1275579 九、發明說明： 【發明所屬之技術領域】 一種 本發明係有關於-種奈米複合材料，特収 土-⑽環氧樹脂奈米複合材料及其製造方法。 ' 【先前技術】1275579 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a nanocomposite material, a special earth-(10) epoxy resin nano composite material, and a method for producing the same. 'Prior art
元件是指半導體積體電路製作完錢，再與其他電子 於—聯線結射，成為—電子產品，以 =功能的所有製程。電子構裝的主要功能有四，分別是電能 ' mf#U#it(SlgnalDlstrib^〇n) ^ 失（Heat Dlssipat_)與保護支持（pr— _ §卿⑽）。 南分子材料應用最多的電子構裝，是印刷電路板。电人電 =電路板大都採用複合材料積層板，外層銅料經 璃纖要求的印刷電路板。複合材料是將強化纖維（如玻 社人、、-&，截維或有機纖維等）與樹脂（熱固性樹脂或熱塑性樹脂) 、^而成的-種結構性材料。複合材料不但有優異的機械強 度，同時亦有極佳的尺寸安定性。目前印刷電路板材料以採用 玻璃纖維最為普遍，因熱固性樹脂在尺寸安定性及耐熱性上較 熱塑性樹脂為佳’故樹脂材料以採用熱固性樹脂為主，其令又 以採用環氧樹脂最為普遍。 〃 而奈米複合材料（Nanocomposite)為分散相粒徑介於 ⑻nm之複合材料，充份發揮分子層級之結構特性，如粒 控小、高視徑比、層狀補強結構、離子鍵結等性質，以達奈米 級複合材料低補強材含量之輕量化目標，並具高強度、高剛性、 间耐熱性、低吸水率、低透氣率等高功能性質。 先别對般環氧樹脂在構裝材料所要求的特性包括低應 0806-A21144TWF(N2)；david 6 ⑧ 1275579 « _ 1 - 力、高熱傳導性、高耐熱性、耐濕性、耐腐蝕性、以及電氣性 等。在其性質要求日益嚴格的前提下，我們將奈米級複合材料 所擁有的優異性質應用在構裝材料上。 首先利用具有促進網狀物形成之2-phenylimidazole(2-PI) 與黏土進行插層改質動作，而後將無機層材分散在環氧樹脂 中，並且誘使網狀型高分子的形成發生在無機層材之層間中， 如此一來，不僅可以利用奈米混成效應使其機械性質增強，亦 可使封裝材料所需求的性質如低吸濕率、高耐熱性、優異的尺 寸安定性大幅改善。 ^ 美國專利US Pat_ 6548576揭示使用兩種不同的epoxy resin，包括約含有2〜13%的DGEBA以及40〜70%的phenol formaldehyde resin，可以製備出在溫度範圍-65°C〜150°C，不會 有熱衰退現象的環氧樹脂。其利用調控兩種不同的樹脂比例， 來使其達到具有良好熱穩定性。 美國專利US Pat. 5554670揭示以兩種不同的硬化劑包括 BDMA以及BTFA對相同的環氧樹酯（DGEBA)所合成出的奈米 複合材料進行交聯，其層間距大於1 〇〇埃。 Φ 美國專利us Pat· 5760106揭示出改質劑在黏土的層間分散 情形有五種，而其中分散較均勻者對形成脫層（exf〇Hateci)的機 會越大’文中並指出分散性最好者，其tensile strength或是 tensile modulus皆表現得最好。 • 美國專利US Pat. 5853886揭示以許多不同的硬化劑包括 - JEFFAMINE D230、D400、D4000、T304、T3000 以及 T5000(分 子鏈的長短不同）來製備各種不同的環氧樹脂-黏土奈米複合材 料’其中以Τ5000(分子鏈最為長）所做出來的d-spacing會最大。 歐洲專利EP Pat. 08446661揭示出以環氧樹g旨、硬化劑以 0806-A21144TWF(N2)；david 7 ⑧ 1275579 及蒙脫土的比例在DDP/DER331/MMT=1 : 1 : 0.75時，其 d-spacing=34.38A，而後改變其比例在 1 ·· 3 : 2.5 時， d-spacing=32.92A，而改用長碳鏈的改值劑後d-spacing被撐得 最開，同時機械性質與玻璃轉移溫度亦獲得改善。 期刊POLYMER (42) 2001 5947-5952其結果顯示出只需要 些微的硬化劑MPDA即可達到良好的分散，如果濃度太高，會 造成intercalated現象增多。由XRD看出，MPDA的量如果太 多的話，會造成分散性不好，d-spacing依MPDA控制，可以由 34.5A 到 180人。The component refers to the process in which the semiconductor integrated circuit is made and then combined with other electrons to form an electronic product to all functions of the function. The main functions of the electronic assembly are four, namely electric energy 'mf#U#it(SlgnalDlstrib^〇n)^Heat Dlssipat_ and protection support (pr__§§(10)). The most widely used electronic component of South Molecular Materials is the printed circuit board. Electrician = Most of the circuit boards use composite laminates, and the outer copper is printed on the printed circuit board required by the glass. The composite material is a structural material obtained by using a reinforcing fiber (such as a glass, a -&, a cut-off or an organic fiber) and a resin (a thermosetting resin or a thermoplastic resin). Composite materials not only have excellent mechanical strength, but also excellent dimensional stability. At present, the use of glass fibers for printed circuit board materials is most common, and thermosetting resins are superior to thermoplastic resins in terms of dimensional stability and heat resistance. Therefore, resin materials are mainly made of thermosetting resins, and epoxy resins are most commonly used. 