佳。 19 201009008 表1 \ 撓曲 (M 強度 Pa) 撓曲模數 (GPa) 破斷 延伸 率 (% ) 短樑 強度 (MPa) Gic值 [kj/m2) Gnc值 [kj/m2) 〇度 方向 90度 方向 〇度 方向 90度 方向 應用例1 1191 102.2 98.4 7.7 1.54 71.2 0.666 2.544 應用例2 1207 108.4 99.9 7.9 1.74 75.2 0.931 2.658 應用例3 1222 95.9 99.4 7.8 1.42 73.8 1.030 2.488 應用例4 1230 93.4 106.8 7.9 1.35 73.7 0.929 2.530 應用例5 1175 103.8 100.6 8.0 1.68 70.8 0.751 2.741 應用例6 1188 104.3 99.4 8.1 1.75 74.8 0.840 2.774 應用例7 1201 93.6 105.7 7.9 1.40 72.0 1.021 2.52B 應用例8 1180 88.2 112.0 8.0 1.21 71.2 0.992 2.396 應用 比較例1 1164 99.37 ----— 97.0 — 7.8 ----- 1.50 __ 71.3 0.524 2.283 由表1可知’就撓曲性質而言，不論是添加經胺改質Examples 5 to 8 were prepared in the same manner as in Examples ^ to *, respectively, in which the epoxy resin composition of the present invention was prepared, except that the amine-modified carbon nanotube of the step (2) was Replacement with epoxy-modified carbon nanotubes <Comparative Example 1 > Comparative Example 1 was prepared in the same manner as in Example ", except that the comparative example was not added. Any carbon nanotubes. Preparation of Composite Material-Laminated Sheet of the Invention<Application Example 1> The composite material to be prepared in this application example is a laminate comprising a weight ratio of 37 ❹ U: a tough 5 L epoxy resin composition and 63 wt% of ruthenium carbon fiber. . This application example is prepared by firstly weighing the weighed dust epoxy resin composition of Example 1 into an appropriate amount of methyl ethyl ketone to form a resin solution and pouring the resin solution into a drum-type fiber winding. The prepreg machine (speaking from the σ ^ agent Jinmen Chemical Co., Ltd.; model BSD hidden _49 (10) 55) in the tree in the groove, then put a good amount of 12κ carbon fiber into the drum fiber wrapped 16 201009008 around the pre-dip In the machine, the carbon fiber is combined with the epoxy resin in the resin solution to obtain a prepreg in the form of a sheet, and the prepreg is cut into a size of 2〇(10)2〇(10), and then laminated by hand stacking method. The required thickness is obtained to obtain a plate, and then the plate is placed in a mold - a high temperature and high pressure composite material forming machine (constructed from Taiwan billion company) for heat M, and the process conditions are raised to (10)' in 1 minute. And holding the temperature under (10) for 3 〇 minutes, and finally the mold (4) to the room, until it is naturally cooled to room temperature, a laminate can be taken from the mold. Eight φ <Application Examples 2 to 8 > Application Examples 2 to 8 were prepared in the same manner as those of the application, except that the enhanced epoxy resin composition of Example 1 was The additive type epoxy resin composition of Examples 2 to 8 was substituted for ruthenium <Application Comparative Example 1 > Application Comparative Example 1 was to prepare a laminate in the same manner as in Application Example 1, except that: example! The enriched epoxy resin composition was replaced by the toughened epoxy resin composition of Comparative Example 1. Testing of various properties • Before conducting tests on various mechanical properties, the inventors will first apply the test specimens according to the test specimen specifications of the different tests described below! The laminated sheets of the comparative example 1 and the application of the comparative example 1 were cut into the required test piece size, and it should be particularly noted that the following tests were carried out at room temperature. Flexural property 丨 ural . f ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural ural The screw head pressing speed is 6.3 mm/min, and the length, width and thickness