〃 Nanocomposite is a composite material with a dispersed phase particle size of (8) nm, which fully exerts the structural characteristics of molecular layers, such as small particle size control, high aspect ratio, layered reinforcing structure, ionic bonding and other properties. The lightweight target of low-reinforcing material content of Danai-grade composite materials has high functional properties such as high strength, high rigidity, heat resistance, low water absorption and low air permeability. First, the characteristics required for the epoxy resin in the package material include low should be 0806-A21144TWF (N2); david 6 8 1275579 « _ 1 - force, high thermal conductivity, high heat resistance, moisture resistance, corrosion resistance And electrical and so on. Under the premise that the nature of the requirements is increasingly strict, we apply the superior properties of nano-composites to the construction materials. Firstly, the intercalation modification operation is carried out by using 2-phenylimidazole (2-PI) which promotes the formation of a network, and then the inorganic layer is dispersed in the epoxy resin, and the formation of the network-like polymer is induced to occur. In the interlayer of the inorganic layer material, not only the nano-mixing effect can be utilized to enhance the mechanical properties, but also the properties required for the packaging material such as low moisture absorption rate, high heat resistance, and excellent dimensional stability can be greatly improved. . ^ US Pat. No. 6,548,576 discloses the use of two different epoxy resins, including about 2 to 13% DGEBA and 40 to 70% phenol formaldehyde resin, which can be prepared at temperatures ranging from -65 ° C to 150 ° C. An epoxy resin that has a thermal decay phenomenon. It utilizes the regulation of two different resin ratios to achieve good thermal stability. U.S. Patent No. 5,554,670 discloses the crosslinking of nanocomposites synthesized from the same epoxy resin (DGEBA) with two different hardeners, including BDMA and BTFA, with a layer spacing greater than 1 angstrom. Φ US Pat. No. 5,760,106 reveals that there are five kinds of modifiers in the interlayer dispersion of clay, and the more uniform dispersion, the greater the chance of forming delamination (exf〇Hateci). Its tensile strength or tensile modulus perform best. • US Pat. No. 5,853,886 discloses the preparation of various epoxy-clay nanocomposites with a number of different hardeners including - JEFFAMINE D230, D400, D4000, T304, T3000 and T5000 (different lengths of molecular chains). Among them, d-spacing is the largest with Τ5000 (the longest molecular chain). European Patent EP Pat. 08446661 discloses that in the case of epoxy resin, the hardener is in the ratio of 0806-A21144TWF (N2); david 7 8 1275579 and montmorillonite at DDP/DER331/MMT=1:1:0.75, D-spacing=34.38A, and then change the ratio at 1 ·· 3 : 2.5, d-spacing=32.92A, and d-spacing is the most open after changing the long carbon chain modifier, and the mechanical properties The transfer temperature with the glass was also improved. The results of the journal POLYMER (42) 2001 5947-5952 show that only a small amount of hardener MPDA is needed to achieve good dispersion. If the concentration is too high, the intercalated phenomenon will increase. It can be seen from XRD that if the amount of MPDA is too large, the dispersion will be poor, and d-spacing can be controlled by MPDA, which can be from 34.5A to 180 people.
期刊 J. APPL· POLYM. SCI. (78) 2000 808-815 指出，在加 入硬化劑BDMA情況下，3%、5%在cure 180。〇，1小時後，clay 的 peak 在 2-10°4貞測不到。而以 N-N_dimethyl benzylamine 為催 化劑或者是促進劑（DMB A當作是coupling agent)，在XRD分析 下可以確定，適當的加入催化劑可以使在cure條件一樣時，更 容易達到exfoliated。 【發明内容】 本發明係提供一種改質型層狀黏土，包括一層狀黏土，其 插層有二改質劑，包括咪唑（imidazole)化合物及四級銨鹽。 本發明另提供一種黏土-驗酸環氧樹脂複合材料，包括一驗 醛環氧樹脂，以及一如上述之改質型層狀黏土，均勻分散於該 盼酸環氧樹脂中。 本發明再提供一種黏土 -酚醛環氧樹脂複合材料之製造方 法，包括下列步驟。提供一如上述之改質型層狀黏土，混合該 改質型層狀黏土與一硬化劑，以及將上述含有硬化劑之改質黏 土與一酚醛環氧樹脂進行交聯反應，使該改質黏土均勻分散於 0806-A21144TWF(N2)；david 8 ⑧ 1275579Journal J. APPL· POLYM. SCI. (78) 2000 808-815 states that 3% and 5% are in cure 180 with the addition of hardener BDMA. Hey, after 1 hour, the peak of the clay is not detected at 2-10°4. With N-N_dimethyl benzylamine as the catalyst or promoter (DMB A as the coupling agent), it can be confirmed by XRD analysis that the proper addition of the catalyst makes it easier to exfoliated when the cure conditions are the same. SUMMARY OF THE INVENTION The present invention provides a modified layered clay comprising a layered clay having two modifiers, including an imidazole compound and a quaternary ammonium salt. The present invention further provides a clay-acid-proven epoxy resin composite comprising an aldehyde-reactive epoxy resin and a modified layered clay as described above, uniformly dispersed in the epoxy resin. The present invention further provides a method of producing a clay-phenolic epoxy resin composite comprising the following steps. Providing a modified layered clay as described above, mixing the modified layered clay with a hardener, and crosslinking the modified clay containing the hardener with a phenolic epoxy resin to effect the modification The clay is evenly dispersed in 0806-A21144TWF (N2); david 8 8 1275579
、 I I -該酚醛環氧樹脂中，形成一黏土 -酚醛環氧樹脂複合材料。 【實施方式】 本發明係提供一種改質型層狀黏土，包括一層狀黏土，其插 層有二改質劑，包括味唆(imidazole)化合物及四級銨鹽。 上述兩改質劑係等比例混合插層於層狀黏土中，且其在層狀 黏土中的重量百分比大體介於1 〇〜40wt%。。米嗤化合物可包括2-曱基咪唑、4-甲基咪唑、2-乙基咪唑、4-乙基咪唑、2-酚基咪唑或 4-酚基咪唑。四級銨鹽可包括氣化苯二曱烃銨（benzalkonium I chloride，BKC)。層狀黏土可包括矽礬石類黏土（sniectite clay)、蛭 石（vermiculite)、管狀高嶺土(halloysite)、絹雲母(sericite)或雲母 (mica)，而矽蓉石類黏土（smectite clay)可包括蒙脫土 (montmorillonite)、皂土（saponite)、富鋁蒙脫土（beidellite)、矽鐵 石（nontronite)或鋰皂土 (hectorite)。本發明層狀黏土的陽離子交換 當量(cation exchange capacity，CEC)大體介於 50〜200meq/100g。而 改質型層狀黏土的層間距係大於16埃。 本發明另提供一種黏土-酚醛環氧樹脂複合材料，包括一酚醛 | 環氧樹脂，以及一如上述之改質型層狀黏土，均勻分散於酚醛環 氧樹脂中。 酚醛環氧樹脂可包括雙酚A(bisphenol A)酚醛環氧樹脂，其固 含量大體介於93〜99.5%。在上述改質型層狀黏土中更包括插層〆 硬化劑’例如為盼搭樹脂（phenolic novolac)或四漠雙紛 - A(tetrabromo bisphenol A)樹脂，其含量大體介於15〜3〇%。在複合 材料中，硬化劑與酚醛環氧樹脂兩者間的重量比大體介於 0.2〜0.5，而改質型層狀黏土大體佔整個複合材料的〇·5〜7重量百 分比。 0806-A21144TWF(N2);david 9 1275579 本發明複合材料的層間距係大於50 #。其吸水性係低於 〇.6〇/。，㈣剝離強度係大於61b/m，玻璃轉換溫度(咖⑴腿k麵 temperature，Tg)係南於攝氏13〇度，而於玻璃轉換溫度前的溫度 知脹係數(coefficient 〇f thermal expansi〇n，CTE)係低於 6〇卯m/〇c。 本發明再提供一種黏土 ·酚醛環氧樹脂複合材料之製造方 ί包括下列步驟。