of the test piece are 120 mm, 24 mm and 2.4 mm, respectively. The test results are shown in the following table. The unit of flexural strength is milk; the unit of the flexural modulus & coffee, the higher the value of the bending strength, the flexural modulus and the breaking elongation, the better the bending property, and the 90 described in the table [ The direction of the direction and the direction of the twist are the angles between the direction of the force and the arrangement of the carbon fibers. Short beam strong skin Zhejing Before the strong beam test, the inventor must first test the fiber weight fraction (w7) in the laminate produced by the above application examples and comparative examples according to the astm 〇3171 method, and calculate according to the following formula Fiber volume fraction (ν^: V/~ Wy/P/-f Wr/P, Xl〇〇% in the above formula, V/ is the fiber volume fraction (%), which is the fiber weight fraction (%), Wr is the resin weight fraction (%), P/ is the fiber density (g/cm3), and is the resin density (g/cm3). Then, the test piece is subjected to the short beam in the form of a wrapped beam according to the ASTM D2344 specification. Strength (sh(m~(10)) test, where the screw head pressing speed is L0 mm/min, the length, width and thickness of the test piece are 18 mm, 6 mm and 3 mm, respectively, and the test span is 12 Mm (that is, the thickness ratio of the test span of 3⁄4彳 to the test # is 4 ·· 1}, and the results are shown in Table 1. The unit of the short beam strength is Mpa, which represents the layer-to-layer The stress is transmitted in the male cut mode, so the high value means the stronger the interlaminar shear strength. 漭丨铽18 201009008 1 ·Mode I (Mode I)—Double cantilever (Double Ca Ntilever Beam; DCB) Test The inventors performed destructive tests on the test specimens in the form of double cantilever beams according to ASTM D5528, with a test speed of 2 mm/min and a test specimen length, width and thickness of 125 mm, respectively. 25 mm and 3.3 mm, and a pre-crack with a length of 63 mm and a crack width of 0.08 mm, and the measured fracture toughness GIC values are shown in Table 1. The higher the test value, the better the fracture toughness. 2. Mode II - End Notched Flexure (ENF) test by the inventors according to Leif A Carlsson and R Byron Pipes, Experimental Characterization of Advanced Materials, p. 167-p. Destructive tests were carried out on the test pieces in a three-point bending manner, in which the screw head pressing speed was 5 mm/min, and the length, width and thickness of the test pieces were 110 mm, 25 mm and 3.5 mm, respectively. A pre-crack with a length of 25 mm and a crack width of 0.08 mm and a test span of Φ 100 mm. In addition, the measured fracture toughness GIIC values are shown in Table 1 below. The higher the value, the better the fracture toughness. 19 201009008 Table 1 \ Flexure (M intensity Pa) Flexural modulus (GPa) Breaking elongation (%) Short beam strength (MPa) Gic value [kj/m2) Gnc value [kj/m2) Temperature direction 90 degree direction twist Direction of application in the direction of 90 degrees Example 1 1191 102.2 98.4 7.7 1.54 71.2 0.666 2.544 Application example 2 1207 108.4 99.9 7.9 1.74 75.2 0.931 2.658 Application example 3 1222 95.9 99.4 7.8 1.42 73.8 1.030 2.488 Application example 4 1230 93.4 106.8 7.9 1.35 73.7 0.929 2.530 Application example 5 1175 103.8 100.6 8.0 1.68 70.8 0.751 2.741 Application Example 6 1188 104.3 99.4 8.1 1.75 74.8 0.840 2.774 Application Example 7 1201 93.6 105.7 7.9 1.40 72.0 1.021 2.52B Application Example 8 1180 88.2 112.0 8.0 1.21 71.2 0.992 2.396 Application Comparison Example 1 1164 99.37 - ---- 97.0 — 7.8 ----- 1.50 __ 71.3 0.524 2.283 It can be seen from Table 1 'In terms of flexural properties, whether it is added by amine modification