首先，提供一如上述之改質型層狀黏土，接 著曰改貝型層狀黏土與一硬化劑，之後，將上述含有硬化劑 之改貝黏土與-I轉環氧樹脂進行交聯反應，使改質黏土均句分 散於祕環氧樹脂中，形成—黏土着_氧樹脂複合材料。 本發明黏土_酚醛環氧樹脂複合材料亦可用於銅猪基板之製 作’包括下列步驟。首先，將黏土着駿環氧樹脂複合材料與玻纖 布/冗於含次槽中。接著，將含浸過之玻纖布置於溫度大約攝氏 170〜190度的烘箱中歷時大約3〜5分鐘形成膠片。之後，將膠片裁 切、堆璺及熱壓。經最後裁邊後，即製作完成含有黏土身酸環氧 樹月曰複合材料的銅笛基板(C 〇pper clad laminate，CCL)。 以下藉由數個實施例以更進一步說明本發明之特徵和優點。 【實施例】 實施例1 改質型層狀黏土（PK-805)的製作 首先，將30克的PK_805黏土（石夕鐵石）加入27〇〇毫升的去 離子水中，攪拌過夜，進行膨潤處理。同時，製備適量的改質 劑’將等比例的2-酚基咪唑（2-ΡΙ)與氯化苯二甲烃銨（ΒΕΝ)加入 適置去離子水中，攪拌使其完全溶解。接著，將改質劑慢慢加 入上述黏土溶液，並以1Ν的鹽酸調整其值在3〜4之間，擾 拌過仪。之後，將溶液放入離心瓶中離心，離心後，將水溶液 0806-Α21144TWF(N2)；david 10 1275579 :’取下層沈殿黏土，再利用去離子水膨潤、攪 心數次，直到上層水溶液滴入硝酸銀，不會有氯化銀复： =為止。下層黏土放人冰箱後’再放人冷康乾燥機中待完全= 燦，即完成本發明改質型層狀黏土的製作。此改質型 的層間㈣18.G1埃。若改質劑改為等比例混合的2_;㈣唾 (2-MI)與氯化苯二甲烃銨（BEN)，則製作出來的改黏 的層間距為17.65埃。 、玉層狀黏土 實施例2 改質型層狀黏土（PK-8〇2)的製作 首先，將30克的ΡΚ_802黏土（蒙脫土）加入27〇〇 離子水中，授拌過夜，進行膨潤處理。同時，製備適量的^ 劑’將等比例的2-紛基Μ與氯化苯二甲经銨加人適量— 水中，搜拌使其完全溶解。接著，將改質劑慢慢加人上述黏立 溶液，独1Ν的鹽酸調整其ΡΗ值在3〜4之間，㈣過夜。之 後，將溶液放入離心瓶中離心，離心後，將水溶液丟棄 層沈殿黏土，再利用去離子水膨潤、攪拌。重複離心、數次’ 到上層水溶液滴人械銀，不會有氯化銀的白色沈_止。^ 層黏土放人冰箱後’再放人冷綠_巾待完全乾燥，即 本發明改質型層狀黏土的製作。此改質型層狀黏土的層間：為 Π.14埃。若改質劑改為等比例混合的孓甲基咪唑（2_μι)盘 苯二甲经銨(腦)，則製作出來的改質型層狀黏土的層間距為 16.05 埃。 …、 實施例3 改質型層狀黏土（Kunipia-F)的製作 0806-A21144TWF(N2)；david 1275579 %, I I - The phenolic epoxy resin forms a clay-phenolic epoxy resin composite. [Embodiment] The present invention provides a modified layered clay comprising a layered clay intercalated with two modifiers, including an imidazole compound and a quaternary ammonium salt. The above two modifiers are intercalated and intercalated in the layered clay, and the weight percentage thereof in the layered clay is generally between 1 〇 and 40% by weight. . The rice bran compound may include 2-mercaptoimidazole, 4-methylimidazole, 2-ethylimidazole, 4-ethylimidazole, 2-phenolimidazole or 4-phenolimidazole. The quaternary ammonium salt may include benzalkonium I chloride (BKC). The layered clay may include sniectite clay, vermiculite, tubular kaolinite, sericite or mica, and smectite clay may include Montmorillonite, saponite, beidelite, nontronite or hectorite. The cation exchange capacity (CEC) of the layered clay of the present invention is generally between 50 and 200 meq/100 g. The layered clay of the modified layered clay is greater than 16 angstroms. The present invention further provides a clay-phenolic epoxy resin composite material comprising a phenolic aldehyde resin, an epoxy resin, and a modified layered clay as described above, uniformly dispersed in a phenolic epoxy resin. The phenolic epoxy resin may include a bisphenol A phenolic epoxy resin having a solid content of generally from 93 to 99.5%. In the above modified layered clay, an intercalated crucible hardener is further included, for example, a phenolic novolac or a tetrabromo bisphenol A resin, and the content thereof is generally between 15 and 3%. . In the composite material, the weight ratio between the hardener and the novolac epoxy resin is generally between 0.2 and 0.5, and the modified layered clay generally accounts for 〇 5 to 7 by weight of the entire composite. 