或經％氧改質的奈米碳管，該等試片的〇度方向之撓曲強度 (即軸向強度）趨勢上會隨著奈米碳管的添加量增加而有些 微上升的情形，而撓曲模數也是趨勢上會隨著添加量增加而 1顯著地提昇’至於該等試片的90度方向之撓曲強度（即 杈向強度）皆於奈米碳管的添加量達0 4 wt%時有最大值， 發明人認為添加量超過0.4 wt%後，橫向強度之所以會下降 的原因是因為奈米碳管的量較多時會引發團聚現象，而撓曲 莫數則是會隨著添加量增加而有些微提昇。 就短樑強度而言，該等試片所呈現的趨勢與如度方向 撓曲強度相同，同樣地，在奈米碳管的添加量達0.4 wt% 20 201009008 時有最大值，而當添加量超過〇·4 wt%時便因團聚處會發生 應力集中現象而使得層間剪切強度下降。 就破壞韌性而言，不論是添加經胺改質或經環氧改質 的奈米碳管，該等試片的破壞韌性Gic或Gnc值皆因添加奈 米碳管而提昇。其中，就模式Ϊ的破壞韌性而言，以添加 0.7 wt%之經改質的奈米碳管的試片的效果為最佳。就模式 π的破壞韌性而言，以添加〇 4 wt%之經改質的奈米碳管= 試片的效果為最佳。相對於未添加奈米碳管的試片的破壞 • 韌性G|c;添加〇·7 wt%之經胺改質的奈米碳管試片的破壞 物ft提昇比例tBj達96.7 % ;添加0.7 wt%之經環氧改質的 奈米碳管的試片的破壞韌性提昇比例高達95 〇 % 。而相對 於未添加奈米碳管的試片的破壞韌性G„c，添加0.4 wt%之 、星胺改貝的奈米碳官的試片的破壞物性提昇比例為^ 6 4 % ，添加0.4 wt%之經環氧改質的奈米碳管的試片的破壞韌性 提昇比例為21.5 % 。 自上可知，以實施例1至8之本發明增韌型環氧樹脂 ^ 組成物所製得的複合材料（亦即應用例i至8之積層板）， 二未加、..巫改質的奈米碳管的環氧樹脂組成物所製得的複 Z材料相比’確實具有較佳的機械性質及破壞韌性，尤其 是=壞初性所提昇的百分比是超乎意外的高，且其破壞物Or the carbon nanotubes modified by % oxygen, the flexural strength (ie, axial strength) of the test piece in the twist direction tends to slightly increase as the amount of carbon nanotubes increases. The flexural modulus is also a trend that will increase significantly as the amount of addition increases. 1 As for the flexural strength of the test specimens in the 90-degree direction (ie, the tensile strength), the amount of carbon nanotubes added is 0. When there is a maximum value at 4 wt%, the inventors believe that the reason why the lateral strength decreases after the addition amount exceeds 0.4 wt% is because the agglomeration phenomenon is caused when the amount of the carbon nanotubes is large, and the flexural number is Will increase slightly as the amount of addition increases. As far as the strength of the short beam is concerned, the test piece exhibits the same tendency as the flexural strength of the degree of the same direction. Similarly, when the amount of carbon nanotubes added is 0.4 wt% 20 201009008, the maximum value is obtained, and when the amount is added, When it exceeds 〇·4 wt%, stress concentration occurs at the agglomeration, and the interlaminar shear strength decreases. In terms of fracture toughness, whether the amine modified or epoxy-modified carbon nanotubes were added, the fracture toughness Gic or Gnc values of the test pieces were increased by the addition of carbon nanotubes. Among them, in terms of the fracture toughness of the mode ,, the effect of adding a test piece of 0.7 wt% of the modified carbon nanotube was the best. In terms of the fracture toughness of the mode π, the effect of adding a modified carbon nanotube of 4 wt% = test piece is optimal. The damage of the test piece relative to the unfilled carbon nanotubes • Toughness G|c; the addition of 〇·7 wt% of the amine-modified carbon nanotube test piece has a ft-lifting ratio tBj of 96.7 %; The damage toughness of the test piece of the wt% epoxy-modified carbon nanotubes was as high as 95%. With respect to the fracture toughness G„c of the test piece to which the carbon nanotube was not added, the reduction property of the test piece of 0.4% by weight of the nanocarbon official of the star-amine-modified shell was ^64%, and 0.4 was added. The fracture toughness increase ratio of the wt% epoxy-modified carbon nanotube test piece was 21.5 %. As described above, the toughened epoxy resin composition of the present invention of Examples 1 to 8 was obtained. The composite material (that is, the laminated sheets of the application examples i to 8), the composite Z material obtained by the epoxy resin composition of the unmodified, so-called modified carbon nanotubes is indeed better than The mechanical properties and the toughness of the fracture, especially the percentage increase of the bad initiality is unexpectedly high, and its damage