0806-A21144TWF(N2); david 9 1275579 The layer spacing of the composite of the present invention is greater than 50 #. Its water absorption is less than 〇.6〇/. (4) The peel strength is greater than 61 b/m, and the glass transition temperature (cafe (1) leg k-plane temperature, Tg) is about 13 degrees Celsius south, and the temperature-expanding coefficient before the glass transition temperature (coefficient 〇f thermal expansi〇n , CTE) is less than 6〇卯m/〇c. The present invention further provides a clay-phenolic epoxy resin composite material comprising the following steps. First, a modified layered clay as described above is provided, followed by tampering with the shell-shaped layered clay and a hardener, and then the above-mentioned modified clay containing the hardener is cross-linked with the -I-epoxy resin. The modified clay is dispersed in the secret epoxy resin to form a clay-based oxy-resin composite. The clay-phenolic epoxy resin composite of the present invention can also be used in the manufacture of copper pig substrates' including the following steps. First, the clay is made of epoxy resin composite material and fiberglass cloth/remaining in the secondary tank. Next, the impregnated glass fibers are placed in an oven at a temperature of about 170 to 190 degrees Celsius for about 3 to 5 minutes to form a film. After that, the film is cut, stacked and hot pressed. After the final trimming, a C 〇pper clad laminate (CCL) containing a clay acid eucalyptus composite was produced. The features and advantages of the present invention are further illustrated by the following examples. [Examples] Example 1 Production of modified layered clay (PK-805) First, 30 g of PK_805 clay (Shizhite) was added to 27 ml of deionized water, stirred overnight, and subjected to swelling treatment. At the same time, an appropriate amount of modifier was prepared. The equal proportion of 2-phenolimidazole (2-indene) and chlorodimethylammonium chloride (hydrazine) were added to deionized water and stirred to completely dissolve. Next, the modifier was slowly added to the above clay solution, and the value was adjusted to 3 to 4 with 1 Torr of hydrochloric acid to disturb the apparatus. After that, the solution is placed in a centrifuge bottle and centrifuged. After centrifugation, the aqueous solution is 0806-Α21144TWF (N2); david 10 1275579: 'The lower layer of the hall clay is removed, and then deionized with water to swell and stir for several times until the upper aqueous solution is dropped. Silver nitrate, there will be no silver chloride complex: = so far. After the lower layer of clay is placed in the refrigerator, it is placed in a cold-drying dryer to be completely = can be used to complete the production of the modified layered clay of the present invention. This modified type of interlayer (four) 18.G1 angstroms. If the modifier is changed to 2_; (iv) saliva (2-MI) and chlorodimethylammonium chloride (BEN), the modified layer spacing is 17.65 angstroms. Jade layered clay Example 2 Preparation of modified layered clay (PK-8〇2) First, 30 grams of ΡΚ_802 clay (montmorillonite) was added to 27 〇〇 ionized water, and the mixture was stirred overnight for swelling treatment. . At the same time, an appropriate amount of the agent is prepared to add an equal proportion of the 2-indenyl hydrazine and the chlorinated phthalic acid to the appropriate amount in the water, and the mixture is completely dissolved. Next, the modifier is slowly added to the above-mentioned viscous solution, and the hydrazine value of the hydrazine is adjusted to be between 3 and 4, and (4) overnight. Thereafter, the solution is placed in a centrifuge bottle for centrifugation, and after centrifugation, the aqueous solution is discarded into the layer of the hall clay, which is then swollen and stirred with deionized water. Repeat the centrifugation, several times to the upper aqueous solution to drop the artificial silver, there will be no white sinking of silver chloride. ^ After the layer of clay is placed in the refrigerator, 'there is a cold green _ towel to be completely dried, that is, the production of the modified layered clay of the present invention. The interlayer of this modified layered clay is Π14 angstroms. If the modifier is changed to a proportionally mixed hydrazine methylimidazole (2_μι) disk of phthalic acid via ammonium (brain), the resulting layered clay has a layer spacing of 16.05 angstroms. ..., Example 3 Production of modified layered clay (Kunipia-F) 0806-A21144TWF(N2);david 1275579 %
首先，將30克的Kunipia-F黏土（蒙脫土）加入2700毫升的 去離子水中，攪拌過夜，進行膨潤處理。同時，製備適量的改 質劑，將等比例的2-酚基咪唑與氯化苯二甲烃銨加入適量去離 子水中，攪拌使其完全溶解。接著，將改質劑慢慢加入上述黏 土溶液，並以1N的鹽酸調整其pH值在3〜4之間，攪拌過夜。 之後，將溶液放入離心瓶中離心，離心後，將水溶液丟棄，取 下層沈澱黏土，再利用去離子水膨潤、攪拌。重複離心數次， 直到上層水溶液滴入硝酸銀，不會有氣化銀的白色沈澱為止。 下層黏土放入冰箱後，再放入冷凍乾燥機中待完全乾燥，即完 成本發明改質型層狀黏土的製作。此改質型層狀黏土的層間距 為17.48埃。若改質劑改為等比例混合的2-甲基咪唑（2-MI)與氯 化苯二甲烃銨（BEN)，則製作出來的改質型層狀黏土的層間距為 17.66 埃。 實施例4 奈米複合材料的製作 首先，將適量的PK-805改質黏土加入單曱基醚丙二醇 (propylene glycol monomethyl ether，PM)的溶劑中授拌，使其完 全溶解。接著，將適量的硬化劑-齡酸樹脂（phenolic novolac)加 入上述黏土溶液中，使其與改質黏土混合插層。之後，將酚醛 環氧樹脂（novolac epoxy)加入黏土溶液中，擾拌使其均勻分散。 接著，將此樹脂溶液倒入模具中，並置於真空烘箱，將溶劑抽 乾。之後，放入熱風循環烘箱中，進行材料硬化，硬化溫度為 攝氏190度，歷時90分鐘，取出後，即為本發明黏土-酚醛環 氧樹脂複合材料。 雖然本發明已以較佳實施例揭露如上，然其並非用以限定 0806-A21144TWF(N2)；david 1275579 4 β . 本發明。任何熟習此技藝者，在不脫離本發明之精神和範圍内， 當可作些許之更動與潤飾。