阿；見有的環氧樹脂系複合材料，而破斷延伸率也是符 合業界標準，由A y , 此可知’本發明增韌型環氧樹脂組成物在 '•製作成複口材料時，其破壞韌性的確可以被大幅地提 高’且同時兼顧有良好的機械性^ 21 201009008 本案發明人認為之所以有如此出其意外的良好功效， 應是與該增韌型環氧樹脂組成物中的聚合物⑴與經改質的 奈米碳管之間具有強的介面結合強度有很大的關係，因為 當前述兩者之間有較強的介面接合強度時，會導致形成奈 米碳管架橋及拔出所需的能量增加，進而能吸收更多的破 壞能量。此外’該聚合物（I)還會以塑性變形來鈍化裂紋尖 端並吸收破壞能量，而該經改質的奈米碳管則是在微觀上 扮演了應力傳遞的功能，以提高形成塑性變形所需能量， 並利用可能形成的奈米碳管架橋及拔出來吸收破壞能量。 _ 综上所述，本發明增韌型環氧樹脂組成物因同時含有 聚合物（I)和經改質的奈米碳管，且該二者之間的介面結合 強度強，使得以其所製得的複合材料或其它製品能具有較 佳機械性質及破壞韌性，且經改質的奈米碳管的添加量僅 需小於1 wt% ，就可以達到相當好的性質，更進一步地， 使用者藉由控制該基質混合物中的聚合物⑴及該經改質的 奈米碳管的用量，即可調配出符合不同機械性質及破壞韌 性要求的增韌型環氧樹脂組成物，進而製得適用於不同應❹ 用邊域的複合材料’所以使用本發明增動型環氧樹脂組成 物此在成本低的條件下製得性質良好且應用範圍更廣的複 合材料或其它製品，故確實能達成本發明之目的。 淮以上所述者，僅為本發明之較佳實施例而已，當不 f X此限定本發明實施之範圍’即大凡依本發明申請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 22 201009008 參A; see epoxy resin composites, and the elongation at break is also in line with industry standards, by A y, it can be seen that 'the toughened epoxy resin composition of the present invention is made when it is made into a composite material. Destructive toughness can indeed be greatly improved 'and at the same time have good mechanical properties ^ 21 201009008 The inventor of this case believes that the reason for this unexpected good effect should be the polymerization with the toughened epoxy resin composition. There is a strong relationship between the strong interfacial bonding strength between the material (1) and the modified carbon nanotubes, because when there is a strong interfacial bonding strength between the two, the formation of the carbon nanotube bridge and The energy required to pull out increases, which in turn absorbs more damage energy. In addition, the polymer (I) will passivate the crack tip and absorb the damage energy by plastic deformation, and the modified carbon nanotube plays a role of stress transmission at the microscopic level to improve the formation of plastic deformation. Energy is required, and the carbon nanotube bridges that may be formed are used and pulled out to absorb the energy of destruction. _ In summary, the toughened epoxy resin composition of the present invention contains both the polymer (I) and the modified carbon nanotubes, and the interface bonding strength between the two is strong, so that The obtained composite material or other articles can have better mechanical properties and fracture toughness, and the modified carbon nanotubes can be added in an amount of less than 1 wt%, which can achieve quite good properties, and further, use By controlling the amount of the polymer (1) and the modified carbon nanotubes in the matrix mixture, a toughened epoxy resin composition that meets different mechanical properties and fracture toughness requirements can be formulated to obtain a toughened epoxy resin composition. It is suitable for composite materials with different edge areas. Therefore, the use of the actuated epoxy resin composition of the present invention produces a composite material or other product having a good property and a wider application range under low cost conditions, so The object of the invention is achieved. The above is only the preferred embodiment of the present invention, and does not limit the scope of the present invention, which is a simple equivalent change and modification of the scope of the invention and the description of the invention. All remain within the scope of the invention patent. 22 201009008 Participation
【圖式簡單說明】 無 【主要元件符號說明】 無 23[Simple description of the diagram] None [Key component symbol description] None 23
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