因此本發明之保護範圍當視後附之 申請專利範圍。First, 30 g of Kunipia-F clay (montmorillonite) was added to 2700 ml of deionized water, stirred overnight, and swollen. At the same time, an appropriate amount of modifier is prepared, and an equal proportion of 2-phenolimidazole and benzyldimethylammonium chloride are added to an appropriate amount of deionized water and stirred to completely dissolve. Next, the modifier was slowly added to the above clay solution, and the pH was adjusted to 3 to 4 with 1 N hydrochloric acid, and stirred overnight. Thereafter, the solution is placed in a centrifuge bottle for centrifugation, and after centrifugation, the aqueous solution is discarded, and the lower layer of precipitated clay is taken, and then swollen and stirred with deionized water. The centrifugation was repeated several times until the upper aqueous solution was dropped with silver nitrate, and there was no white precipitate of vaporized silver. After the lower layer of clay is placed in the refrigerator, it is placed in a freeze dryer to be completely dried, that is, the production of the modified layered clay is completed. The layered clay of this modified layered clay has a layer spacing of 17.48 angstroms. If the modifier is changed to a mixture of 2-methylimidazole (2-MI) and chloromethylammonium chloride (BEN) in equal proportions, the resulting layered clay has a layer spacing of 17.66 angstroms. Example 4 Preparation of Nanocomposite First, an appropriate amount of PK-805 modified clay was added to a solvent of propylene glycol monomethyl ether (PM) to be completely dissolved. Next, an appropriate amount of a phenolic novolac was added to the above clay solution to mix and intercalate with the modified clay. Thereafter, a novolac epoxy resin was added to the clay solution, and the mixture was uniformly dispersed. Next, the resin solution was poured into a mold, placed in a vacuum oven, and the solvent was drained. Thereafter, it was placed in a hot air circulating oven to harden the material, and the hardening temperature was 190 ° C for 90 minutes. After taking out, it was the clay-phenolic epoxy resin composite material of the present invention. Although the present invention has been disclosed above in the preferred embodiments, it is not intended to limit the invention to 0806-A21144TWF (N2); david 1275579 4 β. Anyone skilled in the art can make some changes and refinements without departing from the spirit and scope of the invention. Therefore, the scope of protection of the present invention is to be seen in the appended claims.
0806-A21144TWF(N2)；david ⑧ 1275579 ♦ ^ 【圖式簡單說明】 無。 【主要元件符號說明】 無00806-A21144TWF(N2);david 8 1275579 ♦ ^ [Simple description] None. [Main component symbol description] No 0
0806-A21144TWF(N2)；david 14 ⑧0806-A21144TWF(N2);david 14 8